WO2004063795A1

WO2004063795A1 - Highly safe silicone-containing material for ocular lens and process for producing the same

Info

Publication number: WO2004063795A1
Application number: PCT/JP2004/000071
Authority: WO
Inventors: Masaki Baba; Tsuyoshi Watanabe
Original assignee: Menicon Co., Ltd.
Priority date: 2003-01-10
Filing date: 2004-01-08
Publication date: 2004-07-29
Also published as: ATE507501T1; JP4235204B2; DE602004032420D1; CN100529842C; JPWO2004063795A1; US20060142410A1; EP1582910A1; EP1582910A4; EP2180366A1; CN1723411A; EP2180366B1; EP1582910B1; US8124668B2

Abstract

A safe ocular lens material which is excellent in oxygen permeability, surface wettability by water, and lubricity/wettability, is reduced in surface tackiness, has excellent flexibility and resilience, and gives a final product inhibited from releasing monomers therefrom. The ocular lens material comprises (A) at least one compound having a polydimethylsiloxane structure and an ethylenically unsaturated group bonded thereto through a urethane bond and (B) at least one pyrrolidone derivative having a methylene group as a polymerizable group.

Description

Akira Itoda A highly safe silicone-containing ophthalmic lens material and its manufacturing method

The present invention relates to an ophthalmic lens material and a method for producing the same. More specifically, the present invention relates to a contact lens, an intraocular lens, and a human cornea, which have high oxygen permeability, excellent flexibility, excellent surface water wettability, and excellent surface lubricity / ease. The present invention relates to an ophthalmic lens material which can be preferably used as a corneal onlay, a corneal inlay and the like, and a method for producing the same. Background art

1-Vinyl-2-pyrrolidone (N-VP) is used to produce industrially useful and typical water-soluble polymers. However, since it has a vinyl group, it has a disadvantage that its copolymerizability with alkyl (meth) acrylate or alkyl (meth) acrylamide, which is frequently used in industry, is low. For this reason, when polymerizing a material using NVP, particularly when performing UV polymerization that cures in a short time, unreacted monomer tends to increase.

Use of 1-methyl-3-methylene_2-pyrrolidone having a pyrrolidone skeleton (hereinafter, referred to as 1,3-MMP) to improve the polymerizability and produce water-soluble polymers useful in various industries Is described in JP-A-58-152017. In addition, a water-containing contact lens material containing 1,3-MMP as a main component is described in Japanese Patent Publication No. 1-158847 and Japanese Patent Publication No. 6-182177. . 1,3-MMP has an amide group adjacent to a methylene group, and is known in the technical field to which the present invention belongs. It is a compound with a structure similar to that of the frequently used alkyl (meth) acrylamide. Therefore, 1,3-MMP has good compatibility with alkyl (meth) acrylamido-alkyl (meth) acrylate and is excellent in copolymerizability. For example, Japanese Patent Publication No. Hei 6-82177 discloses a hydrogel having a high water content of 70% by weight or more obtained by copolymerizing 1,3-MMP and N-VP. These documents describe that use of 1,3-MMP as a main component can provide a hydrated gel with excellent flexibility. However, hydrated gels with a high water content can produce only contact lenses that have high flexibility but poor shape retention. Furthermore, the oxygen permeability of the contact lens made of a highly water-containing gel as described in these patent documents is significantly lower than the oxygen permeability of water, and the wearing state during continuous wearing or napping is poor. Considering this, it cannot be said that the necessary oxygen for the cornea can be permeated sufficiently.

On the other hand, in recent years, many silicone hydrated gel materials using a hydrophobic silicone compound as a main component have been reported for the purpose of improving oxygen permeability to a cornea of a lens. The use of a silicone compound has low water wettability on the surface of the material, and in order to improve this, copolymerization of a highly hydrophilic monomer, N-VP, is disclosed in U.S. Patent No. 5,486,577. It is described in the specification of No. 9. However, as described above, N_VP has low polymerizability, and therefore, when a copolymer is used as a medical device, there is a high possibility that it will remain as an unreacted monomer in product materials. Also, providing a residue-free and safe medical device requires a lot of effort. Therefore, in order to improve this problem, U.S. Pat. No. 5,486,579 describes that in order to improve the copolymerizability with N--VP, the polymerizability of other polymerizable components is increased. The structural design of the monomer is used to unify the base. However, in order to use components with various functions, it is necessary to design and manufacture monomers for all polymerizable components. It is very difficult for any trader.

Japanese Patent Application Laid-Open No. 6-214197 describes a contact lens composed of 1,3-MMP and a silicone-containing (meth) acrylate and / or a fluoroalkyl (meth) acrylate. Among them, silicone-containing (meth) acrylates and / or fluoroalkyl (meth) acrylates used as materials for oxygen-permeable contact lenses are used for the purpose of imparting shape retention and mechanical strength. Copolymerization is described. The contact lens material targeted here has a moisture content of about 37 to 58% by weight and an oxygen permeability coefficient of about 26 to 35, and is worn in continuous use or when napping. In consideration of this, it cannot be said that it has sufficient oxygen permeability. In addition, silicone-containing (meth) acrylates and copolymers containing Z or fluoroalkyl (meth) acrylate and a hydrophilic monomer as main components described in Japanese Patent Application Laid-Open No. Hei 6-214,197 have shape retention. Insufficient properties and mechanical strength. In the production of a hydrogel containing silicone, the compatibility of the components constituting the material is important. In the case of a material comprising a silicone-containing monomer and a strongly hydrophilic monomer, the material tends to undergo phase separation, and it is difficult to obtain a transparent material. Organic solvents are often used in such poorly compatible polymerizations. For example, Japanese Patent No. 32499123 discloses a method for producing a contact lens using an organic diluent in an amount of 5 to 60% by weight. In the production method, a method is described in which a solvent is removed by evaporating the solvent at a specific temperature. However, in fact, in these documents, the amount of organic solvent used is as large as several tens of percent, and when sufficient organic solvent is used to obtain a transparent material, the polymer is not freed by radical chain transfer to the organic solvent. The degree of polymerization tends to decrease, and a decrease in the strength of the material itself is inevitable. Also, for the same reason, the amount of the monomer polyol dissolved from the material is increased. Furthermore, it is cumbersome and difficult to remove a large amount of organic solvent from the system, and it is not suitable for mass production.

The present invention has been made in view of the above prior art, and has excellent oxygen permeability, surface water wettability, lubricity, and Z easiness, has low surface tackiness, and has excellent flexibility and rebound. It is an object of the present invention to provide an ophthalmic lens material having a property and a manufacturing method thereof. Furthermore, we will improve the low polymerizability seen in systems using N-VP as a hydrophilic component, establish a system that can reduce residual components in lens manufacturing, and suppress monomer leaching from final products. The aim was to provide a safe ophthalmic lens material. Disclosure of the invention

As a result of intensive studies to obtain an ophthalmic lens material having the above characteristics, a compound having an ethylenically unsaturated group and a polydimethylsiloxane structure through a specific urethane bond, and 1,3-MMP A pyrrolidone derivative in which the polymerizable group is a methylene group, for example, 1-alkyl-3-methylene1-2-pyrrolidone, monoalkyl-5-methylene-12-pyrrolidone, pentaalkyl-3-methylene1-2_ The present inventors have found that an ophthalmic lens material containing pyrrolidone as an essential component has the above properties, and have completed the present invention. That is, the present invention relates to (A) at least one compound having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond and (B) at least one pyrrolidone derivative whose polymerizable group is a methylene group. Including ophthalmic lens materials.

The present invention also relates to a method for producing an ophthalmic lens material,

a) At least one compound having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond (A), a hydrophilic monomer (B) containing at least one pyrrolidone derivative whose polymerizable group is a methylene group ) Obtaining a mixed solution containing a photopolymerization initiator and Z or a thermal polymerization initiator, and b) introducing the mixed solution into a mold,

c) irradiating the mixed solution in the mold with UV light and / or heating to obtain a cured ophthalmic lens material;

d) after removing the ophthalmic lens material, subjecting the ophthalmic lens material to a surface treatment to impart hydrophilicity and Z or stain resistance;

e) removing unreacted material from the ophthalmic lens material; and

f) hydrating the ophthalmic lens material;

The present invention relates to a method for producing an ophthalmic lens material containing: BEST MODE FOR CARRYING OUT THE INVENTION

The ophthalmic lens material of the present invention comprises at least one compound (A) having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond and at least one pyrrolidone derivative having a polymerizable group as a methylene group ( B).

The compound (A) has an elastic bond called a urethane bond, reinforced without losing the flexibility and oxygen permeability of the material by the siloxane portion, and imparts elastic repulsion to eliminate brittleness. It is a component that imparts the property of improving mechanical strength. Further, since the compound (A) has a silicone chain in the molecular chain, it can impart high oxygen permeability to the product.

The compound (A) has an ethylenically unsaturated group, which is a polymerizable group, at both ends of the molecule, and is copolymerized with other copolymerization components via such a polymerizable group. It has the excellent property of imparting not only a physical reinforcing effect by entanglement of molecules but also a chemical bonding (covalent bond) to the material. That is, the compound (A) acts as a polymer crosslinkable monomer. Compound (A) has the general formula (1):

A ¹ — U ¹ — (-S ¹ -U ² _) _n -S ² -U ³ -A ² (1)

[Wherein A ¹ is a general formula (2):

_Y 21 _ _Z 21 _ _R 31 _ (2)

(Wherein, Y ²¹ is (meth) Akuriroiru group, vinyl group or Ariru group, Z ² ¹ represents an oxygen atom or a direct bond, R ³¹ is a direct bond or a C 1 to 1 2 linear, branched or aromatic Which represents an alkylene group having a ring);

A ² is a general formula (3):

(Wherein, Upsilon ²² is (meth) Akuriroiru group, vinyl group or Ariru group, Zeta ² ² represents an oxygen atom or a direct bond, R ³⁴ is a direct bond or a C 1 to 1 2 linear, branched or aromatic A group represented by the following formula (indicating an alkylene group having a ring) (provided that Υ ²¹ in the general formula (2) and Υ ²² in the general formula (3) may be the same or different);

U ¹ is a general formula (4):

_ _X 21 1 _ _E 21 _ _X 25 _ _R 32 _ (4)

(Wherein X ²¹ and X ²⁵ are each independently selected from a direct bond, an oxygen atom and an alkylene glycol group, and Ε ²¹ is a —NHCO— group (where X ²¹ is a direct bond , X ²⁵ is an oxygen atom or an alkylene glycol group, Ε ²¹ forms a urethane bond with X ²⁵ , or a C ΟΝΗ— group (where X ²¹ is an oxygen atom or an alkylene glycol group) And X ²⁵ is a direct bond, Ε ²¹ forms a urethane bond with X ²¹ ) or derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, cycloaliphatic and aromatic systems Divalent group (however, in this case, X ²¹ and X ²⁵ are each independently an oxygen atom and an alkylene Selected from the call group, E ²¹ forms two urethane bonds in between the X ²¹ and X ^25), R ³² represents an alkylene group which have a straight-chain or branched-chain having 1 to 6 carbon atoms ) A group represented by;

S ¹ and S ² are each independently of the general formula (5):

R ²³ R ²⁵ R ²⁷

I I I

-(-S i -0-)-(-S i -0-) _r S i-(5)

I I I

p 24 p 26 28

(Wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group or a phenyl group, and K is An integer of 10 to 100, L is 0 or an integer of 1 to 90, and K + L is an integer of 10 to 100);

U ² is a general formula (6):

_ _R 37 _ _X 27 _ _E 24 _ _X 28 _ _R 38 _ ( ₆ )

(Wherein, R ³⁷ and R ³⁸ are each independently a linear or branched alkylene group having 1 to 6 carbon atoms; X ²⁷ and X ²⁸ are each independently an oxygen atom or an alkylenedalycol. group; E ²⁴ is a saturated or unsaturated alicyclic aliphatic series divalent group Jiisoshiane Bok from selected from the group of fl cyclic and aromatic systems (provided that in this case, E ²⁴ is X ²⁷ and X ²⁸ Which forms two urethane bonds between)

U ³ is a general formula (7):

One R ³³ -X ²⁶ -E ²² -X ^22- (7)

(Wherein, R ³³ is a linear or branched alkylene group having 1 to 6 carbon atoms, X ²² and X ²⁶ are each independently selected from a direct bond, an oxygen atom and an alkylene glycol group, E ²² is one NHCO— group (where X ²² is an oxygen atom or an alkylene glycol group, X ²⁶ is a direct bond, and E ²² forms a urethane bond with X ²² ), CO NH_ group (however, in this case, X ²² is a direct bond, X ²⁶ is an oxygen atom or an alkylene alcohol group, and E ²² forms a urethane bond with X ²⁶ ) or saturated or A divalent group derived from diisocyanate selected from the group consisting of unsaturated aliphatic, alicyclic and aromatic (where X ²² and X ²⁶ are each independently an oxygen atom or an alkylene glycol group Wherein E ²² forms two urethane bonds between X ²² and X ²⁶ );

n represents 0 or an integer of 1 to 10], and is a polysiloxane macromonomer in which a polymerizable group represented by the formula is bonded to the siloxane main chain through one or more urethane bonds.

In the general formula (1), A ¹ is, as described above, a general formula (2):

_Y 21 _ _Z 21 _ _R 31 _ (2)

(Wherein, Y ²¹ , Ζ ²¹ and R ³¹ are the same as described above), and Α ² is a group represented by the general formula (3):

_ _Κ 34_ _Ζ 22 _ _{γ 2 2} (3)

(Wherein, Y ^{^22,} Ζ ²² and R ³⁴ are as defined above) is a group represented by.

Upsilon ²¹ and Upsilon ²² is each a polymerizable group, in that the hydrophilic monomer first and (D) can be readily copolymerized, Akuriroiru group is particularly preferred.

