WO2005026826A1

WO2005026826A1 - Soft ocular lens material and process for producing the same

Info

Publication number: WO2005026826A1
Application number: PCT/JP2003/011684
Authority: WO
Inventors: Mouad Lamrani; Eri Ito
Original assignee: Menicon Co., Ltd.
Priority date: 2003-09-12
Filing date: 2003-09-12
Publication date: 2005-03-24

Abstract

A process for contact lens production in which a hydroxylated compound having low copolymerizability can be copolymerized with a silicon compound in a reaction atmosphere causing no polymerization inhibition and a lens material satisfactory in transparency and strength, which are essential properties required of optical materials, is obtained; and a contact lens or ocular lens material obtained by the process. The process for producing a soft ocular lens material comprises: (1) a step in which a hydroxylated polymerizable compound is mixed with a trialkylamine to obtain a mixture solution; and (2) a step in which a polymerizable silicon compound is added to the mixture solution obtained in the step (1) and the resultant mixture is subjected to a polymerization reaction to thereby obtain a polymer.

Description

Akira Itoda Soft ophthalmic lens material and its manufacturing method

The present invention relates to a method for producing a copolymer suitable for a soft ophthalmic lens material which has a high oxygen permeability and enables long-term wearing in which lipid stains are unlikely to adhere, and a contact lens (CL obtained by the production method) ) And intraocular lens (IOL). Background art

Conventionally, it has been considered that a copolymer of a silicon-containing compound and a hydroxyl group-containing compound is appropriate for the construction of a contact lens material having high oxygen permeability and low adhesion of lipid stains. However, both components have low compatibility and copolymerizability due to their contradictory properties, and it has been difficult to obtain a good polymer as a contact lens material. Furthermore, the biggest problem was that the copolymer became cloudy and did not have the function as an optical product.

Therefore, research has been conducted to improve the copolymerizability of an amphiphilic substance by interposing an organic solvent such as alcohols and ketones as an amphipathic substance. By this method, it was confirmed that copolymerization of both components having low copolymerizability was possible, and that a copolymer having excellent transparency was obtained.

However, solution polymerization generally produces a polymer with lower polymerizability and lower crosslink density than bulk polymerization. In the above method, the polymerization reaction in an environment containing an organic solvent sufficient to obtain a polymer having excellent transparency, which is an essential requirement for an ophthalmic lens, is more fragile than in the case where it is not used. This has been confirmed. Disclosure of the invention

The present invention makes it possible to copolymerize a hydroxyl group-containing compound with a low copolymerizability and a gayne-containing compound in a reaction environment that does not inhibit the polymerization reaction, and has good transparency which is essential as an optical material, and The present invention relates to a method for producing a contact lens for obtaining a lens material having high strength that cannot be obtained by using an organic solvent, and a contact lens or intraocular lens material obtained by the method.

That is, the present invention relates to a method for producing a soft ophthalmic lens material comprising a polymer containing a hydroxyl group-containing polymerizable compound and a silicon-containing polymerizable compound, comprising the following steps.

(1) mixing a hydroxyl group-containing polymerizable compound and a trialkylamine to obtain a mixed solution, and

(2) A step of obtaining a polymer by adding a gayne-containing polymerizable compound to the mixed solution of (1) and subjecting it to a polymerization reaction.

It is preferable that the alkyl chain of the trialkylamine has 6 or less carbon atoms.

The hydroxyl-containing polymerizable compound is preferably a hydroxyalkyl (meth) acrylate.

The silicon-containing polymerizable compound is selected from acrylate-type urethane group-containing dimethylsiloxane macromonomer, tris (trimethylenoxy) silyl propyl acrylate, tris (trimethylsiloxy) silyl propyl methacrylate, and J-rate. Preferably, the alkyl chain of the trialkylamine has 4 or less carbon atoms.

Preferably, the trialkylamine is triethylamine. The hydroxyl group-containing polymerizable compound is 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, —It is preferable that it comprises one or more selected from hydroxybutyl acrylate.

It is preferable that the polymerization reaction (2) is a double reaction by light or heat.

Further, the present invention relates to a contact lens obtained by the manufacturing method described above.

