JP4980573B2 - Transparent gel and ophthalmic lens material comprising the same - Google Patents

Description

  The present invention relates to a transparent gel having a mutual network structure of a specific polyimide silicone resin and a hydrophilic polymer obtained by polymerizing a hydrophilic monomer, particularly a culture substrate for cells and organs, a container for use in storage, and an ophthalmic lens. The present invention relates to materials (for example, contact lens (hereinafter abbreviated as “CL”) materials, intraocular lens materials, corneal inlay materials, etc.).

  Conventionally, as a material for CL, a macromonomer having a polymerizable group introduced at both ends of polydimethylsiloxane has been used. However, the synthesis of the macromonomer is complicated, and there are problems in the control of the molecular weight and the rate of introduction of the polymerizable group. Further, since the macromonomer functions as a crosslinking agent, there are limitations in obtaining preferable physical properties. In addition, since it has a high molecular weight, its polymerizability is not assured, and in some cases, a problem that stable polymerization cannot be achieved has been pointed out.

  As a silicone resin having no polymerizable group, Patent Document 1 describes a polyimide silicone resin having excellent heat resistance, mechanical strength, solvent resistance, and the like. However, for this resin, properties such as oxygen permeability and water content required for use as CL have not been studied, and since these materials are not hard and transparent gels themselves, It was not suitable as a culture substrate or ophthalmic lens material. Furthermore, it is described here only for use in color filters, light emitting diodes, laser diode protective films, liquid crystal light distribution films, liquid crystal display devices, etc. in semiconductor devices, and this resin is used for ophthalmic lenses such as CL materials. It was not supposed to be used as a material.

  Another material for ophthalmic lenses is a hydrophilic polymer obtained by polymerizing a hydrophilic monomer. Patent Document 2 describes a polyvinyl alcohol hydrogel excellent in transparency that can be used for CL or a cell culture substrate. However, this hydrogel is obtained by irradiating radiation after formalizing polyvinyl alcohol, and properties such as oxygen permeability and shape retention have not been studied. I couldn't get any ophthalmic lens material.

  In addition to this, in order to improve gel strength, a method of polymerizing by adding a polymer, particularly polyacrylate, to a hydrophilic monomer is known. However, when the polydimethylsiloxane is used as the polymer, for example, there is a problem that the stickiness peculiar to silicone occurs. When polyimide is used, the strength is improved but the desired gas permeability is obtained. There was no problem. Further, when the addition amount is increased, transparency cannot be ensured and it is not suitable as a lens material.

  Patent Document 3 discloses an ophthalmic lens material comprising a hydrophilic polymer and a polyimide resin, that is, an ophthalmic lens comprising a copolymer obtained by polymerizing a polymerization component comprising a polyimide resin and a nitrogen atom-containing monomer. The materials are listed. However, when an ophthalmic lens material is produced using the polyimide resin described herein, the material is colored, and thus the transparency is poor. Further, oxygen permeability has not been studied. Therefore, in order to obtain a satisfactory ophthalmic lens material, further improvements in transparency and oxygen permeability were required.

JP 2004-149777 A JP-A-7-255941 Japanese Patent Laid-Open No. 9-68680

  The present invention comprises a polyimide silicone resin that is easy to synthesize and purify, and a hydrophilic polymer obtained by polymerizing a hydrophilic monomer, and has excellent properties such as gel strength, transparency, oxygen permeability, and refractive index, cells, organs, etc. It is an object of the present invention to provide a transparent gel that can be used as a culture substrate, a container for use in storage, and an ophthalmic lens material.

  As a result of diligent research to solve the above problems, a transparent gel comprising a hydrophilic polymer obtained by polymerizing a specific polyimide silicone resin and a hydrophilic monomer, and having a mutual network structure of the polyimide silicone resin and the hydrophilic polymer is a gel. The present inventors have found that it is excellent in strength, transparency, oxygen permeability, refractive index, and the like, and have reached the present invention.