Each of Ζ ²¹ and あり²² is an oxygen atom or a direct bond, preferably an oxygen atom.

Each of R ³¹ and R ³⁴ is a direct bond or an alkylene group having a straight, branched or aromatic ring having 1 to 12 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms.

U ¹ , U ² and U ³ each represent a group containing a urethane bond in the molecular chain of the compound (Α).

In U ¹ and U ^3, E ²¹ and E ²² are, as described above, it Represents a CONH— group, an NHCO— group, or a divalent group derived from diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic groups. Here, the divalent group derived from diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic groups includes, for example, ethylene diisocyanate, 1,3-diisocyanate Divalent groups derived from saturated aliphatic diisocyanates such as propane and hexamethylene diisocyanate; 1,2-diisocyanatocyclohexane; bis (4-isoisocyanatocyclohexyl) methane; Divalent groups derived from alicyclic diisocyanates such as isophorone diisocyanate; divalent groups derived from aromatic diisocyanates such as tolylene diisocyanate and 1,5-diisocyanate naphthalene; 2, 2 'Diisocyanate Divalent groups derived from unsaturated aliphatic diisocyanates such as getyl fumarate. Among these, a divalent group derived from hexamethylenediisocyanate, a divalent group derived from tolylene diisocyanate, and isofhorondidisocyanate are relatively easy to obtain and easy to impart strength. Preferred is a divalent group derived from mono.

In U ¹ , when E ²¹ is an —NHCO— group, X ²¹ is a direct bond, X ²⁵ is an oxygen atom or an alkylene glycol group, and E ²¹ is represented by X ²⁵ and a formula: —NHCOO— To form urethane bonds. When E ²¹ is a —CONH— group, X ²¹ is an oxygen atom or an alkylene glycol group, X ²⁵ is a direct bond, and E ²¹ is represented by X ²¹ and a formula: 10 CONH—. To form urethane bonds. Further, when E ²¹ is a divalent group derived from the above diisocyanate, X ²¹ and X ²⁵ are each independently selected from an oxygen atom and preferably an alkylene glycol group having 1 to 6 carbon atoms. is, E ²¹ forms two urethane bonds in between the X ²¹ and X ^25. R ³² is § alkylene group having a linear or branched chain of from 1 to 6 carbon. In U ^2, E ²⁴ is, as described above, represents a saturated or unsaturated aliphatic divalent group derived from Jiisoshianeto selected from the group consisting of alicyclic and aromatic systems. Here, saturated or unsaturated aliphatic, divalent group derived from a Jiisoshianeto selected from the group consisting of alicyclic and aromatic, example wherein U ¹ and when the U ³ the same divalent Group. Among these, divalent groups derived from hexamethylene diisocyanate, divalent groups derived from tolylene diisocyanate, and divalent groups, which are relatively easily available and easily impart strength. A divalent group derived from sophorone disocyanate is preferred. Also, E ²⁴ forms two urethane bonds in between the X ²⁷ and X ^28. X ²⁷ and X ²⁸ are each independently an oxygen atom or preferably an alkylene glycol group having 1 to 6 carbon atoms, and R ³⁷ and R ³⁸ are each independently a linear or branched chain having 1 to 6 carbon atoms. Is an alkylene group having

In U ^3, R ³³ is an Al Quillen group having a linear or branched chain of from 1 to 6 carbon. If it is E ²² gar NHCO- group, X ²² is oxygen atom or an alkylene glycol group, X ²⁶ is a direct bond, E ²² is X ²² and wherein: the urethane bond represented in one NHCOO- To form Also, in the case of E ²² gar CONH- group, X ²² is a direct bond, X ² ⁶ is an oxygen atom or an alkylene glycol group, E ²² is X ²⁶ and formula represented in one OCONH- To form a urethane bond. Further, when E ²² is a divalent group derived from the above diisocyanate, X ²² and X ²⁶ are each independently selected from an oxygen atom and preferably an alkylene glycol group having 1 to 6 carbon atoms. , E ²² forms two urethane bonds in between the X ²² and X ^26.

Here, X ²¹ , X ²⁵ , X ²⁷ , X ²⁸ , X ^22, and preferably, alkylene glycol having 1 to 20 carbon atoms in X ²⁶ is, for example, a general formula: (8):

One O— (C _x H _2x —〇) _y- (8)

(Wherein, x represents an integer of 1 to 4 and y represents an integer of 1 to 5).

As described above, S ¹ and S ² are both groups represented by the general formula (5).

In the general formula (5), R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ^27, and R ²⁸ each independently represent an alkyl group having 1 to 6 carbon atoms or a fluorine-substituted alkyl group, as described above. Or a phenyl group.

Examples of the fluorine-substituted alkyl group include, for example, a group represented by — (CH ₂ ) _m —C _n F _{2n + 1} (m = l to: 10, n = l to: L 0) Specific examples include side-chain groups such as 3,3,3-trifluoro-n-propyl, 2- (perfluorobutyl) ethyl, and 2- (perfluorooctyl) ethyl. Or a branched fluorine-substituted alkyl group such as 2- (perfluoro-5-methylhexyl) ethyl group. In the present invention, when the compound (A) having such a fluorine-substituted alkyl group is used and the amount thereof is increased, the anti-lipid contamination of the obtained ophthalmic lens material tends to be improved.

K is an integer of 10 to 100; L is 0 or an integer of 1 to 90; K + L is preferably an integer of 10 to 100, and more preferably 10 to 80. When K + L is larger than 100, the molecular weight of compound (A) becomes large, the compatibility with the pyrrolidone derivative and other hydrophilic monomers becomes poor, and the compound (A) dissolves uniformly during compounding. When the polymerization does not occur, the phase separation occurs during the polymerization, and the opacity tends to be exhibited, and a uniform and transparent ophthalmic lens material tends not to be obtained.If it is less than 10, the oxygen permeability of the obtained ophthalmic lens material is low. And tend to be less flexible. Further, n is preferably 0 or an integer of 1 to 10. If n is greater than 10, the molecular weight of compound (A) will increase, and the compatibility with the pyrrolidone derivative and other hydrophilic monomers will be poor, and the compound (A) will not dissolve uniformly at the time of compounding or will not be polymerized. Occasionally, phase separation causes cloudiness, and there is a tendency that a uniform and transparent ophthalmic lens material cannot be obtained. n is more preferably 0 or an integer of 1 to 5.

Compound (A) is represented by the general formula (9):

A ¹ -U ¹ -T ¹ -U ⁴ -(-S ¹ -U ^2- ) _n -S ² -U ⁵ -T ² -U ³ -A ² (9)

[Where Α Α ² , \ U ² , U ³ , SS ² , and η are the general formula

It is the same as (1), and U ⁴ and U ⁵ are the same as U ¹ and U ³ respectively. However, Upsilon ²¹ in AA ^2, for Upsilon ²² is a (meth) Akuriroiru group, vinyl group or Ariru group.

Τ ¹ and Τ ² are represented by the general formula (10):

-Q- (CH ₂ CHD_Q-) _n — (10)

(In the formula, D is a hydrogen atom, a methyl group or a hydroxyl group, Q is a direct bond or an oxygen atom, and n is 5 to 10,000.)

Or the general formula (1 1):

One (M) _x — (1 1)

(Where M is 1,3-MMP, N_VP, (meth) acrylic acid, (meth) acrylic acid salt, N, N-dimethylacrylamide, N, N-getylacrylamide, 2-hydroxyethyl ( (Meth) A hydrophilic monomer unit selected from acrylate, tetrahydrofuran, oxetane, oxazoline, 2-methacryloyloxetylphosphorylcholine, etc. The polymer chain of the polymer composed of these units is branched even if it is linear. X may be bonded in a random shape or a block shape. , 000) is a hydrophilic polymer-containing segment or a hydrophilic oligomer-containing segment represented by). The polymerizable group represented by) is bonded to the siloxane main chain through one or more urethane bonds. It is a polysiloxane mac mouth monomer.

Compound (A) may further have a hydrophilic polymer structure. With this structure, the compatibility between the compound (A) and the hydrophilic monomer is improved, and the water wettability of a material composed of the compound (A) and the hydrophilic monomer can be improved. The structure of the hydrophilic polymer part is polyethylene glycol, polypropylene glycol, polybier alcohol, polybierpyrrolidone, poly (meth) acrylic acid, poly (meth) acrylate, poly (2-hydroxyethyl (meth) acrylate) ), Polytetrahydrofuran, polyoxetane, polyoxazoline, getylacrylamide, poly (2-

Examples include one or more polymers obtained by polymerizing a zwitterionic group-containing monomer such as (rylcholine). The molecular weight of the hydrophilic polymer structure is from 100 to 1,000, 000, preferably from 1,000 to 500,000. When the molecular weight is less than 100, there is a tendency that sufficient hydrophilicity cannot be imparted to dissolve the compound (A) in the hydrophilic monomer. On the other hand, when the molecular weight exceeds 1, 000, 000, the hydrophilic / hydrophobic domains become large, and it tends to be difficult to obtain a transparent material.

Representative examples of compound (A) include, for example, compounds of the formula:

(Hereinafter, referred to as compound (A-1)) represented by the formula:

o Compounds represented by 00 (hereinafter, referred to as compound (A-2)) and the like. These can be used alone or in combination of two or more.

At least one pyrrolidone derivative (B) in which the polymerizable group used in the present invention is a methylene group, for example, 1_alkyl-3-methylene-2-pyrrolidone, 1_alkyl_5-methylene-1-pyrrolidone, 5-Alkyl-3-methylene-1-pyrrolidone is a component that imparts excellent flexibility and water wettability to ophthalmic lens materials, and further improves the feeling of wearing. In the reaction system, N-pinylpyrrolidone, which is a hydrophilic monomer, is used. Compared to the case, at least one pyrrolidone derivative (B) in which the polymerizable group is a methylene group has high polymerizability, so that elution of unreacted monomers remaining in product materials can be suppressed. . In particular, when the amount of at least one pyrrolidone derivative (B) in which the polymerizable group with respect to all polymerizable components is a methylene group is increased, the surface water wettability and lubricity of the ophthalmic lens material are improved. Properties can be imparted. Specifically, the amount of the at least one pyrrolidone derivative (B) in which the polymerizable group is a methylene group is preferably 5 to 60% by weight, more preferably 10 to 100% by weight, based on all polymerizable components. ~ 55% by weight. If the amount of the at least one pyrrolidone derivative (B) in which the polymerizable group is a methylene group is less than 5% by weight, the desired water wettability and surface lubricity cannot be achieved, and the material cannot be easily wetted. Water wettability on the surface tends to be poor. On the other hand, when the content exceeds 60% by weight, the oxygen permeability becomes dominant in the moisture content, and there is a tendency that sufficient oxygen cannot be supplied to the cornea when the wearing state during continuous wearing or napping is considered.

The at least one pyrrolidone derivative (B) in which the polymerizable group is a methylene group used in the present invention includes 1-methyl-13-methylene-12-piperidone, 1-ethyl-13-methylene-12- Pyrrolidone, 1-methyl-5-methylene-12-pyrrolidone, 1-ethyl-5-methylene-12-pyrrolidone, 5-methyl-13-methylene-12-pyrrolidone, 5-ethyl-3-methylene-1-pyrrolidone, 1- _π-propyl-1 3-methylene-1 2-pyrrolidone, 1-π-propyl-1 5-methylene-1 2-pyrrolidone, 1-i-propyl 3-methylene-1 2-pyrrolidone, 1-i-propyl-1 Examples include, but are not limited to, 5-methylene-12-pyrrolidone, 1-p-butyl-3-methylene-12-pyrrolidone, and 1-1-ptyl-3-methylene-12-pyrrolidone. These can be used alone or in combination of two or more. At least these polymerizable groups are methylene groups. Among them, one of the pyrrolidone derivatives has high hydrophilicity, a material with excellent hydrophilicity can be obtained by using a small amount, and the production method is relatively easy, so that 1-methyl-3-methylene-1- Pyrrolidone, 1-methyl-15-methylene-12-pyrrolidone, 5-methyl-3-methylene-12-pyrrolidone are preferred.

In the present invention, a silicone compound (C) other than the compound (A) is contained as an ophthalmic lens material in order to further improve the oxygen permeability of the obtained ophthalmic lens material and to impart flexibility. Preferably.

Examples of the silicone compound (C) include a silicone-containing alkyl (meth) acrylate, a silicone-containing styrene derivative, and a silicone-containing fumaric acid diester. These can be used alone or in combination of two or more.

In this specification, “〜 (meth) acrylate” means “〜acrylate and Z or メタ methacrylate”, and the same applies to other (meth) acrylate derivatives.