Furthermore, the present invention relates to an intraocular lens obtained by the manufacturing method described above. BEST MODE FOR CARRYING OUT THE INVENTION

First, at the time of copolymerization of a hydroxyl group-containing compound and a gayne-containing compound, the characteristics of the hydroxyl group, which is a copolymerization inhibiting element, are once lost to carry out copolymerization. After a copolymer having excellent transparency is obtained, it is possible to remove the substance which has temporarily lost the function of 7 acid groups and to impart hydroxyl group properties to the copolymer. Specifically, a certain amount of trialkylamine is mixed with a hydroxyl group-containing compound and then subjected to a copolymerization reaction. Probably, the formation of a complex between the hydroxyl group and the trialkylamine reduces the affinity of the hydroxyl group and the silicon-containing component.

The trialkylamine used in the present invention is not particularly limited, but is preferably a trialkylamine having an alkyl chain of 6 or less carbon atoms in that it does not cause steric hindrance during complex formation.

Specific examples thereof include trimethylamine, triethylamine, tripipropylamine, triptylamine, tripentylamine, trihexylamine and the like. Among them, a trialkylamine having an alkyl chain of 4 or less carbon atoms is preferable, and it does not hinder steric hindrance in forming a complex. Triethylamine is preferred in terms of handling and good handling.

The molar ratio of the trialkylamine and the hydroxyl group-containing polymerizable compound is 1:

The mixing ratio is preferably 1. If the amount of trialkylamine is large, the polymer component tends to be destroyed (hydrolyzed). If the amount of hydroxyl group is large, copolysynthesis with the silicon-containing component tends to decrease.

The hydroxyl group-containing polymerizable compound used in the present invention includes a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and a hydroxyl group and an active unsaturated group at both ends. And hydroxyalkyl (meth) acrylates.

The hydroxyl group-containing compound is a component used for imparting stain resistance such as lipid stain resistance and hydrophilicity to ophthalmic lenses such as contact lenses and intraocular lenses.

Typical examples are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, Examples thereof include hydroxyalkyl (meth) acrylates having an alkyl group having 1 to 20 carbon atoms, such as 2,3-dihydroxy-1-methylpropyl (meth) acrylate, which may be used alone or in combination of two or more. Can be used. Among them, 2-hydroxyethyl acrylate (2-HEA) and 2-hydroxyethyl are particularly effective in imparting stain resistance and hydrophilicity to ophthalmic lenses and are easy to handle. Methacrylate (2-HEMA), 2-hydroxypropyl acrylate (2-HPA), 2-hydroxypropyl methacrylate (2-HPMA), 2-hydroxybutyl acrylate (2-HBA) ) And 2-hydroxybutyl methacrylate (2-HBMA) are preferred.

The content of the hydroxyl group-containing polymerizable compound is the same as that of the hydroxyl group-containing polymerizable compound. 100 weight in total with the silicon-containing polymerizable compound? In the case of ό, the content is 5% by weight or more, more preferably 10% by weight or more, and still more preferably 15% by weight or more, in order to sufficiently impart stain resistance and hydrophilicity to the ophthalmic lens. Further, in order to eliminate the possibility that the oxygen permeability of the ophthalmic lens is reduced, the content is 95% by weight or less, more preferably 90% by weight or less, and further preferably 85% by weight or less.

Further, the silicon-containing polymerizable conjugate used in the present invention is a component mainly used for imparting oxygen permeability to an ophthalmic lens.

The silicon-containing polymerizable compound has a general formula (I-1):

Α ^1- (one U ¹ — S ¹ —) _n -U ² -S ² -U ³ -A ² (1— 1)

Wherein A ¹ and A ² are each independently an active unsaturated group, an active unsaturated group having an alkylene group having 1 to 20 carbon atoms, or an active unsaturated group having an alkylene glycol group having 1 to 20 carbon atoms. Group,

U ¹ is a diurethane group forming a urethane bond with both adjacent A ¹ and S ¹ or with S ¹ and S ¹

U ² is a diurethane group that forms a urethane bond with both adjacent A ¹ and S ² or with S ¹ and S ² ,

U ³ is a diurethane group forming a urethane bond with both adjacent S ² and A ^2, and S ¹ and S ² are each independently a formula:

One R ¹ —〇一

(Wherein, R ¹ and R ² are each independently an alkylene group having from 20 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently substituted with a fluorine atom Linear, branched or cyclic carbon number of 1 to 20 which may be Or an alkyl group of the formula: A ³ — U ⁴ — R ¹ — O— R ² — (where A ³ is an active unsaturated group, an active unsaturated group having an alkylene group having 1 to 20 carbon atoms, or 1 carbon atom. An active unsaturated group having an alkylene glycol group of up to 20; U ⁴ represents a urethane group forming a urethane bond with adjacent A ³ and R ¹ ; R ¹ and R ² are the same as defined above; X is an integer of 1-1500, y is 0 or an integer of 1-1499, and x + y is an integer of 1-1500)

n represents 0 or an integer from 1 to 10]