  That is, the present invention comprises a transparent polyimide silicone resin having a structural unit represented by the following general formula (1) and soluble in an organic solvent, and a hydrophilic polymer obtained by polymerizing a hydrophilic monomer. The present invention relates to a transparent gel having a mutual network structure of a polyimide silicone resin and a hydrophilic polymer.

[Wherein X is a tetravalent organic group having 4 or more carbon atoms, and a plurality of —CO— groups are not bonded to one carbon atom of X, and Z is represented by the general formula (2 Is a diamine residue represented by

(In the formula, R ^{9 to} R ¹² are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, and these may be the same or different. A is an integer of 1 to 100. )]
X in the general formula (1) is

It is preferable that

  More preferably, the transparent polyimide silicone resin further contains a structural unit represented by the following general formula (3).

[In the formula, X is a tetravalent organic group having 4 or more carbon atoms, and a plurality of —CO— groups are not bonded to one carbon atom of X; ), One or more selected from diamine residues represented by general formula (5) or general formula (6)

(Wherein R ^{1 to} R ⁶ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different)

(Wherein R ⁷ and R ⁸ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different)

]

]

  X in the general formula (3) is

More preferably.

  The diamine residue represented by the general formula (2) is 5 to 95 mol% with respect to all diamine residues, and is represented by the general formula (4), the general formula (5), or the general formula (6). It is preferable that the diamine residue is 5 to 95 mol%.

  The hydrophilic monomer is preferably a nitrogen atom-containing monomer.

  The nitrogen atom-containing monomer is more preferably N-vinylpyrrolidone, N, N-dimethylacrylamide and / or N-methyl-3-methylidenepyrrolidone.

  A in the general formula (2) is preferably 5 to 80.

  As for the ratio of the said transparent polyimide silicone resin: hydrophilic polymer, it is more preferable that it is 10: 90-40: 60 by weight ratio.

  The present invention also includes a step of polymerizing a hydrophilic monomer after dissolving a transparent polyimide silicone resin having a structural unit represented by the general formula (1) and soluble in an organic solvent in a hydrophilic monomer solution. It is related with the manufacturing method of the transparent gel containing.

  In the said manufacturing method, it is preferable that the structural unit represented by the said General formula (3) is further contained in transparent polyimide silicone resin.

  In the manufacturing method, when the transparent polyimide silicone resin is dissolved in the hydrophilic monomer solution, it is preferable to further include a step of adding a crosslinking agent, and the crosslinking agent is more preferably allyl methacrylate or diethylene glycol diallyl ether. . As a compounding quantity of a crosslinking agent, it is preferable that it is 0.1 to 10 weight% in all the mixtures.

  The polymerization is preferably performed in a mold.

  The present invention further relates to an ophthalmic lens material comprising the transparent gel.

  According to the present invention, a transparent gel having a mutual network structure of a specific polyimide silicone resin and a hydrophilic polymer obtained by polymerizing a hydrophilic monomer and having excellent properties such as gel strength, transparency, oxygen permeability, and refractive index is obtained. It is done. Moreover, since this transparent gel is excellent also in the ultraviolet absorptivity, it can be used as various ophthalmic lens materials including CL and intraocular lenses.

  The polyimide silicone resin used in the present invention is easily synthesized and purified, and is excellent in terms of molecular weight control. Moreover, since it does not have a polymerizable group, it is possible to suppress polymerization shrinkage during polymerization (mold polymerization) in a resin mold and improve shape accuracy. By adjusting the ratio between the soft segment (silicone component) and the hard segment, the length of the soft segment, the structure of the hard segment, the molecular weight of the copolymer, etc., the gas permeability, gel strength, and the like can be set to desired levels. Furthermore, since the adhesiveness of the lens surface is suppressed, when used as an ophthalmic lens material, adsorption to the cornea can be avoided.

  The transparent gel of the present invention comprises a specific polyimide silicone resin and a hydrophilic polymer obtained by polymerizing a hydrophilic monomer, and has an inter-network (IPN) structure of the polyimide silicone resin and the hydrophilic polymer.