Silicone-containing alkyl (meth) acrylates include, for example,

Acrylate, methylilebis (trimethylsiloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl (meth) acrylic Tris, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, tris (trimethylsilyloxy) silylpropylglyceryl (meth) acrylyl — And mono [methylbis (trimethylsiloxy) siloxy] bis (trime Tylci mouth xy) silylpropyl glyceryl (meth) acrylate, trimethacrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate

Lil (meth) acrylate,

Glyceryl (meth) acrylic acid, methylbis (trimethylsiloxy) methyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylic methylcyclohexyl) silylpropyl (meth) acrylate, and the like. As the silicone-containing styrene derivative, for example, a compound represented by the general formula (12):

(Wherein, p represents an integer of 1 to 15, Q represents 0 or 1, and r represents an integer of 1 to 15). In the silicone-containing styrene derivative represented by the general formula (12), when p or r is an integer of 16 or more, it is difficult to purify or synthesize the styrene derivative, and furthermore, the hardness of the obtained ophthalmic lens material. When q is an integer of 2 or more, synthesis of the silicone-containing styrene derivative tends to be difficult. Examples of the silicone-containing styrene derivative represented by the general formula (12) include tris (trimethylsiloxy) silylstyrene, bis (trimethylsiloxy) methylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, and tris (trimethylsilylstyrene). Siloxy) Siloxydimethylsilylstyrene, [bis (trimethylsiloxy) methylsiloxy] dimethyl Silyl styrene, (trimethylsiloxy) dimethylsilyl styrene, heptamethyltrisiloxanyl styrene, nonamethyltetrasiloxanyl styrene, pentadecamethylhepxyl oxanyl styrene, heneicosamyldecasiloxanyl styrene, hepatocosamethyl Tridecasiloxanil

Pentamethyldisiloxy) silylstyrene, tris (trimethylsiloxy) siloxybis (trimethylsiloxy) silylstyrene, bis (heptamethyltricyclooxy) methylsilylstyrene, tris [methylbis (trimethylsiloxy) siloxy] silylstyrene, trimethylsiloxybis [ Tris (trimethylsilicyloxy) siloxy] silyl styrene, heptix (trimethylsilicone oxy) trisilyl styrene, nonamethyltetrasiloxydimethyl thimethylsiloxyl) Siloxy] silyl styrene, (tristrimethylsilicyl oxyhexamethyl) Tetrasiloxy [tris (trimethylsiloxy) siloxy] trimethylsiloxysilylstyrene, nonakis (trimethylsiloxy) tetrasilylstyrene, bis (tridecamethylhexaoxy) methyl Silyl styrene, heptamethyl cyclotetrasiloxane siloxanyl styrene, such as descriptor methyl cyclotetrasiloxane siloxy bis (trimethylsiloxy) Shirirusuchi trimethyl silyl styrene to. As the silicone-containing fumaric acid ester, for example, the general formula (13):

R ¹ 〇

I II

R ² -S i-CH ₂ rO-C-CH R ⁴

I II I

R ³ HC-CO- ^ CHa ^ S i -R ⁵ (13)

II I

〇 R ⁶ (Wherein R ¹ R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a methyl group or a formula:

CH ₃

I

CH ₃ -S i-1 0—

I

CH ₃

And m and n each independently represent an integer of 1 to 3).

Examples of the compound represented by the general formula (13) include bis (3- (trimethylsilyl) propyl fumarate, bis (3- (pentamethyldisiloxanyl) propyl) fumarate, and bis (3- (1,3,3 , 3-tetramethyl-11- (trimethylsilyl) oxy) disiloxanyl) propyl) fumarate, bis (tris (trimethylsiloxy) silylpropyl) fumarate and the like. These can be used alone or in combination of two or more.

Of these, silicone-containing alkyl (meth) acrylates are preferred from the viewpoints of imparting flexibility of the material and copolymerizability of the compound (A) and the pyrrolidone derivative (B). From the viewpoint of imparting flexibility, tris (trimethylsiloxy) silylpropyl (meth) acrylate is more preferred.

When the silicone-containing alkyl (meth) acrylate of the silicone compound (C) is used, the amount used is preferably from 3 to 65% by weight, more preferably from 5 to 60% by weight, based on all polymerizable components. It is. When the amount of the silicone-containing alkyl (meth) acrylate is less than 3% by weight, the obtained ophthalmic lens material tends to be brittle and inferior in flexibility with high elastic modulus. On the other hand, if it exceeds 65% by weight, the elasticity decreases, but the resilience of the material is inferior and the surface tackiness tends to increase. When the silicone-containing styrene derivative is used among the silicone compounds (C), the amount used is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, based on all polymerizable components. is there. If the amount of the silicone-containing styrene derivative is less than 1% by weight, the resulting ophthalmic lens material tends to be unable to sufficiently improve oxygen permeability and mechanical strength. On the other hand, if it exceeds 30% by weight, the flexibility of the obtained ophthalmic lens material tends to decrease.

The amount of the silicone-containing fumaric acid diester used in the silicone compound (C) is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, based on all polymerizable components. It is. When the amount of the silicone-containing fumaric acid diester used is less than 1% by weight, the oxygen permeability of the obtained ophthalmic lens material tends not to be sufficiently improved. On the other hand, if it exceeds 50% by weight, sufficient mechanical strength tends not to be obtained.

The ophthalmic lens material of the present invention preferably contains N-substituted acrylamide (D). By containing the N-substituted acrylamide (D) as an ophthalmic lens material, it can act as a compatibilizer for the silicone component together with the pyrrolidone derivative (B) and produce a uniform transparent hydrogel having excellent transparency.

Ophthalmic lens material obtained using pyrrolidone derivative (B) alone without N-substituted acrylamide (D) due to poor compatibility with silicone-containing components such as compound (A) and silicone compound (C) There is a tendency for transparency to decrease. In contrast, in the present invention, by using the N-substituted acrylamide (D) simultaneously with the pyrrolidone derivative (B), the compatibility with the silicone-containing component is improved, and the transparency of the obtained ophthalmic lens material is improved. Can be improved.

N-substituted acrylamides (D) include N, N-dimethylacrylamide, N, N-getylacrylamide, N- (2-hydroxyethyl) Acrylamide, N-isopropylacrylamide, acryloyl morpholine and the like can be mentioned. Of these, N, N-dimethylacrylamide, N, N-getylacrylamide, and acryloylmorpholine are preferred because compatibility can be improved with a small amount.

In the present invention, when N-substituted acrylamide (D) is used, it is preferably 3 to 40% by weight, more preferably 5 to 35% by weight, based on the total polymerizable components. If the amount of N-substituted acrylamide (D) is less than 3% by weight, the polymerization system tends to become cloudy and the transparency of the ophthalmic lens material tends to decrease. On the other hand, when the content exceeds 40% by weight, the N-substituted acrylamide tends to easily take up lipids in tears due to amphipathicity and easily stain as an ophthalmic lens. At this time, if the use of the open mouth derivative (B) is reduced to further obtain a desired oxygen permeability, the water wettability and lubricity of the surface of the ophthalmic lens material tend to be impaired. .

When the pyrrolidone derivative (B) and the N-substituted acrylamide (D) are used in combination as the ophthalmic lens material of the present invention, the ratio of the pyrrolidone derivative (B) to the N-substituted acrylamide (D) [(B) / (D) (weight ratio)] is preferably 40 Z because if the pyrrolidone derivative (B) is small, the surface water wettability and lubricity of the ophthalmic lens material may be impaired. 60 or more, more preferably 45 Z55 or more, and even more preferably 50 Z50 or more.When the pyrrolidone derivative (B) is large, the polymerization system becomes cloudy and the ophthalmic lens material is transparent. In addition, the hardness of the material itself increases, which may adversely affect the feeling of wearing. Therefore, it is preferably 100 Z0 or less, more preferably 95-5 or less, and even more preferably 90/0 or less. 10 or less.

When the silicone compound (C) and the N-substituted acrylamide (D) are further added to the compound (A) and the pyridone derivative (B), which are essential components, as the ophthalmic lens material of the present invention, The percentage is as follows It is preferable to set as follows.

The ratio of the sum of the compound (A) and the silicone compound (C) to the sum of the pyrrolidone derivative (B) and the N-substituted acrylamide (D) [{(A) + (C)} / {(B) + ( D)} (weight ratio) means that if (B) + (D) is large, the oxygen permeability of the ophthalmic lens material depends on the water content, and it is impossible to obtain high oxygen permeability. Therefore, the ratio is preferably 30 to 70 or more, more preferably 35/65 or more, and further preferably 40/60 or more. In addition, when the amount of (A) + (C) is large, the flexibility of the ophthalmic lens material is lost, and the material becomes hard and stiff and has a sticky surface, which adversely affects the feeling of wearing. It is preferably 70Z30 or less, more preferably 67/33 or less, and even more preferably 65/35 or less.

At the same time as the proportion of (A) + (C) and (B) + (D) [{(A) + (C)} / {(B) + (D)} (weight ratio)] The ratio of the compound (A) to the silicone compound (C) [(A) / (C) (weight ratio)] is such that when the silicone compound (C) is large, the surface of the ophthalmic lens material becomes noticeably sticky. In addition, the shape retention of the material is reduced, so that it is preferably at least 25Z 75, more preferably at least 27/73, even more preferably at least 30/70. Further, when the amount of the compound (A) is large, the flexibility of the ophthalmic lens material is lost, and the material becomes hard and brittle. Therefore, it is preferably 75/25 or less, more preferably 73Z27 or less, and further preferably 70/30 or less. It is as follows.

Further, in the present invention, a hydrophilic monomer (E) other than the N-substituted acrylamide (D), which is copolymerized with the pyrrolidone derivative (B), can be used. By adding a hydrophilic monomer (E) as an ophthalmic lens material, the resulting ophthalmic lens material is given flexibility and surface water wettability, improving the feeling of wearing, and imparting lubricity / easiness of lubrication can do. Examples of the hydrophilic monomer (E) that can be used in the present invention include (meth) acrylamide; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. (Alkyl) aminoalkyl (meth) acrylates such as 2-alkylaminoethyl (meth) acrylate and 2-butylaminoethyl (meth) acrylate; ethylene glycol mono (meth) acrylate, propylene glycol Alkylene glycol mono (meth) acrylates such as poly (meth) acrylate; polyethylene glycol mono (meth) acrylate and polyalkylene such as polypropylene glycol mono (meth) acrylate Ricol mono (meth) acrylate; ethylene glycol aryl ether; ethylene glycol biel ether; (meth) acrylic acid; aminostyrene; hydroxystyrene; vinyl acetate; glycidyl (meth) acrylate; aryl glycidyl ether; vinyl propionate; N, N-dimethylmethacrylamide, N, N-getylmethacrylamide, N- (2-hydroxyethyl) methacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine; N-vinyl-2-pyrrolidone, N-vinyl 3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-3-ethyl —2-pyrrolidone, N-vinyl— 4, 5 —dimethy Roux-2-pyrrolidone, N-vinyl-5,5-dimethyl-1-piperidone, N-vinyl-3,3,5_trimethyl_2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-methyl 1-piperidone, N-vinyl-4-monomethyl-1-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl 2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone Don, N—vinyl—4,4-dimethyl—2-piperidone, N—viel—2—force prolactam, N—vinyl—3-methyl—2-force prolactam, N—vier—4-methyl—2—force Lactam, N—vinyl—7—methyl-1-2—prolactam, N—vinyl—7—ethyl—2-proprolactam, N—vinyl—3,5-dimethyl-2-proprolactam, N—vinyl—4, N-Vinyl lactams such as 6-Dimethyl-1-2-prolactam, N-Biel-3,5,7-Trimethyl-2-caprolactam; N-Vinylformamide, N-Biel-N-methylformamide, N-Vinyl- N-vieramides such as N-ethylformamide, N-vinylacetamide, N-vinyl_N_methylacetamide, N-vinyl-N-ethylethylacetamide, N-vinylphthalimide and the like. Among these hydrophilic monomers (E), (meth) acrylamide, hydroxyalkyl (meth) acrylate, and alkylene are preferable because they have excellent compatibility with silicone-containing components and can impart hydrophilicity to ophthalmic lens materials. Glycol mono (meth) acrylate, (meth) acrylic acid, N-vinyl lactam and N-vinyl amide are preferred. These can be used alone or in combination of two or more.

For example, in a system using a component such as biel acetate which is hydrolyzed by an acid or a base, the ophthalmic lens material is manufactured and then treated with an acid or a base to make the ophthalmic lens material more flexible. Properties and surface water wettability.

In order to further impart desired properties to the obtained ophthalmic lens material, alkyl (meth) acrylate, fluorine-containing alkyl (meth) acrylate, a hardness adjusting monomer, polymerizable and non-polymerizable ultraviolet absorbers Agents, pigments, UV-absorbing pigments and the like can also be used as monomers (F).

Alkyl (meth) acrylate is used to adjust the hardness of ophthalmic lens materials. It is a component that imparts quality and softness.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, n -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, _n -dodecyl (meth) acrylate, t-butyl (meth) Acrylate, pentyl (meth) acrylate, t-pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, nonyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate , Such as cyclohexyl (meth) acrylate Jo, branched or cyclic alkyl (meth) Akurireto the like. These can be used alone or in combination of two or more.

Fluorine-containing alkyl (meth) acrylate is a component that improves the anti-lipid contamination of ophthalmic lens materials.

As the fluorine-containing alkyl (meth) acrylate, for example, the general formula (14):

CH ₂ = CR ⁴ COOC _s H _(2s _ _{t + 1)} F _t (14)

(Wherein, R ⁴ is a hydrogen atom or CH ₃ , s is an integer of 1 to 15, and t is an integer of 1 to (2s + 1)).

Specific examples of the compound represented by the general formula (14) include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3-tetrafluoro-t-pentyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,4,4 , Four —Hexafluoro-t-hexyl (meth) acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3 3,4,4-Hexafluorobutyl (meth) acrylate, 2,2,2,2 ', 2', 2'-hexafluoro mouth isopropyl (meth) acrylate, 2,2,3,3,4,4 4-Heptafluorobutyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,

4,4,5,5,5-Nonafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluor heptyl

(Meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctyl (meth) acrylate, 3,3,4,4,5 , 5, 6, 6, 7, 7, 8, 8, 8—Tridecafluoroctyl (meth) acrylate, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 6, 7, 7, 7-Tridecafluo heptyl (meth) acrylate, 3, 3, 4, 4, 5,

5,6,6,7,7,8,8,9,9,10,10—Hexadecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7 , 8, 8, 9, 9, 10, 10, 1 0_Heptadecafluorodecyl (meth) acrylate, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8 , 9,9,10,10,11,11-octadecafluoroundecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8 , 8, 9,

9, 1 0, 1 0, 1 1, 1 1, 1 1 _ Nonadecafluoroundecyl (meth) acrylate, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, , 8, 9, 9, 10, 10, 10, 1 1, 1 1, 1 2, 1 2—Eicosafluorododecyl

(Meta) acrylate. These can be used alone or in combination of two or more.