Macro-monomers represented by

General formula (1-2):

B ¹ — S ³ — B ¹ (1-2)

[Wherein, B ¹ is an active unsaturated group having a urethane bond,

S ³ is the formula: 7

R ¹ —〇-1 R i-1 R ² — O— R ¹ —

(Wherein, R ¹ and R ² are each independently an alkylene group having 1 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently substituted with a fluorine atom. May be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a formula: A ³ — U ⁴ — R ¹ — 0— R ² — (where A ³ is an active unsaturated group An active unsaturated group having an alkylene group having 1 to 20 carbon atoms or an active unsaturated group having an alkylene glycol group having 1 to 20 carbon atoms, and U ⁴ is a urethane which forms a urethane bond with adjacent A ³ and R ^1. indicates gender group, a group R ¹ and R ² are represented by same) and said, X is 1 to 1 500 of the integer, y is 0 or from 1 to 1499 integer, x + y is an integer from 1 1500 Shown) Shows the group represented]

The macromonomer represented by is preferably used.

In the above general formula (1_1), as the active unsaturated groups represented by A ¹ and A ² , as described above, for example, (meth) acryloyl group, vinyl group, aryl group, (meth) Acryloyloxy, vinyl carbamate and the like. Among these, an acryloyloxy group and a vinyl group are preferable, since acryloyloxy and vinyl groups are preferred because they can impart more flexibility to the lens material for leisure and have excellent copolymerizability with other polymerization components. Xy groups are preferred.

When the active unsaturated group has an alkylene group or an Rsl alkylene glycol group, the alkylene group or the alkylene glycol group preferably has 1 to 20, more preferably 1 to 10, carbon atoms.

In addition, the formulas represented by S ¹ and S ^{2 in the} general formula (1-1):

-OR ² —〇一 R

'y R'

(Wherein RR ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , x and y are the same as defined above), wherein R ¹ and R ² preferably have 1 carbon atom alkylene group ~ 5, R ³ ~R ⁸ is preferably an alkyl group having 1 to 5 carbon atoms, also expression shows such ^{^{R 3 ~R 8: AS- IJA- R}} 1 - O- R 2 - medium of A ³ represents the same active unsaturated group as in the above-mentioned examples. When the active unsaturated group has an alkylene group or an alkylene glycol group, the alkylene group or the alkylene glycol group has 1 to 20, preferably 1 carbon atom. It is preferably from 10 to 10. X is preferably an integer of 1 to 500, y is 0 or an integer of 1 to 499, and x + y is preferably an integer of 1 to 500. Further, in the general formula (1-1), n is preferably 0 or an integer of 1 to 5.

On the other hand, in the general formula (I-12), examples of the active unsaturated group having a urethane bond represented by B ¹ include a (meth) acryloyl isocyanate group and a (meth) acryloyl oxyiso group. Examples include a cyanate group, an aryl isocyanate group, and a vinyl benzyl J reisocyanate group. The group represented by S ^{3 in the} general formula (1-2) is the same as the group represented by S ¹ and S ² in the general formula (1-1).

From the viewpoint of the effect of imparting mechanical strength and flexibility, typified by shape recovery properties, is great, even with the power of the macromonomer.

A ^x -U ² -S ² -U ³ -A ²

(Wherein eight ^{^{^{1, A 2, U 2,}}} U 3 and S ² are as defined above) macro port monomer and formula represented by:

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

(Wherein A ¹ Α ² , υ U ² , U ³ , S ¹ and S ² are the same as described above, and n ′ represents an integer of 1 to 4).

H> ₃ CHa GHQ

A-CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -SiO-fSi0 ^ Si— CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ -A

(Where A is the formula:

A represents an integer of 20 to 50)

Are preferred.

The above-mentioned gayne-containing polymerizable compounds can be used alone or in combination of two or more.

However, from the viewpoint of great effect of simultaneously imparting high oxygen permeability and flexibility to the ophthalmic lens, a silicon-containing (meth) acrylate is preferable, and particularly, it can be exemplified by the following formula (1-3). A methacrylate type urethane group-containing dimethylsiloxane macromonomer, tris (trimethylsiloxy) silylpropyl acrylate, and tris (trimethylsiloxy) silylpropyl methacrylate are preferred.

