JPH03210523A - Nonhydrous intra-ocular insert - Google Patents

Abstract

PURPOSE:To obtain the nonhydrous contact lens which does not require boiling disinfection by forming the contact lens of a copolymer essentially consisting of ester methacrylate and/or acrylate and a specific organosiloxane monomer and crosslinkable monomer which are respectively specific. CONSTITUTION:The contact lens is formed of the ester methacrylate and/or acrylate at <=50pts.wt. ratio, the organosiloxane monomer expressed by formula I at 0 to 50pts.wt. and the crosslinkable monomer expressed by formula II at 10 to 50pts.wt. In the formulas R1, R2, R5, R6, R9, R11, X1 to X8 are selected from 1 to 6C alkyl groups, arom. groups, etc.; l, l', m, m', j, j' denote 0 to 10 integer; (n) denotes 1 to 10; (k) denotes 0 or 1; R14 denote a hydrogen atom or methyl group; (q) denotes 1 to 5 integer. The nonhydrous soft contact lens which does not require the boiling disinfection is obtd. in this way.

Description

[Detailed description of the invention] [Industrial application field]

TECHNICAL FIELD The present invention relates to intraocular inserts such as substantially non-hydrous soft contact lenses.

[Background of the invention]

Water-containing soft contact lenses lack shape stability, must be frequently sterilized by boiling, and furthermore have problems such as being easily contaminated. Therefore, soft contact lenses made of non-hydrous polymers such as polydimethylsiloxane have been proposed, but these lenses have a water-repellent surface that makes them difficult to fit into the eyes, and the surface has been treated with wood-loving properties to improve fit. However, there are problems such as the treatment effect decreasing over time. In addition, Mitchell Dien et al. proposed a contact lens made mainly of polyacrylic acid ester that is comfortable to the eyes (Japanese Patent Publication No. 59-33887).This contact lens mainly contains acrylic acid, A hard copolymer consisting of an ester, a methacrylic acid ester, and a small amount of crosslinkable heptamer is prepared, cut into a lens shape, polished, and subjected to an esterification reaction and/or transesterification reaction in an appropriate alcohol. This is a non-hydrous soft contact lens. By the way, non-hydrous soft contact lenses developed by Mitchell Dien et al. do not require boiling sterilization and are easy to fit into the eyes, but they have low mechanical strength and are easily damaged during cleaning operations before and after wearing them. . In addition, the non-hydrous soft contact lens disclosed in JP-A-62-127823 has excellent flexibility, but has insufficient mechanical strength and poor oxygen permeability, so it cannot be used for long periods of time. The problem is that it cannot be worn.

[Disclosure of the invention]