Alkyl (meth) acrylate and fluorine-containing alkyl (meth) acrylate The content of the salt depends on the essential components such as compound (A) and pyrrolidone derivative (B), as well as the polymerization components such as silicon compound (C), N-substituted acrylamide (D) and hydrophilic monomer (E). Preferably, the content is 20% by weight or less, more preferably 10% by weight or less of the whole polymerizable component so that the effect is sufficiently exhibited. Further, in order to sufficiently exhibit the effect of the alkyl (meth) acrylate / fluorine-containing alkyl (meth) acrylate, the amount of the polymer component is at least 0.01% by weight, preferably at least 0.1% by weight. The hardness adjusting monomer is a component that adjusts the hardness of the ophthalmic lens material to impart hardness or softness.

Examples of the hardness-controlling monomer include alkoxyalkyl (such as 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 3-methoxypropyl (meth) acrylate. Alkyl thioalkyl (meth) acrylates such as meth) acrylate; ethyl thioethyl (meth) acrylate, methyl thioethyl (meth) acrylate; styrene; α-methyl styrene; methyl styrene, ethyl styrene, propyl styrene, butyl styrene, t-butyl styrene, isobutyl Alkyl styrenes such as styrene and pentyl styrene; methyl-α-methylstyrene, ethyl-α-methylstyrene, propyl-α-methylstyrene, butyl_α-methylstyrene , T-butyl-α- methylstyrene, Isobuchiru CK-methylstyrene styrene, alkyl one α- methylstyrene such as pliers Lou shed-methylstyrene styrene. These can be used alone or in combination of two or more. The content of the hardness controlling monomer in the polymerization component is 1% by weight or more, and preferably 3% by weight or more, in order to sufficiently impart the desired hardness or softness to the ophthalmic lens material. In order to prevent the oxygen permeability and the mechanical strength of the ophthalmic lens material from decreasing, the amount is preferably 30% by weight or less, and preferably 20% by weight. % Or less.

Polymerizable and non-polymerizable UV absorbers, dyes, and UV-absorbing dyes are components that impart UV-absorbing properties to ophthalmic lens materials or color the materials.

Specific examples of the polymerizable ultraviolet absorber include, for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-14- (meth) acryloyloxy-5-t _Butylbenzophenone, 2-hydroxy 41- (meth) acryloyloxy 2 ', 4, dicyclo-open benzophenone, 2-hydroxy-41- (2'-hydroxy-3'-(meth) acryloyl Benzophenone-based polymerizable UV absorbers such as benzophenone; 2_ (2'-hydroxy-5 '-(meth) acryloyloxyshetylphenyl) 1-2H-benzotriazole, 2- (2'-hydroxy) 5 '― (Meth) acryloyloxyshethylphenyl) 1 5_ 口-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl 1) 2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropyl-3,1t-butylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-Hydroxy-5 '-(2 "-methylacryloyloxyethoxy) -1,3, _t-butylphenyl) -5-methyl_2H-benzotriazoles such as benzotriazole Polymerizable UV absorbers; salicylic acid-derived polymerizable UV absorbers such as phenyl 2-hydroxy-4-methacryloyloxymethyl benzoate; 2-cyano_3-phenyl-2_ (3 '-(meth) acryloyl Oxyphenyl) methyl propenylate, etc. These can be used alone or as a mixture of two or more.

Specific examples of the polymerizable dye include, for example, 1_phenylazole (Meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthylene, 1-naphthylazo-2-hydroxy-3- (meth) acryloyloxy Naphthylene, 1- (a-anthrylazo) 1-2-hydroxy-13- (meth) acryloyloxy naphthalene, 1-1 ((4 '-(phenylenyl) -phenyl) azo) 1-2-hydroxy-1 3 — (Meth) acryloyloxynaphthalene, 1— (2 ', 4, -xylylazo)-2- (meth) acryloyloxynaphthylene, 1- (o-tolylazo) -2- (meth) a Chryloyloxynaphthene, 2- (m- (meth) acryloylamide-l-arino) 1-4,6-bis (1 '-(o_tolylazo) -2'-naphthylamino) -1,3 , 5_ triazine, 2-(m-vinylanilino) _4 one (4,12 6-chloro-1,3,5-triazine, 2- (1 '-(o-triazo) -2'-naphthyloxy) -4-1 (m-vinylanilino) -1-6-chloro-1,3 5-triazine, 2- (p-vinylanilino) -1-4- (1 '-(o-tolylazo) —2'naphthylamino) -1-6-chloro-1,3,5-triazine, N— (1'-(o-tolylazo ) 1-2 '-naphthyl) 1-3-vinylphthalic acid monoamide, N-(1'-(o-tolylazo)-2,1 naphthyl) 1-6-vinylphthalic acid monoamide, 3-vinylphthalic acid mono (4,- (p-sulfophenylazo)-1'-naphthyl) monoester, 6-vinylphthalic acid-(4 '-(p-sulfophenylazo)-1,1-naphthyl) monoester, 3-(meth) a Chryloylamide 4-phenyl phenophenol, 3- (meta) Acryloylamide 4 -— (8′-hydroxy-1,3,, 6′-disulfo 1′—naphthylazo) —phenol, 3-1 (meth) acryloylamide 4 -— (1,1-phenylazo-1,2,1 Naphthylazo) 1-phenol, 3- (meth) acryloylamide-4-1 (p-phenol, 2-amino-4-1 (m- (2'-hydroxy-1 1,1-naphthylazo) anilino) 1-6-isopropenyl-1,3,5-triazine, 2-amino-4- (N-methyl-1-P- (2'-hydroxy-1,1-naphthylazo) anilino) 1-6_isopro Zinyl _ 1,3,5-triazine, 2-amino-41- (m- (4-hydroxy-1, 1-phenylazo) anilino) 1-6-isopropenyl-1,3,5-triazine, 2- 1-amino-1 (N-methyl-1p- (4'-hydroxyphenylazo) anilino) 1-6-isopropenyl-1,3,5-triazine, 2-amino-1-4-

(m- (3,1-Methyl-11,1-Phenyl-15, -hydroxy_4,1-Vilazolylazo) anilino) -1-6-Isoprovenyl 1,3,5-triazine, 2-Amino-4-1 (N-methyl-p — (3,1-Methyl-1-phenyl-5'-hydroxy-4,1-pyrazolylazo) anilino) 1-6 _______________, 1,3,5-Triazine, 2-amino- 4 -— (p-phenylazoririno) Azo-based polymerizable dyes such as 1-6-isopropenyl_1,3,5-triazine, 4-phenylazo-7- (meth) acryloylamide-1-naphthol; 1,5- Bis ((meth) acryloylamino) 1,9-anthraquinone, 1-1 (4'-Pierbenzylamide) 1,9,10-anthraquinone, 4-amino-11,4,1-vinylbenzo 1,9-anthraquinone, 5-amino-1 11 (4 ' 1,9-Anthraquinone, 8-Amino-1- (4'-vinylbenzoylamide) 1,9,10-Anthraquinone, 4-212-111 (4,1-vinylbenzoylamide) 1,9-anthraquinone, 4-hydroxy —1— (4 ′ —vinylbenzoylamide) 1,9,10—anthraquinone, 1-one (3′—bulbenzoylamide) 1,9,10—anthraquinone, 1 One (2, one bierbenzylamide) one 9, 10—anthraquinone, one one

(4, -Isopropenylbenzoylamide) 1-9,10-anthraquinone, 1- (3'-Isopropenylbenzoylamide) 1,9,10-anthraki Non, 1- (2,1-isopropenylbenzoylamide) —9,10-anthraquinone, 1,4-bis (4′-vinylbenzoylamide) 1,9,10-anthraquinone, 1,4-one Bis (4'-isopropenylbenzoylamide) 1,9-anthraquinone, 1,5'-bis (4,1-vinylbenzoylamide) _9,10-anthraquinone, 1,5_bis (4'-isopropyl Benzoyl benzoylamide) —9,10—anthraquinone, 1-methylamino 4_ (3,1-vinylbenzoylamide) 1,9,10—anthraquinone, 1-methylamino-4-1 (4 ′ —vinylpentyzo) 1-, 10-anthraquinone, 1-amino-4-1 (3'-bierphenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (4,1-vinyl Enilamino) 1 9, 10—anthraquinone-2 Sulfonic acid, 1-amino-1 4- (2'-vinylbenzylamino) 1,9,10-anthraquinone 1-2-sulfonic acid, 1-amino-1 4- (3 '-(Men) acryloylaminophenyl Mino) 1, 9, 10-anthraquinone 1-2-sulfonic acid, 1-amino-1 41- (3 '-(meth) acryloylamino benzylamino) 1, 9, 10-anthraquinone-2-sulfonic acid, 1-1 (/ 3 —Ethoxycarbonylarylamino) 1,9—Anthraquinone, 1 — (/ 3-Carboxyarylamino) 1,9,10—Anthraquinone, 1,5 —Gee (] 3-Ripoxyarylamino) One 9, 10-anthraquinone, one one (/ 3-isopropoxyl ponylarylamino)-5-benzoylamide nine, ten-anthraquinone, two, (3 'one (meth) acryloylamide doanilino) (3 'one (3 "—sulfur 4" Noanthraquinone-1 "-yl) 1-amino-anilino-1-6-chloro-1,3-triazine, 2_ (3 '-((meth) acryloylamidoanilino) 1-41- ( 3 '— (3 "—Sulfo 4" —Aminoanthraquinone-1 ”One-yl) One-Amino-Arrino) One 6-Hydrazino-1,3,5-Triazine, 2, 4 One bis-one ((4 "-methoxyanthraquinone-1" -yl)

6— (3,1-vinylanilino) 1 1,3,5-triazine, 2— (2,1 vinylphenoxy) -4-(4,1 (3 "-sulfo 4" —aminoanthrachinone 1 "1-ylamino) ) -Anilino) 16-chloro-1,3-, 5-trianazine and other anthraquinone-based polymerizable dyes; o-nitroanilinometyl (meth) acrylate and other nitro-based polymerizable dyes; (meth) acryloylation Examples include phthalocyanine-based polymerizable dyes such as tetraamino copper phthalocyanine and (meth) acryloyluidani (dodecyl-neilated tetraamino copper phthalocyanine), etc. These can be used alone or in combination of two or more.

Specific examples of the polymerizable ultraviolet absorbing dye include, for example, 2,4-dihydroxy-3 (p-styrenoazo) benzophenone, 2,4-dihydroxy_5- (p-styrenoazo) benzophenone, 2,4-dihydroxy -3-(p- (meth) acryloyloxymethylphenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy _ 3— (p- (meth) acryloyloxhetylphenylazo) benzophenone, 2,4-dihydroxy-1-5- (p- (meth) acryloyloxhetylphenylazo ) Benzophenone, 2,4-dihydroxy_3— (p- (meth) acryloyloxyprohylphenylphenylazo) benzophenone, 2,4-dihydroxy- 15- (P— (meth) acryloy Benzophenone, 2,4-dihydroxy-13- (0- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy 5- (o- (meth) a (Cryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy_3— (o— (meth) acryloyloxyshethylphenylazo) benzophenone, 2,4-dihydroxy-5_ ( O— (Meth) acryloyloxyshethylphenylazo) benzophenone, 2,4-dihydroxy-3- (o— (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5— (o — (Me evening) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-1 3— (p- (N, N-di (meth) acryloyloxysylamino) phenylazo) benzophenone, 2 , 4-Dihydroxy-1-5- (p- (N, N-di (meth) acryloyloxyshetylamino) phenyl azo) benzophenone, 2,4-dihydroxy-1 3 — (o _ (N, N — Di (meth) acryloyloxhetylamino) phenylazo) benzophenone, 2,4-dihydroxy_5— (o— (N, N—di (meth) acryloylethylamino) phenylazo) Benzophenone, 2,4-dihydroxy 3- (p- (N-ethyl-N- (meta) acryloyloxyshethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (p- (N- Ethyl—N— (Meth) acryloyloxyshetylamino) Fenilazo) Benzophenone, 2,4-dihydroxy-3 -— (o_ (N—Ethyl N— (Meth) acryloyloxy Shetylamino) phenylazo) Benzophenone, 2,4-dihydroxy-5— (o— (N—ethyl-1N— (Men) acryloyloxyshetylamino) phenylazo) benzophenone, 2,4-dihydroxy-13 — (P— (N-ethyl-N- (meta) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (p _ (N-eluene N— (meth) acryloylamino) phenyl Azo) benzophenone, 2,4-dihydroxy-1- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy_5- (0— (N-ethyl-N (Meth) acryloylamino) phenylazo) Benzophenone-based polymerizable ultraviolet-absorbing dyes such as benzophenone and 2-hydroxy-41- (p-styrenoazo) benzoate And benzoic acid-based polymerizable ultraviolet absorbing dyes such as nyl. These can be used alone or in combination of two or more.

The content of the polymerizable UV absorber, the polymerizable dye and the polymerizable UV-absorbable dye is greatly affected by the thickness of the lens. The amount used is 3 parts or less, preferably 0.01 to 2 parts, based on 100 parts of the total amount of the polymerization components. If these amounts exceed 3 parts, the mechanical strength of the ophthalmic lens material tends to decrease. Furthermore, considering the toxicity of ultraviolet absorbers and dyes, they tend to be unsuitable as materials for ophthalmic lenses such as contact lenses that come into direct contact with living tissues and intraocular lenses that are implanted in living bodies. In the case of pigments in particular, if the amount is too large, the color of the lens becomes deeper, the transparency is reduced, and the lens tends to be less permeable to visible light. If the ophthalmic lens to be produced has a low water content and no elution of non-polymerizable UV absorbers, dyes, and UV-absorbing dyes, 2_ (4,6-diphenyl-2-1) , 3,5-triazine-2-yl) 1-5- (hexyloxy) phenol, 2- (5-chloro-2H-benzotriazo-l-2-yl) —6 -— (1,1-dimethylethyl)- Non-polymerizable components such as 4-methylphenol can also be used.