  In the present invention, “transparent” means that the visible light transmittance (% T) is 80% or more.

  The polyimide silicone resin used in the present invention contains a structural unit represented by the following general formula (1).

[Wherein X is a tetravalent organic group having 4 or more carbon atoms, and a plurality of —CO— groups are not bonded to one carbon atom of X, and Z is represented by the general formula (2 Is a diamine residue represented by

(In the formula, R ^{9 to} R ¹² are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, and these may be the same or different. A is an integer of 1 to 100. )]

  In the present invention, it is preferable that the transparent polyimide silicone resin further includes a structural unit represented by the following general formula (3).

[In the formula, X is a tetravalent organic group having 4 or more carbon atoms, and a plurality of —CO— groups are not bonded to one carbon atom of X; ), One or more selected from diamine residues represented by general formula (5) or general formula (6)

(Wherein R ^{1 to} R ⁶ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different)

(Wherein R ⁷ and R ⁸ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different)

]

]

  The polyimide silicone resin used in the present invention is a reaction product of a diamine and a tetracarboxylic dianhydride, and includes a thermosetting group in the structure of the reaction product and is soluble in an organic solvent. It is characterized by being transparent.

  As the thermosetting group, a carboxyl group, an amino group, an epoxy group, a hydroxyl group, etc. are generally known, but a phenol group is preferable in that it does not easily react with a carboxyl group and an amino group in consideration of the production process of polyimide. .

  A diamine that is a raw material of the polyimide silicone resin will be described.

  In the present invention, a diamine containing a diaminosiloxane residue is used as the diamine residue. Examples of the diaminosiloxane residue include those represented by the general formula (2).

(In the formula, R ^{9 to} R ¹² are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. alkyl groups such as Group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, aryl group such as phenyl group and xylyl group, aralkyl group such as benzyl group and phenethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, etc. In addition to trialkoxysilylated alkyl groups such as 2- (trimethoxysilyl) ethyl groups, alkoxy groups such as methoxy groups, ethoxy groups, and propoxy groups, aryloxy groups such as phenoxy groups, cyano groups, etc. Of these, a methyl group, an ethyl group, or a phenyl group is preferable, and a is 1 to 1. It is an integer of 00. When a in the general formula (2) exceeds 100, the viscosity of the transparent polyimide silicone resin increases, it becomes difficult to handle, and it becomes difficult to produce a transparent gel. From the viewpoint of ease of production of the transparent gel, rigidity of the transparent gel, and oxygen permeability, a is preferably from 5 to 80. 10 to 20 are more preferable.)

  The diaminosiloxane residue is preferably included in the total diamine residue in an amount of 5 to 100 mol%. More preferably, it is 5-95 mol%, More preferably, it is 50-95 mol%, Most preferably, it is 60-90 mol%. If it is less than 5 mol%, the rigidity of the transparent gel increases excessively and the oxygen permeability tends to decrease.

  In the present invention, for example, it is preferable to use a diamine containing a diamine residue represented by the general formula (4), the general formula (5), or the general formula (6).

(In the formula, R ^{1 to} R ⁶ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and these may be the same or different. Examples of R ^{1 to} R ⁶ include a methyl group and an ethyl group. , A propyl group, a butyl group, a pentyl group, a hexyl group and the like, and a methyl group is preferred.

(In the formula, R ⁷ and R ⁸ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and these may be the same or different. Examples of R ^{7 to} R ⁸ include a methyl group and an ethyl group. , A propyl group, a butyl group, a pentyl group, a hexyl group and the like, and a methyl group is preferred.

  Such diamine residues other than diaminosiloxane residues are preferably contained in an amount of 95 mol% or less in all diamine residues. More preferably, it is 5-95 mol%, More preferably, it is 5-50 mol%, Most preferably, it is 10-40 mol%. If it exceeds 95 mol%, the content of diaminosiloxane residue will decrease, the solubility in organic solvents will tend to decrease, the rigidity of the transparent gel will increase excessively, and the oxygen permeability will decrease. End up.