A first object of the present invention is to provide a water-free soft contact lens that does not require boiling sterilization. A second object of the present invention is to provide a water-free soft contact lens that is resistant to staining by lachrymal fluid components. A third object of the present invention is to provide a water-free soft contact lens with good oxygen permeability. A fourth object of the present invention is to provide a water-free soft contact lens with high mechanical strength. The object of the present invention is to combine a methacrylic ester and/or acrylic ester with an organosiloxane monomer represented by the following general 2 (1) (where X1 to X are C1 to C6 alkyl groups, aromatic groups and selected from the group consisting of Y groups, where Y group is CHt-C-
R+3 0・C−0−(CHtCHtO)p −CH*CHtC
H! ~ and P is an integer of O or 1 eXI~X,
At least one of them is a Y group, R13 is a hydrogen atom or a methyl group, R8, R2., R1.., R
5-R7, R9 to R+i are selected from the group consisting of a C+ to Ch alkyl group, an aromatic group, and a Z group, and the Z group is R,.R,-5i-0-R1.., and R1, R8 does not represent a group, R+ ORs
or selected from the group consisting of an alkyl group, an aromatic group and a Z group with C+=Ci, 1.
1゛, -1-゛, j, j' are integers from θ to 10, n is from 1 to
an integer of 10, k is O or 1), and a monomer represented by the following catalytic formula (2) l4 CH = CC00 (CHz) so - (however, Ro is a hydrogen atom or a methyl group, and q is 1 This is achieved by a water-free intraocular insert characterized by being composed of a copolymer containing as an essential component an integer of ~5. In addition, in this non-hydroscopic intraocular insert, methacrylic acid ester and/or acrylic acid ester is 50 parts by weight or less, organosiloxane heptamine represented by general formula (1) is 10 to 50 parts by weight, general Preferably, the proportion of the crosslinkable hexamer represented by formula (2) is 10 to 50 parts by weight. Among the monomer components of the copolymer constituting the non-hydroscopic intraocular insert such as the non-hydroscopic soft contact lens of the present invention, the methacrylic acid esters include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n- -propyl methacrylate, 1-
Propyl methacrylate, t-butyl methacrylate,
n-pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-hebutyl methacrylate, n-octyl methacrylate, n-
Decyl methacrylate, n-dodecyl methacrylate,
n-tetradecyl methacrylate, n-hexadecyl methacrylate, lauryl methacrylate, etc. (preferably n-butyl methacrylate, 2-ethylhexyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-hebutyl methacrylate, n-octyl methacrylate) , n-decyl methacrylate and n
-dodecyl methacrylate, etc.), the alkoxyalkyl ester group is -CHIC
)1!0R1-cHICL(Oli)C1ls, CHz
CHzC)lzOR, CI(CHs)CHtOR,CH
methacrylic acid alkoxyalkyl ester having an alkoxyalkyl group represented by zCFhCHzCHtOR (in which R is an alkyl group having 1 to 7 carbon atoms), other cyclohexyl methacrylate, benzyl methacrylate,
Examples include phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, and tetrahydrofurfuryloxyethyl methacrylate. Incidentally, two or more kinds of these methacrylic acid esters can be used in combination. Furthermore, among the monomer components of the copolymer constituting the non-hydroscopic intraocular insert of the present invention, as the acrylic ester,
For example, methyl acrylate, ethyl acrylate, n-
Butyl acrylate, n-pentyl acrylate, n-
hexyl acrylate, n-hebutyl acrylate, 2
- Ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-tetradecyl acrylate, n-hexadecyl acrylate, lauryl acrylate, cyclohexyl acrylate (preferably n-butyl acrylate,
Acrylic acid alkyl esters such as n-pentyl acrylate, n-hexyl acrylate, n-hebutyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate), CHxCHxOR, CHtCH
t(OR)CHs. CHtC[ltC[I, 01? , -C1l(CH3
) CH, OR, -CHtCHtCH1CH2OR (in the group, R is an alkyl group having 1 to 7 carbon atoms) acrylic acid alkoxyalkyl ester having an alkoxyalkyl group, other benzyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonyl Examples include phenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, and 1°3-dioxolane acrylate. In addition, two or more types of these acrylic esters can be used in combination. Both of the above acrylic ester and methacrylic ester can also be used in combination. Furthermore, among the monomer components of the copolymer constituting the water-free intraocular insert of the present invention, the monomer represented by the above general formula (1) is, for example, methacryloxyethoxypropylpentamethyldisiloxane, acryloxy Ethoxypropylpentamethyldisiloxane, methacryloxyethoxypropylheptamethyltrisiloxane, acryloxyethoxypropylheptamethyltrisiloxane, methacryloxyethoxypropyltris(trimethylsiloxy)silane, acryloxyethoxypropyltris(trimethylsiloxy)silane, methacryloxy Ethoxypropylphenyltetramethyldisiloxane, acryloxyethoxypropylphenyltetramethyldisiloxane, methacryloxyethoxypropyltribenzyldiethyldisiloxane, acryloxoethoxypropyltribenzyldiethyldisiloxane, methacryloxyethoxypropyl n-pentylhexamethyldisiloxane Siloxane, acryloxyethoxypropyl n-pentylhexamethyltrisiloxane, methacryloxyethoxyprobildi-n-propylpentamethyltrisiloxane, acryloxyethoxyprobildi-n-propylpentamethyltrisiloxane, methacryloxyethoxypropylphenyl octamethyltetrasiloxane , acryloxyethoxypropylphenyl octylmethyltetrasiloxane, methacryloxyethoxypropyl isobutyltetramethyldisiloxane, acryloxyethoxypropylisobutyltetramethyldisiloxane, methacryloxyethoxypropylmethylbis(trimethylsiloxy)silane, acryloxyethoxypropyl