In the ophthalmic lens material of the present invention comprising the compound (A) having a bifunctional polymerizable group and the pyrrolidone derivative (B) as the main components, the polymerizable component remains very little, and is basically a crosslinking agent. Do not need. However, a crosslinking agent (G) can be added to control the flexibility and hardness of the material.

Examples of the crosslinking agent (G) used in the present invention include: aryl methacrylate, vinyl methacrylate, 4-vinylbenzyl methacrylate, 3-vinylbenzyl methacrylate, methacryloyloxyshetyl acrylate, ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, diethylene glycol diaryl ether, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate Rate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (p-methacryloyloxyphenyl) hexafluoropropane, 2,2- Bis (m-methacryloyloxyphenyl) hexafluoropropane, 2,2-bis (o-methacryloyloxyphenyl) hexafluoropropane, 2,2-bis (p-methacryloyloxyf Enyl) propane, 2,2-bis (m-methacryloyloxyphenyl) propane, 2,2-bis (0-methacryloyloxyphenyl) propane, 1,4-bis (2-methacryloyloxyhexaful) O-isopropyl) benzene, 1,3-bis (2-methacryloyloxyhexafluo) 1,2-bis (2-methacryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2-methacryloyloxyisopropyl) benzene, 1,3-bis (2-methacryloyl) benzene Loyloxyisopropyl) benzene and 1,2-bis (2-methacryloyloxyisopropyl) benzene. These can be used alone or in combination of two or more.

The content of the crosslinking agent (G) should be 1 part or less based on 100 parts by weight (hereinafter referred to as “parts”) of the total amount of the polymerizable components other than the crosslinking agent so as not to make the ophthalmic lens material brittle. And preferably 0.8 part or less. Further, in order to further improve the mechanical strength of the ophthalmic lens material and sufficiently exhibit the effect of imparting durability, it is necessary to add 0.1% to the total amount of 100 parts of the polymerization components other than the crosslinking agent. It is at least 5 parts, preferably at least 0.1 part.

When the cross-linking agent (G) is used in the ophthalmic lens material of the present invention, the compound (A) and the cross-linking agent (G) are used at the same time as a cross-linkable component. The polymerizability can be significantly improved, and various physical properties of the obtained ophthalmic lens material can be improved. The stress relaxation rate of the ophthalmic lens material of the present invention indicates a stress relaxation rate in 30 seconds under a constant load, and the relaxation rate is preferably 8 to 15%, more preferably 8 to 13%. If it is less than 8%, the material is excellent in resilience but tends to be hard and inflexible without elongation. On the other hand, if it exceeds 15%, the material has poor resilience and poor shape recovery, and the amount of movement tends to be small when a contact lens is worn, and in some cases, may be adsorbed. Therefore, it cannot be said that all of them have appropriate resilience as ophthalmic lenses. Further, the tensile modulus of the ophthalmic lens material of the present invention is preferably from 0.2 to 0.8 MPa, and more preferably from 0.2 to 0.7 MPa. If it is less than 0.2 MPa, the material has no stiffness and tends to be difficult to handle due to poor shape retention on the fingers for use as an ophthalmic lens. On the other hand, when the pressure exceeds 0.8 MPa, the material is hard, and the feeling of wearing is deteriorated, and there is a tendency to cause disorders such as corneal and conjunctival staining. For this reason, none of them can be said to have appropriate flexibility as ophthalmic lenses.

Further, in the ophthalmic lens material of the present invention, it is necessary that both the stress relaxation rate and the tensile modulus are in the preferable ranges. Materials that do not fall within the preferred ranges are more likely to cause adsorption or staining of the cornea and conjunctiva, especially when worn continuously or when napping, making the material unsuitable as a contact lens. I can say. For comfortable wearing, the material must have a good balance between the resilience and flexibility.

The water content of the ophthalmic lens material of the present invention is preferably 10 to 60% by weight, and more preferably 32 to 55% by weight. When the water content is less than 10% by weight, the material becomes semi-hard and, for example, when used as a contact lens, the feeling of wearing tends to deteriorate. On the other hand, if the water content exceeds 60% by weight, the oxygen permeability becomes dependent on the water content, and sufficient oxygen cannot be supplied to the cornea in consideration of the wearing state such as continuous wearing or napping. There is a tendency.

The ophthalmic lens material of the present invention can be manufactured by the following procedure. a) at least one compound having an ethylenically unsaturated group and a polydimethylsiloxane structure through a urethane bond (A), and a hydrophilic monomer (B) containing at least one pyrrolidone derivative whose polymerizable group is a methylene group. A) obtaining a mixed solution containing a photopolymerization initiator and Z or a thermal polymerization initiator; b) introducing the mixed solution into a mold;

c) a step of irradiating the mixed liquid in the molding die with UV light, or Z or heating to obtain a cured ophthalmic lens material;

d) after detaching the ophthalmic lens material, subjecting the ophthalmic lens material to a surface treatment to impart hydrophilicity and Z or stain resistance;

e) removing unreacted material from the ophthalmic lens material; and

f) hydrating the ophthalmic lens material.

As described above, the mixed solution contains the compound (A), the pyrrolidone derivative (B), the silicone compound (C) and the N-substituted acrylamide (D) in order to express the characteristics of each polymerizable component. Is preferred. In the present invention, in order to improve the uniformity of the components in the polymerizable component, it is preferable that the mixture contains a water-soluble organic solvent. Specifically, the presence of a very small amount of a non-polymerizable organic solvent with respect to the polymerizable component allows the unreacted monomer to diffuse into the system even after the polymerization reaction has progressed, thereby causing a polymerization reaction. Can be involved. That is, the use of the water-soluble organic solvent can reduce the remaining polymerizable components.

The water-soluble organic solvent used in the present invention includes alcohols having 1 to 4 carbon atoms such as methanol, ethanol, 1-propanol and 2-propanol, or acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile and Select from N-methyl-2-pyrrolidone Is a water-soluble organic solvent. As the organic solvent, one that can dissolve the used polymerizable component may be appropriately selected and used according to the type of the polymerizable component. These may be used alone or as a mixture of two or more.

The water-soluble organic solvent in the present invention can dissolve the polymerizable component for an ophthalmic lens material. The amount used in the mixed solution is preferably 5% by weight or less, more preferably 0.1 to 5% by weight, and even more preferably 0.2 to 4% by weight. If the amount used is less than 0.1% by weight, the amount of residual components during polymerization tends to increase. On the other hand, if it exceeds 5% by weight, the mixture of the polymerizable components to which the diluent has been added becomes non-uniform, phase separation occurs during the polymerization reaction performed later, and the resulting material tends to become cloudy.

Further, since the organic solvent used is water-soluble, it can be easily replaced with water in the subsequent elution treatment step.

In the production of ophthalmic lens materials, a bulk polymerization method has been conventionally used. In this polymerization method, since only the polymerizable components are mixed and co-polymerized, the viscosity of the system increases extremely with the progress of polymerization, and the system cannot diffuse in a high-viscosity system and cannot participate in the polymerization reaction. A large amount of monomer remains. In the production of contact lenses that are medical devices, elution treatment with water or an organic solvent is performed to minimize the residual monomer.

In order to obtain the copolymer constituting the ophthalmic lens material of the present invention, the compound (A) and the pyrrolidone derivative (B) as essential components, and if necessary, the silicone compound (C) and the N-substituted acrylamide (D) The amount of the hydrophilic monomer (E), the amount of the monomer (F) and the amount of the cross-linking agent (G) are appropriately adjusted so as to be within the above ranges, and the polymerization component is heated and subjected to Z or ultraviolet irradiation. Polymerize by the te type method.

If the polymerization component is heated and polymerized by the 铸 method, the desired ophthalmic lens After blending the polymerization component and the radical polymerization initiator in the mold corresponding to the shape of the above, the mold is gradually heated to polymerize the polymerization component. Apply mechanical processing such as polishing. The cutting may be performed over at least one surface or both surfaces of the molded body (copolymer), or may be performed on at least one surface or both surfaces of the molded body (copolymer). It may be performed for a part. The ophthalmic lens material of the present invention is obtained by cutting at least one surface or a part of a molded product (copolymer) in consideration of giving a wide range of uses of products such as special lenses. Is particularly preferred. Cutting at least one surface of such a molded article (copolymer) means performing blanks molding, that is, cutting blanks obtained by polymerization by a 铸 mold method to obtain a desired ophthalmic lens shape. It is a concept that includes The polymerization may be performed by, for example, a bulk polymerization method or a solution polymerization method using a solvent or the like.

Specific examples of the radical polymerization initiator include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, and t-butylhydroperoxide. Oxide, cumene hydroperoxide, lauroyl peroxide, t-butyl peroxyhexanoate, 3,5,5-trimethylhexanoyl peroxide. These can be used alone or in combination of two or more. The amount of the radical polymerization initiator is about 0.001 to 2 parts, preferably 0.01 to 1 part, per 100 parts of the polymerization component. The heating temperature for heating the polymerization component in the mold is 50 ° C. or higher, preferably 60 ° C. or higher, from the viewpoint of shortening the polymerization time and reducing the residual monomer component. In addition, the temperature is 150 ° C. or lower, preferably 140 ° C. or lower, in terms of suppressing volatilization of each polymerization component and preventing deformation of the mold. The heating time when heating the polymerization component in the mold is as follows. The time is at least 10 minutes, and preferably at least 20 minutes, from the viewpoint of shortening the reaction time and reducing the residual monomer component. Further, from the viewpoint of preventing deformation of the mold, the heating time is 120 minutes or less, preferably 60 minutes or less. The heating may be performed by gradually increasing the temperature.

When the polymerization component is polymerized by UV irradiation by UV irradiation, the polymerization component and the photopolymerization initiator are blended into a mold corresponding to the desired ophthalmic lens shape, and then UV irradiation is performed on the mold. Irradiation polymerizes the polymerization components, and the obtained molded body is subjected to mechanical processing such as cutting and polishing as necessary. The cutting may be performed on at least one surface or both surfaces of the molded body (copolymer), or may be performed on at least one surface or part of both surfaces of the molded body (copolymer). May be performed. As the ophthalmic lens material of the present invention, at least one surface of a molded article (copolymer) or a part of the molded article (copolymer) was cut in consideration of giving a wider range of uses of products such as special lenses. It is particularly preferred that it is. Cutting at least one surface of such a molded article (copolymer) means that blanks molding is performed in the same manner as in the case of a molded article (copolymer) obtained by heating the above-mentioned polymerization component. In other words, the concept includes cutting a blank obtained by polymerization by a mold method into a desired ophthalmic lens shape. The polymerization may be performed by a bulk polymerization method or a solution polymerization method using a solvent or the like. In the present invention, polymerization is carried out by irradiation with ultraviolet rays as described above, but electron beam irradiation can be carried out instead of such ultraviolet irradiation. In this case, the heavy component is polymerized without a photopolymerization initiator.

The 铸 -shaped material used for polymerization by ultraviolet irradiation is preferably a general-purpose resin such as polypropylene, polystyrene, nylon, or polyester, which can transmit ultraviolet rays necessary for curing the material, and may be glass. These are formed and processed into a desired shape. For ophthalmic lens shapes After blending a polymerizable component and a photopolymerization initiator, a dye, a UV absorber, and an organic diluent in a type II that has or has not been adapted, the type II is irradiated with ultraviolet light to polymerize the polymerizable component. carry out. The wavelength range of the irradiated UV can be selected according to the function of the ophthalmic lens material. However, it is necessary to select the type of photopolymerization initiator to be used depending on the UV wavelength range to be irradiated.

好ましい The preferred UV illuminance when irradiating the polymerization component in the mold with UV is 1.O mWZ cm ² or more in order to sufficiently cure the material, and 5 O mWZ cm ^{2 for} the purpose of preventing material deterioration. It is as follows. The irradiation time is preferably 1 minute or more in order to sufficiently cure the material. Irradiation with ultraviolet light may be performed in one step, or ultraviolet light of different illuminance may be irradiated stepwise. Furthermore, during the polymerization, heating may be performed simultaneously with the irradiation of ultraviolet rays, whereby the polymerization reaction is promoted, and an ophthalmic lens can be effectively molded.

The heating temperature is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, from the viewpoint of accelerating the reaction. Or less, more preferably 90 ° C. or less. After the polymerization, the obtained molded body is subjected to machining such as cutting and polishing as necessary. The cutting may be performed on at least one or both surfaces of the molded body (copolymer), or may be performed on at least one or both surfaces of the molded body (copolymer). You may go to. The ophthalmic lens material of the present invention is obtained by cutting at least one surface of a molded article (copolymer) or a part of the molded article (copolymer) in consideration of giving a wider range of uses of products such as special lenses. Is particularly preferred. Cutting at least one surface or a part of the molded body (copolymer) means that planks obtained by polymerization by a 铸 method are cut into a desired ophthalmic lens shape. It is a concept that includes. In the present invention, the polymerization is performed by irradiating ultraviolet rays as described above, but electron beam irradiation may be performed instead of such ultraviolet irradiation. In this case, the polymerizable component can be polymerized without a photopolymerization initiator.