In addition, a silicon-containing monomer is preferably used because it is a component that mainly imparts oxygen permeability to the ophthalmic lens material, and also imparts flexibility, particularly, swelling recovery.

Representative examples of the silicon-containing monomer include, for example, pentamethyldisiloxanylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, mono [methylpis (trimethylsilyl) Mouth) siloxy] bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] Rilyl rupprolopirpirul ((meme evening and evening)) クリリクリ卜、 (((((((((((((( Riluluprolopipirul ((metameta)) acrylyl relate, methethyl rubibis ((tritrimethyl methyl rusicilloxoxy)) sicilyl riluethyrurute tetra rametichyrujijishishi mouth mouth Kisasanini Lulu Mechichi Lulu ((Memetata))

Loxanyl propyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiligobis (trimethylsiloxy) silyl propyl (methyl) acrylate, trimethylsiloxydimethylsilyl lip Acrylate; for example, Tris

(Trimethylsiloxy) silylstyrene, methylbis (trimethylsiloxy) silylstyrene, dimethylsilylstyrene, trimethylsilylstyrene, tris (trimethylsiloxy) siloxanyldimethylsilylstyrene,

[Methylbis (tristilsiloxy) siloxanyl] dimethylsilylstyrene, pentamethyldisiloxanylstyrene, heptamethyltrisiloxanylstyrene, nonastiltetrasiloxanylstyrene, penadecametylhephepalumina xanilylstyrene, heneaico Samethyldemethylxanil styrene, heptacostil tridecasiloxanyl styrene, hentria contamethyl pen, decasiloxanyl styrene, trimethylsiloxy penta

B) Silylstyrene, [tris (trimethylsiloxy) siloxanyl] bis (trimethylsiloxy) silylstyrene, methylbis (heptamethyltrisilicyloxy) silylstyrene, tris [methylbis (trimethylsiloxy) siloxy] silylstyrene, trimethylsiloxybis Tris (trimethylsiloxy) siloxy] silylstyrene, heptox kiss (trimethylsiloxy) trisiloxanylstyrene, tris [tris (trimethylsiloxy) siloxy] silylstyrene, [tris (trimethylsiloxy) hexamethyltetrasiloxane] ] [Tris (trimethylsiloxy) siloxy] Tri Methylsiloxysilylstyrene, nonakis (trimethylsiloxy) tetrasiloxanylstyrene, methylbis (tridecamethylhexaoxyxyl) silylstyrene, heptamethylcyclotetracyxanilylstyrene, heptane methylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene General formulas such as tripropyltetramethylcyclotetracyoxaxanylstyrene:

C H = C H

(Where p is an integer of 1 to 15, q is 0 or 1, and r is an integer of 1 to 15)

And the like. These can be used alone or as a mixture of two or more.

In addition, a crosslinkable compound is used as a component to impart optical properties such as transparency to the ophthalmic lens material and to further improve the mechanical strength of the ophthalmic lens material so that the ophthalmic lens material can withstand use as a lens material. May be used.

Representative examples of the crosslinkable compounds include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol (meth) acrylate. ) Acrylate, aryl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropanetri (meth) acrylate, methacryloyloxyethyl acrylate, divinylbenzene, diaryl phthalate, diaryl adipate, diethylene glycol diaryl ether , Triaryl isocyanate To nurate, 1-methylene-1-N-vinylpyrrolidone, 4-bierbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate, 2,2-bis (P- (meth) acryloyloxyphenyl) Kisafluorop Mouth bread, 2,2-bis (m- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (o- (meth) acryloyloxyphenyl) hexa Fluoropropane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) Benzene, 1,3-bis (21- (meth) acryloyloxyhexafluoroisopropyl) Benzene, 1,2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1, 3-bi (2- (meth) acryloyloxyisopropyl) benzene, 1,2-bis (2- (meth) acryloyloxyisopropyl) benzene, and the like, alone or in combination of two or more. They can be used in combination.

Among them, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diaryl adipate, and jetty are particularly effective in providing optical properties and mechanical strength to ophthalmic lens materials and are easy to handle. Preference is given to render coal diaryl ether, particularly preferably ethylene glycol di (meth) acrylate and diethylene glycol diaryl ether.