  In the diamine, since the polyimide silicone resin used in the present invention is transparent in the visible light region, it is preferable that the diamine as the raw material is not colored.

  In addition to the above, a known general diamine can be used simultaneously as a raw material for synthesizing the polyimide silicone resin used in the present invention as long as the transparency is not impaired. For example, aliphatic diamines such as tetramethylenediamine, 1,4-diaminocyclohexane and 4,4′-diaminodicyclohexylmethane, phenylenediamine, 4,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane Aromatic diamines such as these can be used, and these can be used alone or in combination of two or more.

  Next, the tetracarboxylic dianhydride that is a raw material of the polyimide silicone resin used in the present invention will be described. The polyimide silicone resin of the present invention is characterized in that it is transparent in the visible light region, and the raw material tetracarboxylic dianhydride is not colored, and the charge transfer complex known as the cause of coloring Those that are difficult to form are preferred. Aliphatic tetracarboxylic dianhydrides or alicyclic tetracarboxylic dianhydrides are preferred in terms of excellent transparency, but aromatic tetracarboxylic dianhydrides that are superior in heat resistance within the range not colored may be used. Good.

  Examples of the aliphatic tetracarboxylic dianhydride include butane-1,2,3,4-tetracarboxylic dianhydride or pentane-1,2,4,5-tetracarboxylic dianhydride. As the alicyclic tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, dicyclohexyl-3, 4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetra Carboxylic dianhydrides are exemplified, and examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 4,4′-hexafluoropropylidenebisphthalic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, and the like. . 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, Fragrances such as 3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione An aliphatic tetracarboxylic dianhydride having a ring may be used. These tetracarboxylic dianhydrides can be used alone or in combination of two or more. Of these, aromatic tetracarboxylic acids having an aromatic group are preferred in terms of transparency, heat resistance, moderate rigidity of the transparent gel, and refractive index, and 1,3,3a, 4,5,9b-hexahydro-5 is preferred. -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione is more preferred.

  The transparent polyimide silicone resin obtained using the diamine and tetracarboxylic dianhydride has a structural unit represented by the general formula (1) and further the general formula (3). X in these general formulas (1) and (3) is in terms of transparency and heat resistance, appropriate rigidity of the transparent gel, and refractive index.

It is preferable that

  Polyimide silicone resin can be produced by a one-step polymerization method in which diamine and tetracarboxylic dianhydride are used in approximately equimolar numbers in the presence of a solvent and polymerized only at a high temperature, or first, an amic acid is synthesized at a low temperature, Thereafter, any of two-stage polymerization methods in which imidization is performed at a high temperature may be used.

  The ratio of the diamine component to the tetracarboxylic dianhydride component is appropriately determined according to the adjustment of the molecular weight of the polyimide silicone resin, and is usually 0.95 to 1.05, preferably 0.98 to 1.02 in molar ratio. Range. In order to adjust the molecular weight of the polyimide silicone resin, a monofunctional raw material such as phthalic anhydride and aniline can be added. In this case, the addition amount is preferably 2 mol% or less with respect to the total imide skeleton.

  In the case of the one-stage polymerization method, the reaction temperature is 150 to 300 ° C., and the reaction time is 1 to 15 hours. When the two-stage polymerization method is used, polyamic acid synthesis is performed at a temperature of 0 to 120 ° C. for 1 to 100 hours, and then imidization is performed at a temperature of 0 to 300 ° C. for 1 to 15 hours.

  The solvent that can be used at the time of synthesis may be any one that is compatible with the raw material diamine and tetracarboxylic dianhydride and the product polyimide silicone. For example, phenols such as phenol, 4-methoxyphenol 4-methoxyphenol, 2,6-dimethylphenol, m-cresol, ethers such as tetrahydrofuran and anisole, cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, Ketones such as 2-octanone and acetophenone, esters such as butyl acetate, methyl benzoate and γ-butyrolactone, cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate, N, N-dimethylformamide, N, N-dimethyl Examples include amides such as acetamide and N-methyl-2-pyrrolidone.