Specific examples of the photopolymerization initiator include, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Phosphinoxide photopolymerization initiator; methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoine ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n- Benzine photopolymerization initiators such as butyl ether; 2-hydroxy-2-methyl-1-phenylpropane-1-one, p-isopropyl-1-<< hydroxyisobutylphenone, p-t-butyltrichloroacetophenone, 2, 2-dimethoxy-1-phenyl acetophenone Phenone-based photopolymerization initiators such as, α-dichloro-4-phenoxyacetophenone, Ν, Ν-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexylphenyl ketone; 1-phenyl-1,2 _ Propandione _2- (ο-ethoxycarponyl) oxime; thioxanson-based photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosubalone; 2-ethylanthraquinone; benzophenone Acrylate; benzophenone; benzyl and the like. These can be used alone or in combination of two or more. Further, a photosensitizer may be used together with the photopolymerization initiator. The content of the photopolymerization initiator and the photosensitizer is about 0.001 to 2 parts, preferably 0.01 to 1 part, based on 100 parts of the polymerization component.

In both cases where the polymerization component is heated and polymerized and when the polymerization is performed by irradiating ultraviolet rays or electron beams, when the intraocular lens is manufactured, the lens support portion must be manufactured separately from the lens. May be attached to the lens, or may be molded integrally with the lens. In order to improve the surface characteristics of the ophthalmic lens, the following surface treatment can be performed. By these surface treatments, an ophthalmic lens material surface having more excellent water wettability and / or stain resistance can be produced.

Under a dilute gas atmosphere, such as alkenes having 1 to 6 carbon atoms and fluorine-substituted alkanes, nitrogen, oxygen, argon, hydrogen, air, water, silane or a mixture thereof, which are known to those skilled in the art. Low-temperature plasma treatment can be performed under specific conditions. In particular, oxygen alone or oxygen, water, and tetrafluur are expected because of the physical surface modification effect of ion etching and chemical surface modification by radical implantation (introduction of oxygen atoms). Mixtures with dichloromethane, organosilanes, methane, and nitrogen are preferred.

Here, the low-temperature plasma treatment may be performed under reduced pressure (low pressure) or under atmospheric pressure. Low-temperature low-pressure plasma processing or low-temperature atmospheric-pressure plasma processing includes high-frequency RF (for example, 13.56 MHz) and low-frequency AF (for example, 15.0 to 40.0 KHz), microwave (for example, 2.45 MHz). GHz), output (optimal value varies depending on frequency), processing time (from microsecond processing to about 1 hour), gas concentration (low pressure, low pressure, eg 10 to 150 Pa) Thereby, the surface modification effect can be controlled.

For example, when oxygen is used, physical surface modification effect by ion etching and chemical surface modification by radical implantation (introduction of oxygen atoms) are expected. It is also possible to carry out chemical surface modification only by radical implantation. In this case, a pulse modulation type (repeating the process while adjusting the plasma ON / OFF time) or a remote type or down flow type device where the chamber for generating plasma and the chamber for processing substrate are different it can. In addition, when a mixed gas of methane and air is used, a nitrogen-containing carbon deposited film is formed on the surface of the substrate, and when tetramethoxysilane and oxygen are used, a regular and strong silicate film is formed on the surface of the substrate. Is done. This makes it possible to form a very hydrophilic and highly durable surface coating.

The surface produced by these methods is excellent in water wettability and Z or contamination resistance, and is also excellent in durability of its properties, and can be suitably used as an ophthalmic lens material.

Further effective improvement of surface water wettability and Z or stain resistance can be achieved by forming a hydrophilic polymer film on the ophthalmic lens substrate surface.

A method known to those skilled in the art can be used as a method for forming a hydrophilic polymer film. For example, a surface modification method using a plasma polymerized film by performing glow discharge (plasma) in an atmosphere of a gasified hydrophilic monomer can be used. In this case, monomer fragments and active species are recombined randomly with the substrate, and in addition, polymerization of the monomer from the generated radicals occurs, forming an irregular and highly crosslinked polymer film on the substrate surface. Can be done.

The plasma polymerization is performed, for example, under the following conditions.

Plasma gas flow rate (argon, nitrogen, etc .: 1 to 50 s c cm)

Monomer gas flow rate (l to 50 s c cm)

Glow discharge (frequency 13.56 << ^, output 30 ~ 100, pressure 1.0 ~ 30Pa).

The hydrophilic monomer used here is not limited as long as it is a compound that can be gasified under low pressure and heating. Among them, pyridone derivatives such as 1-alkyl-3-methylene-1-pyrrolidone, vinyl lactams such as N-VP,

Acrylamide such as DMA A, (meth) acrylic acid, hydroxyalkyl (Meth) acrylate.

In addition, radicals are generated on the substrate surface by performing plasma treatment in a gas atmosphere such as oxygen, nitrogen, or argon, and then the ophthalmic lens material is immersed in a hydrophilic monomer solution and cured by UV irradiation or heating. To form a polymer film (plasma-initiated graft polymerization method). In this case, the conditions of UV irradiation and heating for forming the polymer film are not particularly limited. It is possible to select the conditions under which the used monomer can be sufficiently cured. For example, as UV irradiation conditions, it is effective to repeatedly perform irradiation for 1 to 30 minutes at an illuminance of 0.5 to 15 mW / cm ² (365 nm) as necessary. In the case of heating, heating at 40 to 100 ° C for 10 to 24 hours is effective. The UV irradiation or heat treatment may be performed in a state of being immersed in the hydrophilic monomer solution or in a state of stirring, or after immersion, in a state where the base material is taken out or dried. Is also good.

Examples of the hydrophilic monomer used herein include pyrrolidone derivatives such as 1-alkyl-13-methylene-12-pyrrolidone, vinyl lactams such as N-VP, acrylamides such as DMAA, (meth) acrylic acid, and hydroxyalkyl ( Contains zwitterions such as (meth) acrylate, 2-methacryloyloxyshethylphosphorylcholine (MPC) and N- (3-sulfopropyl) methacryloyloxyethylene N, N-dimethylammonium betaine (SPE) Compounds and mixtures thereof. In this case, the monomer is graft-polymerized starting from the radical on the surface of the base material. Therefore, in order to form an effective and durable coating, it is preferable to mix a crosslinking agent in the aqueous monomer solution. Crosslinking agents include ethylene glycol dimethacrylate (EDMA), polyethylene glycol di (meth) acrylate, aryl methacrylate (AMA), and diethylene glycol diaryl. Ether and the like. However, there is no particular limitation on the crosslinking agent that can be used. The crosslinking agent can be appropriately selected depending on the monomer and the solvent used. Also, the solvent used is not particularly limited, and examples thereof include water, water-soluble solvents such as methanol, ethanol, 2-propanol, acetone, acetonitrile, and THF. Above all, when considered as an ophthalmic lens, water that can be used as it is as a hydration treatment is most preferable. If the obtained molded product (copolymer) is essentially a water-containing material, a molded product made into an ophthalmic lens shape by cutting or an ophthalmic lens-shaped molded product removed from a mold (2) is used. By immersing in distilled water or physiological saline, the desired ophthalmic lens material shape can be obtained, and at the same time, unpolymerized polymerizable components and organic diluents can be removed. To effectively remove the elutable compound, distilled water or physiological saline may be heated simultaneously with or after hydration of the lens. The heating temperature is preferably lower than the temperature at which the residue can be removed in a short time and lower than the deformation temperature of the ophthalmic lens material, for example, preferably 35 to 100 ° C.

Furthermore, the colorless and transparent lens after the elution treatment can be colored using a vat dye. Vat dyes used include indanthrone, pyranthrone, benzantrone, anthraquinone carbazole, anthraquinoxazole, and indigo dyes. Preferred examples are CI VAT BLUE 4, CI VAT BLUE 6, CI VAT BROWN 1 for indantron systems, C.I.VAT GREEN 1 for pyranthrone systems, and C.I.VAT BROWN 2, for anthraquinone carbazole systems. In the indigo system, CI VAT B LUE 1 and the like can be mentioned.

The steps of dyeing these vat dyes include the following steps.

1) Disperse water-insoluble vat dye in water 2) Reduce dye to water-soluble leuco dye

3) Adsorb leuco dye to substrate

4) Oxidize the dye on the substrate to return to the original water-insoluble dye

5) Wash and remove the reducing solution and excess dye.

The reduction conditions of vat dyes are important because they greatly affect their dyeability. Generally affected by alkali concentration, reducing agent concentration, and reducing / staining temperature. In addition, the solubility of the leuco compound and the affinity for the base material also have a great influence on the dyeing properties. The reduction conditions were as follows: caustic soda concentration: 0.0050-5.0 mol / L, sodium hydrosulfite sodium reducing agent concentration: 0.001-50 g / L, reduction temperature: room temperature-80 ° C, dyeing The temperature is also preferably between room temperature and 80 ° C. The dye concentration is preferably from 0.0001 to 1.0 gZL. Although the immersion time has a correlation with the dye concentration, the immersion for about 30 seconds to 1 hour can control the density of the dyeing.

In addition, dyeing with a water-insoluble vat dye that has been converted into a leuco sulfate ester by a soluble vat dye in advance is also possible. For example, C.I.so1ubii1isedVATBLUE6 in the indantron system, C.I.solobulilisedVAT GREE N1 in the pyrantronic system, and C.I.solublilisedVATBLUE1 in the indigo system. When a soluble vat dye is used, the soluble vat dye can be directly mixed with the raw monomer solution of the ophthalmic lens material and used.

The ophthalmic lens material of the present invention obtained in this way has properties such as high oxygen permeability and high mechanical strength, excellent surface water wettability, and excellent surface lubricity and Z wettability. Since it has both functions, it can be preferably used for, for example, contact lenses, intraocular lenses, artificial cornea, corneal onlay, and corneal inlay. Next, the ophthalmic lens material of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(Manufacture of macromonomer (A1))

75.48 g of isophorone diisocyanate (IPD I) in a 1 L three-necked flask equipped with a nitrogen-necked condenser, a mechanical stirrer, and a thermometer on the side tube previously replaced with nitrogen (0.34 mol) and 0.12 g of iron acetyl acetate (FeAA) were added. Then, 529.90 g of hydroxyl dimethylsiloxane at both ends (degree of polymerization: 40, 7K acid group equivalent: 1,560 gZmol, KF-6002, Shin-Etsu Chemical Co., Ltd .; hereinafter, referred to as DHDMS'.i40) was added. Then, the mixture was stirred in an oil bath heated to 80 ° C for about 4 hours. Next, 39.47 g (0.34 mol) of 2-hydroxyethyl acrylate (HEA) and 0.20 g of p-methoxyphenol (MEHQ) as a polymerization inhibitor were added to a three-necked flask. The mixture was stirred in an oil bath at 80 ° C. After about 3 hours, the reaction was confirmed using —NMR and FTZIR from the reaction solution, and it was confirmed that the desired compound was obtained. Further, the crude compound was extracted and washed with n-hexane and acetonitrile, and the n-hexane layer was recovered, and the organic solvent and the low-molecular compound were distilled off under reduced pressure. 522.33 g (81% yield) of the purified compound was obtained.

XH-NMR (in CDC 1 3 ); δ 0. 06 ρ ρ m (S i- C Η 3, m), 0. 52 (S i - CH 2, 2H, m), 2. 91 (NH_CH 2, 2H, d), 3.02 (CH ₂ -N = C = 0, 2H, s), 3.42 (one O—CH ₂ , 2H, t), 3.61 (_0—CH ₂ , 2H, m ), 4.1 8-4 34. (- _{(〇) CO - CH 2 -, 6H} , m), 4. 54 (NH, 1H, s), 4. 85 (NH, 1H, s), 5. 84 (CH =, 1H, dd), 6.14 (CH =, 1H, dd), 6.43 (CH =, 1H, dd) FTZI R; 1262 and ^{802 cm - 1 (S i -} CH 3), 1094 Contact and 1023 (S i- O- S i) , 1 632 (C = C) 1728 near (C

(Production of macromonomer (A2))

In a 1 L three-necked flask equipped with a Dimroth condenser, a mechanical stirrer, and a thermometer attached to a pre-nitrogen-substituted side tube, add isophorone diisocyanate (IPD I) 44.60 g (0 .20 mol) and 0.07 g of iron acetyl acetonate (FeAcAc). Next, add 90.8 Og of hydroxyl-terminated dimethylsiloxane (degree of polymerization 10, hydroxyl equivalent 1000 gZ mol, KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd .; hereinafter, referred to as DHDMS i10), and add 80 g of oil bath. Heated to ° C and stirred for about 4 hours. Next, a solution prepared by dissolving 0.07 g of iron acetyl acetonate (FeAA) and 156.80 g of polyethylene glycol (having a hydroxyl equivalent of 1020 gZmol, manufactured by A1drich) in 20 OmL of black hole form was added. And refluxed for about 4 hours. After removing a part of the reaction solution and distilling off the solvent under reduced pressure, the hydroxyl value of the obtained intermediate was measured (acetylation method, 4210 g / mol).

7.90 g (0.05 mol) of 2-isocyanateethyl acrylate (IEM) was added to a 50 OmL three-necked flask in which 106.50 g of the above intermediate had been set aside. 0.05 g of P-methoxyphenol (MEHQ) was added as a polymerization inhibitor in a three-necked flask, and stirred in an oil bath at 80 ° C. After about 3 hours, the reaction solution was subjected to confirmation of the reaction using NMR and FT / IR, and it was confirmed that a urethane compound was obtained. Further, the crude conjugate was extracted and washed with n-hexane and methanol, the n-hexane layer was recovered, and the organic solvent and the low-molecular compound were distilled off under reduced pressure. 84.56 g (yield 74%) of the purified compound was obtained. '■ H-NMR (in CD C 1 3); 60. 06 p pm (S i- CH 3, m), 0. 52 (S i - CH 2, 2H, m), 2. 91 (NH- CH ₂ , 2H, d), 3.02 (CH ₂ — N = C = 〇, 2H, s), around 3.5 (—O— CH ₂ , m), 4.18-4.34 (-(O ) CO—CH ₂ —, 6 H, m), 4.54 (NH, 1 H, s), 4.85 (NH, 1 H, s), 5.84 (CH =, 1 H, dd), 6. 14 (CH =, 1H, dd), 6.43 (CH =, 1H, dd)

FT / IR; 1262 and ^{802 cm- 1 (S i - CH} 3), 1094 Contact and 1023 (S i- O- S i) , 1632 (C = C) 1728 near the (C = 0, ester and urethane).