Bylmethylbis(trimethylsiloxy)silane, methacryloxyethoxypropyltris(dimethylcyclohexylsiloxy)silane, acryloxyethoxypropyltris(dimethylcyclohexylsiloxy)silane, methacryloxyethoxypropylpentamethyldisiloxane(trimethylsiloxy) Silane, acryloxyethoxypropylbentamethyldisiloxybis(trimethylsiloxy)silane, methacryloxyethoxypropyl to butamethylcyclotetrasiloxane, acryloxyethoxypropyl to butamethylcyclotetrasiloxane, methacryloxyethoxypropyltetramethyltriprobylcyclo Tetrasiloxane, acryloxyethoxypropyltetramethyltripropylcyclotetrasiloxane, methacryloxyethoxypropyltris(trimethylsiloxy)silane, and the like can be mentioned. Note that two or more types of these organosiloxanes can be used in combination. Furthermore, among the heptamer components of the copolymer constituting the non-hydroscopic intraocular insert of the present invention, monomers represented by general formula (2) include, for example, terephthalic acid di(acryloxypentyl ester, etc.). Among these, monomers in which R14 is a hydrogen atom or a methyl group and q is an integer of 1 to 3 are preferred.Also, for example, a polyhydric alcohol having 10 or less carbon atoms and methacrylic acid or acrylic acid. diesters, triesters, tetraesters, etc., such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1° 3-
Butanediol dimethacrylate, 1, 3-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1
．． 6-hexanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate Crosslinkable supercomponents such as esters can be used in the copolymers that make up the non-hydroscopic intraocular inserts of the present invention. However, it is desirable that such crosslinkable monomer components account for 10% by weight or less of the total copolymerization components. Note that two or more types of these crosslinking monomers can be used in combination. And for the above monomer, dimethyl-2
, 2'-azobisisobutyrate, 2゜2゛-azobis(4-methoxy-2,4"-dimethylvaleronitrile)
, 2.2′-azobis(2°4-dimethylvaleronitrile), 2.2″-azobisisobutylnitrile, benzoyl peroxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, isobutyl peroxide, diisopropyl peroxide A free radical polymerization initiator such as dicarbonate is blended, and polymerization is carried out by ordinary radical polymerization methods. Polymerization methods include thermal polymerization, ultraviolet polymerization, radiation polymerization, etc.
Contact lens manufacturing methods include cast molding (a method using a mold), spin casting, and the like. The amount of monomer used at this time is preferably 0 to 50% by weight, more preferably 20 to 50% by weight of acrylic ester and/or methacrylic ester, and preferably 20 to 50% by weight of the organosiloxane monomer represented by formula (1). 10～
50% by weight, more preferably 20-50% by weight, formula (2
) is preferably 10 to 50% by weight,
More preferably, the content is 20 to 50% by weight, and the content of crosslinking monomers such as triethylene glycol dimethacrylate is preferably 10% by weight or less, and more preferably 1 to 10% by weight. Examples] Examples are shown below, but the present invention is not limited to these specific examples. Example 1 32% by weight of n-butyl methacrylate, 32% by weight of methacryloxypropyltris(trimethylsiloxy)silane, 32% by weight of a 7-mer compound represented by formula (2) (wherein Rla is a hydrogen atom, and q is 2) %, 4% by weight of tetraethylene glycol dumethacrylate as a crosslinking monomer was mixed, and after adding 0.01% by weight of 2.2°-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, the mixed solution was Injected into a contact lens mold and heated to approximately 55°C.
After polymerizing for 24 hours at 75'C, 100''C111
The polymerization was completed by holding at each temperature of 0° C. for 24 hours. After cooling, it is removed from the mold to obtain a colorless and transparent contact lens. Example 2 38% by weight of n-butyl methacrylate, 38% by weight of methacryloxypropyl tris(trimethylsiloxy)silane, 7mer represented by formula (2) (wherein Rla is a hydrogen atom, and q is 2) 20% by weight, 4% by weight of tetraethylene glycol dimethacrylate as a crosslinking agent, and 2.2°-azobis(2,4-
A contact lens is obtained in the same manner as in Example 1 using a lens containing 0.01% by weight of dimethylvaleronitrile. Example 3 29% by weight of n-butyl methacrylate, 27% by weight of methacryloxypropyltris(trimethylsiloxy)silane, 40% by weight of the monomer represented by formula (2) (wherein Rla is a hydrogen atom, and q is 2), 4% by weight of tetraethylene glycol dimethacrylate was mixed as a crosslinkable additive, and 0.01% by weight of 2.2'-azobis(2,4-dimethylvaleronitrile) was added as a polymerization initiator. A contact lens is obtained in the same manner as in Example 1. Example 4 38% by weight of n-butyl methacrylate, 38% by weight of methacryloxyethoxyprobyl tris(trimethylsiloxy)silane, monomer represented by formula (2) (wherein L
4 is a hydrogen atom;
, 4-dimethylvaleronitrile) to which 0.01% by weight was added, a contact lens was obtained in the same manner as in Example 1. Example 5 32% by weight of n-butyl methacrylate, 32% by weight of methacryloxyethoxypropyltris(trimethylsiloxy)silane, a monomer represented by formula (2) (in the formula, R
+4 is a hydrogen atom, q is 2) 32% by weight, 4% by weight of tetraethylene glycol dimethacrylate as a crosslinking monomer, and 2.2°-azobis(
A contact lens is obtained in the same manner as in Example 1 using a lens containing 0.01% by weight of 2,4 dimethylvaleronitrile. The hardness, water wettability (hydrophilic contact angle), light transmittance, tensile strength,
The degree of elongation at break, water content, and oxygen permeability were measured, and the results are shown in Table 1.