  Moreover, it is also possible to make it easy to remove water generated during imidization by azeotropy by using together aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

  When using at least one of diamine and at least one of tetracarboxylic dianhydrides, the reaction method is not particularly limited, for example, a method of co-condensation after mixing all the raw materials in advance, or two or more types used. In this method, the diamine or tetracarboxylic dianhydride is sequentially added while reacting separately.

  Moreover, you may use the method of imidating by adding a dehydrating agent and an imidation catalyst in an imidation process, and heating as needed. In this method, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 1 to 10 mol per 1 mol of diamine.

  Moreover, as an imidation catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. The amount of the imidization catalyst used is preferably 0.5 to 10 mol with respect to 1 mol of the dehydrating agent to be used.

  The polyimide silicone resin used in the present invention has a transmittance in a wavelength region of 380 to 780 nm, that is, a so-called visible light region in an ultraviolet / visible light absorption spectrum measured on a glass plate having a thickness of 1 mm and a film having a thickness of 10 μm. It has a feature of 80% or more.

  The polyimide silicone resin is excellent in solubility in an organic solvent such as a hydrophilic monomer.

  The transparent gel of the present invention comprises the polyimide silicone resin and a hydrophilic polymer obtained by polymerizing a hydrophilic monomer, and this is obtained by polymerizing a mixture obtained by dissolving a polyimide silicone resin in a hydrophilic monomer solution.

  The hydrophilic monomer used in the present invention is not particularly limited, but nitrogen atom-containing monomers such as N-vinylpyrrolidone, N, N-dimethylacrylamide, and N-methyl-3-methylidenepyrrolidone, methacrylic acid, hydroxyethyl ( And (meth) acrylate. Among these, from the viewpoint of suppression of white turbidity due to suppression of the phase separation structure during polymerization, a nitrogen atom-containing monomer is preferable, and N-vinylpyrrolidone, N, N-dimethylacrylamide and N-methyl-3-methylidenepyrrolidone are more preferable. . In particular, N-vinylpyrrolidone is preferable. Two or more of these hydrophilic monomers can be used in combination. Here, N-methyl-3-methylidenepyrrolidone is represented by the following structural formula.

  In the present invention, the ratio between the polyimide silicone resin and the hydrophilic polymer is preferably 10:90 to 40:60, and more preferably 20:80 to 30:70, by weight. If the polyimide silicone resin is less than 10% by weight and the hydrophilic polymer exceeds 90% by weight, the effect of the present invention by the polyimide silicone resin cannot be obtained, and the shape retention of the transparent gel is poor and flattened. As an ophthalmic lens, it tends to be difficult to wear. In addition, when the polyimide silicone resin exceeds 40% by weight and the hydrophilic polymer is less than 60% by weight, the viscosity of the mixed solution becomes high and not only the polymerizability is lowered but also transparency and oxygen permeability can be satisfied. , Tend to harden.

  In the present invention, since the polyimide silicone resin does not have a polymerizable group, volume shrinkage that occurs during polymerization can be suppressed. Therefore, it can polymerize well even within the resin mold. In the polymerization, a known polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator is used.

  A cross-linking agent may be included in the mixture obtained by dissolving the polyimide silicone resin in the hydrophilic monomer in order to impart a reinforcing effect. Although a known crosslinking agent is used, allyl methacrylate and / or diethylene glycol diallyl ether are preferable, and allyl methacrylate is particularly preferable because it has an effect of improving the transparency of the obtained material. When the crosslinking agent is blended, it is preferably 0.1 to 10% by weight of the total mixture, more preferably 0.1 to 5% by weight or less, and 0.2 to 0.6% by weight. More preferably. If the blending amount of the cross-linking agent is less than 0.1% by weight of the total mixture, the shape retention of the transparent gel is poor and flattened, so that it tends to be difficult to wear as an ophthalmic lens such as CL. . On the other hand, if it exceeds 10% by weight, the shape retainability is high, but it is cloudy and rigid, so that it tends to be inferior in wearing feeling as an ophthalmic lens such as CL.