The content of the crosslinkable compound is such that the optical properties and the mechanical strength are sufficient for the ophthalmic lens material with respect to 100% by weight of the total amount of the hydroxyl group-containing polymerizable compound and the silicon-containing polymerizable compound. In order to impart it, the content is preferably at least 0.01% by weight, more preferably at least 0.05% by weight, and the mechanical strength is given to the ophthalmic lens material, but the flexibility is reduced. In order to eliminate the possibility, the content is desirably 15% by weight or less, preferably 10% by weight or less. Further, for the purpose of improving the ultraviolet absorbing property of the ophthalmic lens material, an ultraviolet absorbing agent may be contained.

Examples of the ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 5_cloth_2- (3'-one-butyl-2'-hydroxy-5'-methylphenyl) benzotriazole General formula (II) such as, 2- (5-chloro-2H-benzotriazo-1-yl-2-yl) -6- (1,1-dimethyl) -4-methylphenol

(In the formula, Z ¹ is a hydrogen atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, and Z ² and Z ³ are each independently A hydrogen atom or an alkyl group having 1 to 6 carbon atoms), 2- (2'-hydroxy-1'-methacryloxyethyleneoxy-t-butylphenyl) -l-methylbenzotriazo- Benzotriazole-based UV absorbers such as benzene; 2-hydroxy-14-methoxybenzophenone and benzophenone-based UV absorbers such as 2-hydroxy-4-octoxybenzophenone; salicylic acid derivative-based UV absorbers; hydroxyacetophenone-derived Examples include systematic UV absorbers.

Above all, benzotriazole-based UV absorbers are preferred from the viewpoint of UV-absorbing ability, and especially 2- (5-chloro-2H-benzotriazole-2-yl) 16- (1,1-dimethyl) _4 A compound represented by the general formula (II), such as monomethylphenol, is preferred.

The ultraviolet absorber may have a polymerizable group, There may be none, and there is no particular limitation.

The content of the ultraviolet absorbent is set at 100% by weight of the total amount of the hydroxyl-containing polymerizable compound and the silicon-containing polymerizable compound so as to sufficiently impart ultraviolet absorption to the ophthalmic lens material. Is preferably at least 0.01% by weight, and preferably at least 0.05% by weight. In order to prevent the relative decrease in other functions and the induction of polymerization inhibition by adding more than necessary, It is at most 5% by weight, preferably at most 3% by weight.

When producing the ophthalmic lens material of the present invention, generally, first, a radical polymerization method for generating a radical on an active unsaturated group and subjecting it to a polymerization reaction, such as a thermal polymerization method or a photopolymerization method described below, is used. A radical polymerization initiator, a photosensitizer and the like are added.

Representative examples of the radical polymerization initiator include, for example, thermal polymerization initiators such as azobisbisoptilonitrile, azobisdimethylvaleronitrile, benzoyl peroxide, t-butyl octaperoxide, cumene peroxide; Benzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether,

Benzoin-based photopolymerization initiators such as benzoin-butyl ether and benzoin-n-butyl ether; 2-hydroxy-2-methyl-1-phenylpropane-11-one, p-isopropyl-hydroxy-isobutylphenone,- t-Butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone,, a-Dichloro-4-phenoxyacetophenone, N, N-tetraethyl-1,4,4-diaminobenzophenone, etc. Polymerization initiator; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl 1,2-propanedione-2- (o-ethoxycarponyl) oxime; thioxanthone-based compounds such as 2-chlorothioxanthone and 2-methylthioxanthone Photopolymerization initiator; Dibenzosubalone; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; benzyl and the like.

The photosensitizer alone is not activated by irradiation with ultraviolet light, but when used together with a photoinitiator, functions as a cocatalyst and exerts an effect superior to that when the photoinitiator is used alone. . Examples of such photosensitizers include amines such as 1,2-benzoanthraquinone キ, n-butylamine, di-n-butylamine, and triethylamine; tri-n-butylphosphine, arylthiourea, and s-benzylisothiamine. Uroni mu ρ-toluene sulfite, getylaminoethyl methacrylate and the like. The radical polymerization initiator, the photosensitizer and the like may be used by appropriately selecting one or more of them. These are used in an amount of about 0.2 to 2 parts, preferably 0.02 parts by weight based on 100 parts by weight (hereinafter referred to as "parts") of the hydroxyl-containing polymerizable compound and the silicon-containing polymerizable compound. It is desirable to use about 1 to 1 part.