Claims (1)

[Claims] 1. A methacrylic ester and/or an acrylic ester and an organosiloxane monomer represented by the following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼(1) (However, X_1 to X_8 is selected from the group consisting of C_1 to C_6 alkyl groups, aromatic groups, and Y groups, and the Y group is ▲Formula, chemical formula, table, etc.▼, and p is an integer of 0 or 1.X_1 to X_6 At least one of them is a Y group, R_1_3 is a hydrogen atom or a methyl group, R_2, R_2_', R_
2_″, R_3 to R_7, R_9 to R_1_2 are C_1
-C_6 are selected from the group consisting of alkyl groups, aromatic groups, and Z groups, and the Z group is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_1 and R_8 do not represent groups, and R_1-0
- Indicates an ether bond consisting of R_8 or C_1~
selected from the group consisting of C_6 alkyl group, aromatic group and Z group, l, l', m, m', j, j' are integers of 0 to 10, n is an integer of 1 to 10, k is 0 or 1) and a monomer represented by the following general formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1_4 is a hydrogen atom or a methyl group, and q
is an integer of 1 to 5) as an essential component. (2) In the non-hydroscopic intraocular insert according to claim 1, the methacrylic ester and/or acrylic ester is 50 parts by weight or less, the organosiloxane monomer is 10 to 50 parts by weight, and the general formula ( The proportion of the monomer represented by 2) is 10 to 50 parts by weight.