  Moreover, you may further mix | blend another silicone containing monomer and solvent with a mixture. Examples of the solvent include tetrahydrofuran, isopropanol, acetone, hexane and the like.

In producing the transparent gel of the present invention, it is preferable that the gel is highly purified as in the conventional electronics and optical fields. Specifically, dust having a diameter of 50 μm or more is substantially not detected, dust having a diameter of 0.5 to 50 μm is 3 × 10 ⁴ or less, inorganic and organic residual chlorine is 2 ppm or less, residual alkali metal is 2 ppm or less, residual hydroxyl group Is 200 ppm or less, the amount of residual nitrogen is 5 ppm or less, and the residual monomer is 20 ppm or less. In addition, post-treatment such as extraction may be performed for the purpose of removing low molecular weight substances or removing solvents. Moreover, it is preferable to use the material which reduced impurities, isomers, etc. as much as possible about the raw material of a polyimide silicone resin.

  When producing the transparent gel of the present invention, a hindered phenol-based or phosphite-based antioxidant; silicon-based, fatty acid ester-based, fatty acid-based, if necessary, to ensure stability and releasability , Fatty acid glycerides, beeswax and other natural oils and mold release agents; benzotriazole, benzophenone, dibenzoylmethane, salicylate, and other light stabilizers; polyalkylene glycol, fatty acid glycerides, and other antistatic agents Etc. may be added as appropriate.

Furthermore, for the purpose of cost reduction, strength, heat resistance, etc., conventional polyimide silicone resins can be arbitrarily mixed and used as long as the performance of the transparent gel is not impaired. In addition to satisfying the physical properties as the molding material described above, in CL, in order to obtain a clear visual acuity, specifically, the birefringence of 30 ° obliquely incident light is preferably 50 nm or less, more preferably 25 nm or less. The visible light transmittance of the transparent gel is preferably at least 80% or more, more preferably 90% or more. In order to provide safe CL wear, the transparent gel has an oxygen permeability coefficient (Dk value) of 50 × 10 ⁻¹¹ (cm ² / sec) · (mLO ₂ / (mL · mmHg)) or more, and continuous wear is required. In order to carry out, it is further desirable that it is 70 × 10 ⁻¹¹ (cm ² / sec) · (mLO ₂ / (mL · mmHg)) or more.

  When CL is obtained from the transparent gel of the present invention, the transparent gel is formed into button-shaped lens blanks having an outer diameter of 10 to 15 mm and a thickness of 2 to 5 mm, and this is formed by conventional methods such as cutting or optical processing such as laser. It can be manufactured by processing into a lens. Since the transparent gel of the present invention is excellent in moldability and has a small birefringence, it can be formed into a molded product close to a lens shape. At this time, a brim portion for holding for processing may be provided around the periphery. In either case, it is necessary to suppress the molding distortion as much as possible, and to form a molded product shape in which the portion where the distortion exists is not used as CL.

  In order to improve the wettability of the surface of the transparent gel, plasma treatment or glow discharge treatment can also be performed under atmospheric pressure or reduced pressure. Further, graft polymerization may be performed.

  Since the transparent gel of the present invention is excellent in properties such as gel strength, transparency and oxygen permeability, culture substrates such as cells and organs, containers for use in storage, and ophthalmic lens materials (for example, CL materials, (Intraocular lens material, corneal inlay material) and the like.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The polyimide silicone resin (PISi) used in Examples 1 to 13 was synthesized as follows.