The ophthalmic lens material of the present invention can be manufactured by any known manufacturing method.However, from the viewpoint that the performance of the obtained ophthalmic lens material can be maximized, The polymer component and other components as necessary are classified into two types: a type corresponding to the shape of the front surface of a lens such as a contact lens and an intraocular lens, and a type corresponding to the shape of the rear surface of the lens. It is preferable to prepare a lens by injecting into a mold and sealing, and then performing a polymerization reaction to prepare a siloxane-containing polymer. When an intraocular lens is to be obtained, a shape corresponding to a one-piece intraocular lens in which the lens portion and the support portion are integrated may be used, and the shape of the lens portion and the support portion may be used. You may use the 铸 type.

The method of the polymerization reaction for producing the polymer is not particularly limited, and an ordinary method can be employed. In this respect, a photopolymerization method or a thermal polymerization method is preferred.

As a method of the polymerization reaction, a mixture obtained by mixing a hydroxyl group-containing polymerizable compound and a trialkylamine, and then adding a silicon-containing polymerizable compound and, if necessary, other components, to a mixture of, for example, 3 A method in which the polymerization is carried out by heating at about 0 to 60 ° C for several hours to several 10 hours, and then the temperature is gradually raised to about 120 to 140 in several hours to several hours to complete the polymerization. (Thermal polymerization method), a method of irradiating the mixture with light rays having a wavelength according to the absorption band of activation of a radical polymerization initiator such as ultraviolet rays, and polymerizing the mixture (photopolymerization method); thermal polymerization method and photopolymerization method And a method in which polymerization is carried out in combination with the above. When the above-mentioned thermal polymerization method is used, heating may be performed in a thermostatic chamber or a thermostatic chamber, or electromagnetic waves such as microwaves may be irradiated, and the heating may be performed stepwise. When the photopolymerization method is used, the photosensitizer may be further added.

The siloxane-containing polymer thus obtained is detached from the mold 铸 to obtain the ophthalmic lens material of the present invention.

The ophthalmic lens material may be subjected to mechanical processing such as cutting and polishing as necessary.

Further, the ophthalmic lens material of the present invention can be dyed. That is, after the siloxane-containing polymer is prepared as described above, the dye is dispersed (dissolved) in an organic solvent such as methanol, ethanol, or 2-propanol, and the siloxane-containing polymer is immersed and swollen. The unreacted residual monomer in the xane-containing polymer is eluted, and at the same time, the dye is diffused into the polymer. Subsequently, the dye can be immobilized on the siloxane-containing polymer when the saponification treatment is performed by an alkali treatment.

There is no particular limitation on the dye, for example, C.I. (C.I .: color index, the same applies hereinafter) Reactive Black 5, C.I. Reactive Bull 2 1, Xi 'Eye Reactive Orange 7 8, Xi Reactive Yellow 1 5, Xi Reactive Bull 4, Xi' Eye Reactive Red 1 1, Xi 'Eye Reactive dyes such as Reactive Yellow 86, Shi-I Reactive Blue 163, and Shi-I Reactive Red 180 are preferred. The amount of the dye used is not particularly limited as long as the obtained ophthalmic lens material is sufficiently dyed.

[Miscibility]

Whether or not a homogeneous solution can be obtained without mixing when the specified components are mixed.

(Evaluation criteria)

〇： Homogeneous solution

X: Phase separation occurs

[transparency]

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

(Evaluation criteria)

〇: No fogging, excellent transparency, suitable for contact lenses.

X: It is difficult to use as a contact lens because of cloudiness and poor transparency.

[Surface stickiness]

Check the feel of the surface with your fingers.

(Evaluation criteria)

〇: Smooth feel with no stickiness.

X: Stick to sticky and finger. [Strength]

Using a punching strength tester, a 1/16 inch diameter pressing needle was applied to the center of the test piece, and the load at break (penetration load (g)) of the test piece was measured. However, the values shown in Table 3 are values obtained by converting the thickness of the test piece to 0.2 mm.

[Oxygen permeability]

According to the fat method, the Dk value determined by the ISO (International Standard Oral International Organization of Foreign Standards and Foreign Standards, International Organization for Standardization) was measured.

The compounds used are as follows.