In the embodiment, the following abbreviations are used.

TRIS: Tris (trimethylsiloxy) silylpropyl methacrylate DMAA: N, N-dimethylacrylamide

1,3-MMP 1-methyl-3-methylene-1-pyrrolidone

1,5-MMP 1-methyl-5-methylene-1-pyrrolidone

5, 3-MMP 5-Methyl-1 3-methylene-1 2-pyrrolidone

N i PMP: 1-2-2-propyl-1-methylene-1-pyrrolidone

N—VP: N—vinyl-1-pyrrolidone

MMA: Methyl methacrylate

EDM A: Ethylene Dalicol Dime Cryate

NMP: 1-methyl-2-pyrrolidone

TPO: 2,4,6-trimethylbenzoyl-diphenylphosphinoxide

HMP PO: 2-hydroxy-2-methyl lip mouth piofenone

BAPO: Bis (2,4,6-trimethylbenzoyl) monophenylphosphoxide ADMVN: 2,2'azobis (2,4-dimethylvaleroni

CBDMP: 2- (5-chloro-2H-benzotriazole-2-yl) -1-6- (1,1-dimethylethyl) -14-methylphenol

HPT: 2-(4,6-diphenyl 1,3,5-triazine-1-yl) -5- (hexyloxy) phenol

BZT-MA: 2- (2, -Hydroxy_5 '-(2' '-methacryloyloxyethoxy) -1,3,1-t-butylphenyl) -1,5-methyl-1 2H-benzotriazole

APMA: tetra- (4-methacrylamide) copper phthalocyanine

PAMNp: 1 _phenylazole 3-methacryloyloxy 2-naphthol

The amounts (parts by weight) of the crosslinking agent, the polymerization initiator, the ultraviolet absorber, the coloring agent and the diluent in the table are based on 100 parts by weight of the other polymerizable components. Quantification of residual monomer in the contact lens polymer obtained in Example, quantification of eluate in the treatment solution after hydration treatment, contact lens transparency, surface lubricity, water wettability, contact angle The resilience, tensile elasticity, oxygen permeability, refractive index, water content and lipid adhesion were examined according to the following methods.

(Quantification of residual monomer (HPLC))

After the polymerization, the lens taken out of the mold was immersed in acetonitrile to extract residual components. This extract was analyzed by HPLC, and the residual ratio of 1,3-MMP, 1,5-MMP, 5,3-MMP or N-VP with a relatively large amount of monomer relative to the blended amount was determined. Was calculated. To determine the residual ratio, prepare a solution of 1,3-MMP, 1,5-MMP, 5,3-MMP or N-VP of known concentration in acetonitrile and analyze by HPLC, and A calibration curve was prepared by taking each monomer concentration (ppm) on the X-axis and each peak area analysis value on the y-axis. Residual rate S per amount of pyrrolidone monomer used 1 (%), residual ratio to the total amount of lens S 2 (%) is V: amount of extraction solvent (mL), A: peak area of monomer, a: slope of calibration curve, b: section of calibration curve, W: plate Weight (g), w: expressed as follows, using the weight fraction (%) of the target monomer at the time of blending.

S 1 () = {VX (A-b)} / (aXWXwX 100)

S 2 (%) = {VX (A-b)} / (aXWX 10 000)

(T〇C analysis)

The lens materials of Example 1 and Comparative Example 1 immediately after the polymerization were used as samples. After weighing these samples, they were individually placed in vials containing 2 OmL of ultrapure water, and autoclaved at 121 ° C for 10 minutes. Five samples of the same material were prepared. Immediately after cooling (day 0), the lenses were taken out on days 1, 3, 8, and 14 after processing, and the processing solution was analyzed by TOC. The measurement was performed in NP OC (Non Purgeable Organic Carbon) mode using a total organic carbon meter (T〇C) TOC-V _cs „) manufactured by Shimadzu Corporation, and the results are shown in Table 4. The quantitative value (ppmC) shows the concentration of the extract when the concentration immediately after autoclaving (day 0) is set to 0. In other words, a large value indicates a large amount of elution.

(transparency)

The appearance of the contact lens was visually observed and evaluated based on the following evaluation criteria.

Evaluation criteria

A: No fogging, excellent transparency, and suitable for contact lenses.

B: Slight fogging is observed, but has transparency that is not a problem as a contact lens.

C: Use as a contact lens because of cloudiness and poor transparency Is difficult.

D: Because it is cloudy and extremely poor in transparency, it cannot be used as a contact lens.

(Surface lubricity, water wettability)

We evaluated the lubricity (the adhesion between the lenses and the adhesion between the lens and the fingers) when the contact lenses were folded in two on the fingers and rubbed with the fingers. The water wettability of the lens surface was also visually checked.

Evaluation criteria

A: Good water wettability, good sliding between lenses, and suitable as a contact lens.

B: Slightly lacking in water wettability. Slight creaking is felt when the lenses are rubbed together.

C: There is no adhesiveness between the lens and the finger, but the lens sometimes slips and stops moving.

D: The surface of the lens is sticky, and the adhesion between the lens and fingers is strong.

(Contact angle (bubble method))

The contact angle (°) (bubble method) was measured in saline solution at a temperature of 25 ° C using a contact angle meter G-I, 2MG manufactured by Elma Sales Co., Ltd. Using a syringe, 10 L of air bubbles were attached to the film immersed in the physiological saline solution, and the contact angle values of the air bubbles and the right and left angles of the plate were averaged to obtain a contact angle value. The smaller the contact angle value, the better the water wettability.

(Rebound)

The periphery of the ophthalmic lens material was fixed, and the center was fixed to a device for applying a load with a spherical jig having a tip diameter of 1/16 inch. The ophthalmic lens material was stopped by applying a load of about 20 g, and the stress immediately after the stop (S o (g / mm ² )) was measured. After leaving it for 30 seconds, the stress (S (g / mm ² ) was measured. Using the measured SO and S, the stress relaxation rate (%) was calculated according to the following equation.

When the value of the stress relaxation rate is 15% or more, the ophthalmic lens material has poor resilience, poor shape recovery, and cannot be said to have appropriate flexibility as an ophthalmic lens material.

Stress relaxation rate (%) = {(S o-S) / So} X 100

(Tensile modulus)

A dumbbell-shaped sample with a width of 2 mm and a thickness of 0.3 mm was punched out using a universal instrument testing machine, Mode 14300, and a tensile test was performed. The measurement was performed in a physiological saline solution at 35 ° C, and Young's modulus (MPa) was calculated from the stress-elongation curve. If the Young's modulus is greater than 0.8 MPa, the ophthalmic lens material has high elasticity, and when the lens is worn, there is a high possibility that the ocular lens will have an obstacle such as sticking of the lens or corneal tinning.

(Oxygen permeability coefficient D kj

The oxygen permeability coefficient of the test piece was measured in physiological saline at 35 ° C using a Kakenhi type film oxygen permeability meter manufactured by Rika Seiki Kogyo Co., Ltd. In each case, a cigarette paper was used, and a test piece having a thickness of 0.1 to 0.4 mm was measured in accordance with ISO 9913-1. Calculation was performed taking into account the edge effect, and Menicon EX (manufactured by Menicon) was used as a reference lens standard. The Dk value was normalized to 64. Note the units of oxygen permeability are ^{(X 10 "11 (cmVs ec} ) (mL0 2 / mL X h P a)), which units have been used conventionally in those skilled in the art (X 10- ¹¹ (cmVs ec) (mLOsZmLXmmHg))) multiplied by 0.75.

(Refractive index)

The refractive index (no unit) was measured using an Atago refractometer 1T manufactured by Atago Co., Ltd. in an atmosphere at a temperature of 25 ° C and a humidity of 50%. (Moisture content)

After the test piece was hydrated, the water content (% by weight) of the test piece was measured according to the following equation. Here, W is the weight (g) of the test piece in the equilibrium hydrated state after the hydration treatment, and W is the same. Represents the weight (g) of the test specimen after drying in a dryer at 105 ° C for 16 hours after the hydration treatment.

Moisture content (% by weight) = (WW ₀ ) X 100 / W

(Lipid adhesion test)

The lens was immersed in an artificial eye oil solution consisting of oleic acid, tripalmitin, palmitic acid, cholesterol, cholesterol palmitate and egg yolk lecithin at 37 ° C for 5 hours, and extracted with ethanol and getyl ether. The adhesion amount (mg / cm ² ) was quantified by vanillin phosphate sulfate method.

Examples 1-3 and Comparative Example 1

An ophthalmic lens component obtained by mixing a polymerizable component and a polymerization initiator shown in Table 1 was injected into a contact lens-shaped 铸 (made of polypropylene, corresponding to a contact lens having a diameter of about 13 mm and a thickness of 0.1 mm). . Next, this mold was irradiated with UV light for 60 minutes to carry out photopolymerization to obtain a contact lens-shaped polymer. Tables 2 and 3 show the results of evaluating the amount of unreacted residual monomers in the polymer, and Table 4 shows the results of evaluating the eluate concentration by TOC in the treated solution after hydration. Monomer mixing ratio (parts by weight)

Table 2 Residual monomer ratio (compared to monomer)

Table 3 Residual rate of monomer (to total weight)

Table 4 Change over time in T〇C

Quantitative value (ppmC) 1 item 3 item 8 item 14 item Example 1 (1,3- MMP) 0.9.2 2.1.9.4.8 Comparative Example 1 (N-VP) 5.9 5. 9 8. 9 11. 8 Examples 4 to 31 and Comparative Examples 2 to 5

An ophthalmic lens component obtained by mixing a polymerizable component, a polymerization initiator, a UV absorber, a colorant and a diluent shown in Tables 5 to 9 was injected into a mold (polypropylene) having a contact lens shape. Next, this mold was irradiated with UV light for 30 minutes to carry out photopolymerization to obtain a contact lens-shaped polymer. The obtained polymer was subjected to plasma irradiation (RF output 50 W, pressure 100 Pa) for 3 minutes in an oxygen atmosphere. It was immersed in physiological saline, absorbed, and hydrated to obtain a contact lens. The evaluation results are shown in Tables 10 to 14. Table 5 Mixing ratio of monomers (parts by weight)

Example

4 5 6 7 8 9 10

TRIS 30 30 30 30 27.5 22 22 Macro monomer A1 30 30 30 30 27.5 33 33

DMAA 10 10 10 10 11.3 11.3 11.3

N-VP

1, 3-MMP 30 30 33.7 33.7 33.7

1, 5-MMP 30

5, 3-MMP 30

EDMA 0.4 0.4 0.4 0.4 0.4 0.4 0.4

HMPPO 0.4 0.4 0.4 0.4 0.4 0.4 0.4

APMA APMA APMA APMA PAMNp

Colorant None None

0.01 0.01 0.01 0.01 0.01

(Table 6: Mixing ratio of monomers Part I)

Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5

TRIS 25 37.5 50 40 Macromonomer Al 25 12.5

DMAA 12.5 10 12.5 12.5

N-VP 37.5 40

1, 3- MMP 37.5 57.5

1, 5-MMP

5, 3- MMP

MMA 10

EDMA 0.4 0.4 0.4 0.4 0.4

HMPPO 0.40 0.40 0.40 0.4 Colorant (APMA) 0.01 0.01 0.01 0.01 Table 8 Monomer mixing ratio (parts by weight)

Example

18 19 20 21 22 23 24 25

TRIS 30 27.5 22 22 30 25 30 25

A1 A1 Al Al Al Al A2 A2 Macromonomer

30 27.5 33 33 20 20 30 25

DMAA 10 11.3 11.3 11.3 12.5 13.8 10 12.5

N-VP

1, 3-MMP 30 33.7 33.7 33.7 37.5 41.2 30 37.5

EDMA 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4

TPO TPO HMPPO HMPPO BAPO BAPO HMPPO HMPPO

Photopolymerization initiator

0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4

CBDMP HPT BZT-MA BZT-MA CBDMP HPT None None

UV absorber

0.2 0.2 0.5 0.5 0.2 0.2

APMA 0.01 0.01 None 0.01 0.01 0.01 0.01 0.01

Table 9 Mixing ratio of monomers (parts by weight)

Example

Re 27 28 30 31

TRIS 25 30 9 9 22 30 Macromonomer

30 25 30 33 33 30 A1

DMAA 10 12.5 10 11.3 11. 3 10

1, 3- MMP 30

1, 5- MMP 33. 7

5, 3-MMP 33.7

NiPMP 30 37. 5 30

EDM A 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4

HMPPO 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4

APMA 0.01 0.01 0.01 0.01 0.01 0.01

NMP Ethanol Ethanol Ethanol Diluent

2.5 2.5 2.5 2.5 Table 10 Results of Physical and Chemical Property Evaluation

Example

4 5 6 7 8 9 1 0 Transparency A A A A A A A A Tactile test B B B B A A A Contact angle (°) 28 29 29 26 27 26 26 Stress relaxation (%) 13 13 13 13 13 12 12 Tensile modulus

0.28 0.30 0.28 0.32 0.25 0.39 0.37 (M P a)

D k 78 88 88 92 69 90 90 Moisture content (%) 34 34 30 35 40 40 40 Refractive index 1.426 1.426 1.433 1.424 1.420 1.420 1.420 Residual rate S l (%)

1.4.1.0.5 0.4 .5 MM P Table 11 Physical and chemical property evaluation results

Table 12 Results of physical and chemical characterization

| J undetermined: Poor lens shape retention (deformation) and damage due to insufficient mechanical strength.