Synthesis Example 1 (Synthesis of PISiA)
In a flask equipped with a stirrer, thermometer and nitrogen displacement apparatus, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] 30.0 g (0.1 mol) of furan-1,3-dione and 250 g of N, N-dimethylacetamide were charged and dissolved by stirring. Next, 7.4 g (0.018 mol) of 2.2-bis [4- (4-aminophenoxy) phenyl] propane was added to the flask, and the temperature of the reaction system was maintained at 50 ° C. for 3 hours. Further, 74.0 g (0.082 mol) of diaminosiloxane (average of a is 10) was added dropwise at room temperature. After completion of dropping, the mixture was stirred at room temperature for 12 hours.

  Next, after attaching a reflux condenser with a moisture receiver to the flask, 20.4 g of acetic anhydride and 26.4 g of pyridine were added, the temperature was raised to 50 ° C., and the temperature was maintained for 3 hours.

The obtained solution was poured into methanol as a poor solvent to reprecipitate the resin. When the infrared absorption spectrum of this resin was measured, the absorption based on the polyamic acid which shows that there existed an unreacted functional group did not appear, but the absorption based on an imide group was confirmed at 1770 cm < ^-1 > and 1710 cm < ^-1 >.

  Moreover, it was 31000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent. This resin was dissolved in methyl isobutyl ketone, applied onto a glass substrate, and dried to prepare a film having a thickness of 50 μm. When the light transmittance of this film was measured, the light transmittance at a wavelength of 400 to 700 nm was 80% or more.

Synthesis Example 2 (Synthesis of PISiB)
In a flask equipped with a stirrer, thermometer and nitrogen displacement apparatus, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] 30.0 g (0.1 mol) of furan-1,3-dione and 250 g of N, N-dimethylacetamide were charged and dissolved by stirring. Then, 14.4 g (0.035 mol) of 2.2-bis [4- (4-aminophenoxy) phenyl] propane was added into the flask, and the temperature of the reaction system was maintained at 50 ° C. for 3 hours. Furthermore, 82.4 g (0.065 mol) of diaminosiloxane (average of a is 15) was added dropwise at room temperature. After completion of dropping, the mixture was stirred at room temperature for 12 hours.

  Next, after attaching a reflux condenser with a moisture receiver to the flask, 20.4 g of acetic anhydride and 26.4 g of pyridine were added, the temperature was raised to 50 ° C., and the temperature was maintained for 3 hours.

The obtained solution was poured into methanol as a poor solvent to reprecipitate the resin. When the infrared absorption spectrum of this resin was measured, the absorption based on the polyamic acid which shows that there existed an unreacted functional group did not appear, but the absorption based on an imide group was confirmed at 1770 cm < ^-1 > and 1710 cm < ^-1 >.

  Moreover, it was 40000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent. This resin was dissolved in methyl isobutyl ketone, applied onto a glass substrate, and dried to prepare a film having a thickness of 50 μm. When the light transmittance of this film was measured, the light transmittance at a wavelength of 400 to 700 nm was 80% or more.

Examples 1-12 and Comparative Examples 1-3
The components shown in Table 1 were injected into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens having a diameter of about 14 mm and a center thickness of 0.1 mm). Next, the mold was irradiated with UV light for photopolymerization to obtain a contact lens-shaped polymer. The following evaluation was performed about the obtained polymer. The results are shown in Table 1.

(Visible light transmittance (% T))
After the prepared lens was conditioned in physiological saline, the light transmittance in a wavelength range of 380 to 780 nm was measured using an ultraviolet-visible spectrophotometer UV3150 manufactured by Shimadzu Corporation.

(Moisture content)
After hydrating the gel, the water on the surface was gently wiped and the weight was measured (W1: g). The gel was put into a dryer set at 105 ° C. for 16 hours, and then the gel was dried after cooling to room temperature in a desiccator (W2: g). The water content was calculated by the following formula.
(W1-W2) / W1 × 100 (%)

(Oxygen permeability coefficient (Dk))
Dk of the lens produced by the electrode method was measured. The unit of measurement is × 10 ^-11 (cm ² / sec) · (mLO ₂ / (mL · mmHg)).