• Hydroxy group-containing polymerizable compound

2-HEA: 2-hydroxyethyl acrylate

2-HEMA: 2-hydroxyethyl methacrylate

2-HBMA: 2-hydroxybutyl acrylate

• Trialkylamine

N (E t) 3: Triethylamine

N (i B t) 3: triisobutylamine

N (Me) 3: Trimethylamine

, Silicon-containing polymerizable compounds

S 1: acrylate type urethane group-containing dimethylsiloxane macromonomer represented by the above formula (1-3)

S 2: Tris (trimethylsiloxy) silylpropyl acrylate • Additive

1—B t〇H: 1

Examples 1-3

The hydroxyl group-containing component and trialkylamine shown in Table 1 were mixed in equimolar amounts to obtain a mixed solution. The resulting mixed solution is mixed with a polymerizable compound containing gayne (with mixed solution). ) And 2-hydroxy-2-methylpropiophenone (0.2 part relative to 100 parts of the total of the hydroxyl-containing polymerizable compound and the silicon-containing polymerizable compound) as a polymerization initiator. The obtained mixture was injected into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens having a diameter of 14. O mm and a thickness of 0.08 mm).

Next, this mold was transferred to a constant temperature, and irradiated with ultraviolet rays having a wavelength of 360 nm at about 1 mWZ cm ² for 1 hour using a mercury lamp to carry out photopolymerization. A containing polymer was obtained.

Table 1 also shows the evaluation results of the miscibility.

Comparative Examples 1-2

As shown in Table 1, a contact lens-shaped siloxane-containing polymer was obtained in the same manner as in Example 1 except that no trialkylamine was added. Table 1 also shows the evaluation results of the miscibility. Compatibility test

After mixing the trialkylamine and the hydroxyl group-containing polymerizable compound with both the hydrophilic and hydrophobic components having poor compatibility, the mixture can be made compatible with the silicon-containing polymerizable compound. It becomes possible. By applying this behavior to the polymerization reaction, it has been fatal to ophthalmic lens materials. It was confirmed that a transparent polymer could be obtained from a combination of raw materials that could only yield a polymer with poor transparency. That is, it has become possible to obtain a polymer suitable for an ophthalmic lens substrate as described below. Examples 4 to 12 and Comparative Examples 3 to 5

The polymer components were mixed as shown in Table 2, and a contact lens-shaped siloxane-containing polymer was obtained in the same manner as in Example 1.

Table 2 shows the evaluation results of the transparency and the stickiness of the surface.

Table 2 Polymerization test

First step Second step Polymer characteristics Hydroxyl content ratio 1 Ratio 2 Silicon content ratio 3 Trialkylamine on the surface Transparency

Compound (molar ratio) (weight ratio) Compound (weight ratio) Sticky

4 2-HEMA N (Et) 3 1: 1 30 S1 70 〇〇

5 2-HEMA N (Et) 3 1: 1 30 S2 70 〇〇

2-HEA 20 S1 30

6 N (Et) 3 1: 1 〇〇 2-HEMA 20 S2 30

2-HEA 15 S1 20

7 N (Et) 3 1: 1 〇〇 2-HEMA 15 S2 50

Real

Application 8 2-HBMA N (Et) 3 1: 1 50 S2 50 〇〇 Example 9 2-HEMA N (iBt) 3 1: 1 50 S2 50 〇〇

10 2-HEA N (Et) 3 1: 1 30 S2 70 〇〇

S1 40

11 2-HEA N (Et) 3 1: 1 30 〇〇

S2 30

2-HEMA 15 S1 20

12 N (Et) 3 1: 1 〇〇 2 -HE A 5 S2 60

3 2-HEMA 1 ― 30 S1 70 X 比 ratio

4 2-HEMA 1 ― 30 S2 70 X 〇 Example

5 2-HEA 1 ― 30 S2 70 X 〇

In Table 2, the ratio 1 (molar ratio) indicates the mixing ratio of the hydroxyl group-containing polymerizable compound and the trialkylamine. According to this ratio 1, both components were mixed. Thereafter, the ratio of the hydroxyl group-containing polymerizable compound was mixed at a ratio of 2 (weight ratio), and the ratio of the gayne-containing polymerizable compound was mixed at a ratio of 3 (weight ratio).

Regarding the obtained polymer, its transparency and stickiness on the surface were confirmed, and it was confirmed that the polymer satisfies the required characteristics as an ophthalmic lens material in Examples. According to Comparative Examples 3 to 5, when copolymerization of a hydroxyl-containing component and a silicon-containing component was carried out in an environment in which no trialkylamine was added, the copolymer, which is the most important requirement as an optical product, was transparent. It has been shown to impair sex.