Table 13 Results of evaluation of physical and chemical properties

Table 14 Physical and chemical property evaluation results

Examples 32 and 33

Using the same mixed solution as in Examples 1 and 11, the obtained polymer before hydration was subjected to plasma irradiation (output 50 W, pressure 100 Pa, 3 minutes) under an oxygen atmosphere. After that, the graft-polymerized membrane was immersed in a 5.0 mol% aqueous solution of N-VP (containing 5.0% by weight of diethyleneglycol-diaryldiether) and heated at 60 ° C for 30 minutes. Was formed. Hydration treatment was performed to obtain a contact lens. Table 15 shows the evaluation results. Examples 34 and 35

Using the same mixed solution as in Examples 1 and 11, the obtained polymer before hydration was subjected to plasma irradiation (output 50 W, pressure 100 Pa, 3 minutes) in an oxygen atmosphere, and then Immerse in a 1.0 mol% aqueous solution of MPC (2-methylacryloyloxetylphosphorylcholine) (containing 5.0% by weight of tetraethyleneglycol dimethacrylate) and perform UV irradiation for 10 minutes. Thus, a graft polymerization film was formed. A hydration treatment was applied to obtain a contact lens. Table 15 shows the evaluation results.

Examples 36 and 37

Using the same mixed solution as in Examples 1 and 11, the obtained polymer before hydration was subjected to a glow discharge (TES) in an atmosphere of tetramethoxysilane (TMS) Z oxygen (gas flow ratio of 12 sccm). Pressure 13Pa, RF output 40W, 5 minutes X2 times) to form a plasma polymerized film. Hydration treatment was performed to obtain a contact lens. Table 15 shows the evaluation results.

Examples 38 and 39

Using the same mixed solution as in Examples 1 and 11, the obtained polymer before hydration was subjected to glow discharge (pressure 4 Pa) in an atmosphere of methane (CH4) Z air (gas flow ratio 3Z2 sccm). , AF output 40W, 5 minutes X 2 times) to form a carbon deposited film. Furthermore, normal oxygen plasma and hydration treatment were applied to obtain contact lenses. Table 15 shows the evaluation results. Table 15 Physical and chemical characterization results

Examples 40 and 41

Using the same mixed solution as in Examples 1 and 11, the obtained polymer before hydration was glow-discharged in an atmosphere of tetrafluoromethane (CF4) Z oxygen (gas flow ratio 9/1). (Pressure 13Pa, RF output 300W, 5 minutes). A hydration treatment was performed to obtain a contact lens. Table 16 shows the evaluation results.

Example 42

Using the same mixed solution as in Example 1, the obtained polymer before hydration was subjected to plasma irradiation (output 50 W, pressure 100 Pa, 3 minutes) in an oxygen atmosphere, and then hydration was performed. After the treatment, a contact lens was obtained. Table 16 shows the evaluation results.

Example 43

The polymer before hydration obtained by using the same mixed solution as in Example 11 was irradiated with plasma in an atmosphere of oxygen Z water (gas flow ratio 9/1) (output: 2.5 KW, pressure: 133 Pa, After 3 minutes), a hydration treatment was performed to obtain a contact lens. Table 16 shows the evaluation results.

Example 44

Using the same mixed solution as in Example 1, the obtained polymer before hydration was dissolved in water. A sum treatment was performed to obtain a contact lens. Table 16 shows the evaluation results.Table 16 Physical and chemical property evaluation results

Manufacture of colored lenses with vat dyes

Examples 45 to 50

The contact lenses obtained in the same procedure as in Examples 1, 11 and 21 were used to obtain colored contact lenses using a vat dye by the following method.

The contact lens after the 7K treatment is immersed in a reducing solution consisting of 0.1 g of sodium hydroxide, 0.1 lg of sodium hydroxide, and 19.8 g of purified water. About 2.0 g of the staining solution in which 300 ppm of each of the various vat dyes shown in Fig. 10 were dissolved was mixed with the reducing solution in which contact lenses had been immersed in advance, stirred for 15 minutes, and thoroughly washed. Contact lenses were obtained. Table 17 shows the evaluation results. Table 17 Coloring with Vat dye

Examples 51 to 55

An ophthalmic lens component obtained by mixing a polymerizable component, a polymerization initiator, a UV absorber, a coloring agent, and a diluent shown in Table 18 was injected into a type I (polypropylene) having a contact lens shape. Then, the mold was heated in an oven adjusted to 100 ± 2 ° C for 30 minutes to obtain a contact lens-shaped polymer. The obtained polymer was subjected to plasma irradiation (RF output 50 W, pressure 100 Pa) for 3 minutes in an oxygen atmosphere. The contact lens was immersed in a physiological saline solution and subjected to hydration by absorbing water to obtain a contact lens. Table 19 shows the evaluation results.

8 Monomer mixing ratio (parts by weight)

Table 19 Physical and chemical property evaluation results

Clinical evaluation

The contact lenses described in Examples 4, 8, 17, 17, 32, and 34 gave a good wearing feeling when worn, and no obstruction of the anterior segment was observed. On the other hand, although there was no obstacle in wearing the contact lens described in Comparative Example 2, the wearing feeling was inferior to the contact lens described in the example. In addition, in the wearing test of the contact lens described in Comparative Example 3 having low rebound, The amount of movement was small and slow, and adsorption on the cornea was observed.

From the above results, the contact lens materials shown in Examples 1 to 55 are excellent in transparency and low friction, have high surface water wettability, and are flexible because the stress relaxation rate is 13% or less. Excellent in repellency and repellency, low in residual ratio of monomer, and low in elution into autoclave solution, so high safety. In addition, it can be seen that it is suitable as a contact lens, such as giving a good wearing feeling even when wearing a contact lens.

Further, in a material using the pyrrolidone derivative and a specific silicone-containing macromonomer, the ophthalmic lens manufacturing process can be shortened because the residual ratio of the pyrrolidone derivative in the lens after polymerization is low.

On the other hand, the materials of the comparative examples having composition ranges not included in the claims are excellent in transparency, low friction, flexibility, and surface water wettability, but have a high residual ratio of monomers, and are not suitable for use in autoclaving solutions. Elution is also observed, and adsorption is also observed when the lens is worn. Industrial applicability

According to the present invention, it has excellent transparency, oxygen permeability, flexibility, resilience, surface wettability and lubricity, low surface tackiness, and appropriate mechanical strength. Thus, a contact lens having a low residual ratio, a small amount of monomer eluted into the autoclave solution, a high safety and a good feeling of wearing can be obtained.

In addition, an ophthalmic lens material composed of a pyrrolidone derivative in which the polymerizable group is a methylene group and a specific silicone-containing mac-mouth monomer is excellent in polymerizability, and is excellent in polymerizability. It can be used as a highly safe ophthalmic lens material for corneal onlays and corneal inlays.

Therefore, the present invention is not limited to contact lenses, and is a versatile ophthalmic lens. Provide the material of the lens.

Further, in the present invention, in a contact lens using the pyrrolidone derivative in which the polymerizable group is a methylene group and a specific silicone-containing macromonomer, the residual pyrrolidone derivative in which the polymerizable group in the lens is a methylene group after polymerization is obtained. Since the rate is low, the manufacturing process can be simplified.

Claims

Scope of Word

1. An eye containing (A) at least one compound having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond and (B) at least one pyrrolidone derivative whose polymerizable group is a methylene group. For lens material.

2. The ophthalmic lens material according to claim 1, wherein the polymerizable group contains at least one pyrrolidone derivative having a methylene group in an amount of 5 to 60% by weight.

3. The ophthalmic lens material according to claim 1, wherein the at least one pyrrolidone derivative in which the polymerizable group is a methylene group is 1-alkyl_3-methylene-12-pyrrolidone.

4. The ophthalmic lens material according to claim 3, wherein the 1-alkyl-13-methylene-2-pyrrolidone (B) is 1-methyl-3-methylene-2-pyrrolidone.

5. The ophthalmic lens material according to claim 1, wherein the at least one pyrrolidone derivative in which the polymerizable group is a methylene group is 1-alkyl-5-methylene-12-pyrrolidone. .

6. The ophthalmic lens material according to claim 5, wherein the 1-alkyl-15-methylene-12-pyrrolidone (B) is 1-methyl-5-methylene_2-pyrrolidone.

7. The ophthalmic lens material according to claim 1 or 2, wherein the at least one pyrrolidone derivative in which the polymerizable group is a methylene group is 5-alkyl-13-methylene-12-pyrrolidone. .

8. The ophthalmic lens material according to claim 7, wherein the 5-alkyl-3-methylene-2-pyrrolidone (B) is 5-methyl-3-methylene-2-pyrrolidone.

9. The compound according to claim 1, wherein the siloxane repeating number of the polydimethylsiloxane structure in the compound (A) having an ethylenically unsaturated group and a polydimethylsiloxane structure via the urethane bond is 10 to 100. Ophthalmic lens material.

10. Claims 1, 2 and 3, wherein the tensile modulus is 0.2 to 0.8 MPa and the stress relaxation value in 30 seconds under a constant load is 8 to 15%. An ophthalmic lens material according to paragraph 3, paragraph 4, paragraph 5, paragraph 5, paragraph 6, paragraph 7, paragraph 8, or paragraph 9.

11. Claims 1, 2, 3, 4, 5, 5, 6, 7, 8, or 10 with a water content of 10 to 60% by weight. Item 9. An ophthalmic lens material according to item 9.

12. The method according to claim 1, wherein the water content is 32 to 55% by weight. Item 9. An ophthalmic lens material according to item 9.

13. The ophthalmic lens material according to claim 1, further comprising a silicone compound (C) other than the compound (A) having an ethylenically unsaturated group and a polydimethylsiloxane structure via the urethane bond. .

14. The ophthalmic lens material according to claim 13, wherein the silicone compound (C) is tris (trimethylsi-hydroxy) silylpropyl (meth) acrylate.

15. The ophthalmic lens material according to claim 1, further comprising (D) N-substituted acrylamide.

16. When the N-substituted acrylamide (D) is N, N-dimethylacrylamide, N, N-getylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N- (2-hydroxyethyl) acrylamide One or more N-substituted acrylamides selected from Item 16. The ophthalmic lens material according to item 15 above.

17. The ophthalmic lens material according to claim 1, further comprising at least one or more crosslinking agents.

18. Claims 1, 2, 3, 4, 5, 5, 6, 7, 8, 9, 10, 10 An ophthalmic lens made of the ophthalmic lens material according to any one of the above, Item 12, Item 13, Item 14, Item 15, Item 15, Item 16 or Item 17.

19. A method of manufacturing an ophthalmic lens material,

a) A hydrophilic monomer containing at least one compound (A) having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond, and at least one pyrrolidone derivative whose polymerizable group is a methylene group. (B) and a step of obtaining a mixed solution containing a photopolymerization initiator and Z or a thermal polymerization initiator,

b) introducing the mixture into a mold;

c) a step of irradiating the mixture in the mold with UV light, or obtaining a cured ophthalmic lens material by subjecting the mixture to Z or heating;

d) after detaching the ophthalmic lens material, subjecting the ophthalmic lens material to a surface treatment to impart hydrophilicity and / or stain resistance;

e) removing unreacted material from the ophthalmic lens material; and

f) hydrating the ophthalmic lens material;

A method for producing an ophthalmic lens material comprising:

20. In the mixture, at least one compound (A) having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond, and at least one pyrrolidone derivative whose polymerizable group is a methylene group 20. The method for producing an ophthalmic lens material according to claim 19, wherein (B), the silicone compound (C) and the N-substituted acrylamide (D).

21. The method for producing an ophthalmic lens material according to claim 19, wherein the mixture contains a crosslinking agent.

22. The method according to claim 19, 20 or 20, wherein the mixture contains at least one or more polymerizable or non-polymerizable ultraviolet absorbers, and / or a polymerizable or non-polymerizable dye. 21. A method for producing an ophthalmic lens material according to item 21.

23. The ophthalmic lens material according to claim 19, 20 or 21, wherein the mixture contains 0.1 to 5% by weight of a water-soluble organic solvent. Production method.

24. The water-soluble organic solvent is one or more water-soluble organic solvents selected from alcohols having 1 to 4 carbon atoms, acetone, methylethylketone, dimethylformamide, dimethylsulfoxide, acetonitrile, and N-methyl-2-pyrrolidone. The method for producing an ophthalmic lens material according to claim 23, which is a solvent.

25. The method for producing an ophthalmic lens material according to claim 19, wherein the surface treatment is a plasma treatment.

26. The method for producing an ophthalmic lens material according to claim 25, wherein in the plasma treatment, oxygen or a mixture of oxygen is used.

27. The method for producing an ophthalmic lens material according to claim 26, wherein a mixture of oxygen and water is used in said plasma treatment.

28. The method for producing an ophthalmic lens material according to claim 26, wherein in the plasma treatment, a mixture of oxygen and tetrafluoromethane is used.

29. The method for producing an ophthalmic lens material according to claim 26, wherein a mixture of oxygen and an organic silane is used in said plasma treatment.

30. The method for producing an ophthalmic lens material according to claim 29, wherein the organic silane is tetramethoxysilane.

31. The method for producing an ophthalmic lens material according to claim 26, wherein a mixture of oxygen and methane is used in said plasma treatment.

32. The method for manufacturing an ophthalmic lens material according to claim 26, wherein a mixture of oxygen, nitrogen, and methane is used in said plasma treatment.

33. The method for producing an ophthalmic lens material according to claim 19, wherein said surface treatment is a treatment by a method for coating a hydrophilic polymer film.

34. The method for producing an ophthalmic lens material according to claim 33, wherein the coating method is a plasma polymerization method of a hydrophilic monomer.

35. The method for producing an ophthalmic lens material according to claim 33, wherein the coating method is a plasma-initiated graft polymerization method.

36. The method for producing an ophthalmic lens material according to claim 19, further comprising: (g) coloring the ophthalmic lens material using a vat dye.