Examples 13 to 14 and Comparative Examples 6 to 7

2-hydroxy-2-methylpropiophenone (0.2 part relative to 100 parts of the total amount of the hydroxyl-containing polymerizable compound and the silicon-containing polymerizable compound) as a polymerization initiator, and ethylene glycol as a cross-linking agent. According to Table 3, except that 1-dimethyl acrylate (0.3% by weight based on the total amount of 100% by weight of the hydroxyl-containing polymerizable compound and the silicon-containing polymerizable compound) was used. Example 1 A siloxane-containing polymer in the form of a contact lens was obtained in the same manner. In Examples 13 and 14, 1 mol of triethylamine was mixed with respect to 1 mol of OH groups contained in the hydroxyl-containing polymerizable compound.

Table 3 shows the evaluation results of strength and oxygen permeability.

Table 3 Silicon-containing hydroxyl-containing compounds Polymer properties Compound (weight ratio) Light weight A

Crosslinking agent Additive

Initiator

(Weight part)

S1 strength

S2 2-HEMA 2-HEA (ml * cm / cm

(g)禾少'mniHg) real 13 10 70 15 5 0.3 0.2 N (Et) 3 16 220 160X10- 11 facilities

Example 14 30 50 15 5 0.3 0.2 N (Et) 3 16 160 140X10 - 11 ratio 6 10 70 15 5 0.3 0.2 1 -BtOH 60 30 155X10- 11 Example 7 30 50 15 5 0.3 0.2 1 -BtOH 60 15 140X10- 11

As shown in Table 3, by using the method for manufacturing an ophthalmic lens material of the present invention, a copolymer having high oxygen permeability and excellent lipid stain resistance can be obtained without impairing the transparency essential for an optical material. It can be seen that it can be obtained. In addition, unlike conventional methods using organic solvents such as alcohols and ketones, the method of obtaining a material with excellent transparency does not impair the degree of polymerization and crosslink density, so it is superior in strength as an optical material. It is clear that this is the optimal method for obtaining the required ophthalmic lens material. Industrial applicability

In the production of an optical material in which both a silicon-containing component and a hydroxyl-containing component, which are inferior in copolymerizability, are copolymerized, the use of trialkylamine is essential for optical products without impairing the degree of polymerization and crosslink density. It becomes possible to obtain a copolymer having excellent transparency.

Claims

Scope of Word

1. A method for producing a soft ophthalmic lens material comprising a polymer containing a hydroxyl group-containing polymerizable compound and a gayne-containing polymerizable compound, comprising the following steps.

(2) A step of adding a silicon-containing polymerizable compound to the mixed solution of (1) and subjecting it to a polymerization reaction to obtain a polymer.

2. The method for producing a soft ophthalmic lens material according to claim 1, wherein the alkyl chain of the trialkylamine has 6 or less carbon atoms.

3. The method for producing a soft ophthalmic lens material according to claim 1, wherein the hydroxyl-containing polymerizable compound is a hydroxyalkyl (meth) acrylate.

4. The silicon-containing polymerizable compound is selected from an acrylate type urethane group-containing dimethylsiloxane macromonomer, tris (trimethylsiloxy) silylpropyl acrylate, and tris (trimethylsiloxy) silylpropyl methacrylate. 4. The method for producing a soft ophthalmic lens material according to claim 1, wherein the material comprises one or more kinds.

5. The method for producing a soft ophthalmic lens material according to claim 1, wherein the alkyl chain of the trialgylamine has 4 or less carbon atoms.

6. The method for producing a soft ophthalmic lens material according to claim 1, wherein the trialgylamine is triethylamine.

7. The hydroxyl-containing polymerizable compound may be 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, or 2-hydroxypropyl methacrylate. Claims 1, 2, and 3 comprising one or more selected from acrylates, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, and 2-hydroxybutyl acrylate. 7. The method for producing a soft ophthalmic lens material according to item 4, paragraph 5, paragraph 5 or paragraph 6.

8. The method according to claim 1, wherein the polymerization reaction of (2) is a polymerization reaction by light or heat. A method for producing a soft ophthalmic lens material.

9. A contact lens obtained by the manufacturing method according to claim 1, 2, 3, 3, 4, 5, 6, 7, or 8.

10. An intraocular lens obtained by the manufacturing method according to claim 1, 2, 3, 3, 4, 5, 6, 7, or 8.