(Refractive index)
About the produced lens, the Abbe refractometer (1-T) made from Atago Co., Ltd. was used, and the refractive index (Na-D line) in 20 degreeC was measured.

(appearance)
The appearance of the produced lens on the fingertip was confirmed visually.
◎: Completely transparent ○: Almost transparent △: Some cloudiness is observed ×: Cloudy and opaque

(Shape retention)
The shape retention on the fingertip of the produced lens was confirmed visually.
◎: The shape is completely maintained. ○: The shape is substantially maintained. △: The shape is slightly flat. ×: It is flat and difficult to wear.

In addition, the abbreviation in Tables 1-3 shows the following compounds.
PISi: polyimide silicone resin PIA: polyimide resin NVP: N-vinylpyrrolidone HEMA: hydroxyethyl methacrylate DMAA: dimethylacrylamide MMA: methyl methacrylate TRIAM: diethylene glycol diallyl ether AMA: allyl methacrylate EDMA: ethylene glycol dimethacrylate 1173: Darocur 1173 (manufactured by Ciba Specialty Chemicals)
V-65: 2,2′-azobis (2,4-dimethylvalerotonyl)

Example 13 and Comparative Examples 4 and 5
A contact lens-shaped polymer was obtained in the same manner as in Example 1 except that the components shown in Table 2 were used. The color of the obtained polymer was confirmed visually. The results are shown in Table 2. The PIA used in Comparative Examples 4 and 5 is a polyimide resin having a repeating structure shown below and having a weight average molecular weight of 1.2 × 10 ⁴ .

Examples 14 and 15
After adding the cross-linking agent (AMA) and initiator (D. 1173) in the blending ratio (wt%) described in Tables 3 and 4 to the PISi / NVP (= 20/80) mixture, Example 1 and A contact lens-shaped polymer was obtained in the same manner. The appearance and shape retention of the resulting polymer were evaluated according to the methods described above. The results are shown in Tables 3 and 4.

  It can be seen that the transparent gel according to the present invention is excellent in light transmittance, Dk value, refractive index, and shape retention. In contrast, when a polyimide other than the polyimide silicone resin is used as in Comparative Examples 4 and 5, it is colored yellow and is not suitable for a transparent gel.

  Furthermore, it can be seen from Examples 14 and 15 that the transparency varies depending on the amounts of the crosslinking agent and the initiator, and the transparency is particularly excellent when the blending amount of the crosslinking agent is 0.2 to 0.6% by weight. When the cross-linking agent is 0.7% by weight or more, for example, it tends to become cloudy (appearance: Δ) and shape retention is high (shape retention:）). Tend to be less wearable.

Claims (12)

Visible light transmittance in the form of a film having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (3), soluble in an organic solvent, and having a film thickness of 10 μm (% T) is a transparent polyimide silicone resin is 80% or more, made of hydrophilic polymer obtained by polymerizing a hydrophilic monomer, have a mutual network of transparent polyimide silicone resin and a hydrophilic polymer, the film thickness 10μm film A transparent gel having a visible light transmittance (% T) of 80% or more in shape .

[Where X is

Z is a diamine residue represented by the general formula (2)

(In the formula, R ^{9 to} R ¹² are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, and these may be the same or different. A is an integer of 1 to 100. )]

[Where X is

Y is at least one selected from diamine residues represented by the general formula (6)

] The diamine residue represented by the general formula (2) is 5 to 95 mol% with respect to the total diamine residues, and the diamine residue represented by the general formula (6) is 5 to 95 mol%. The transparent gel according to claim 1 . The transparent gel according to claim 1, wherein the hydrophilic monomer is a nitrogen atom-containing monomer. The transparent gel according to claim 3, wherein the nitrogen atom-containing monomer is N-vinylpyrrolidone, N, N-dimethylacrylamide and / or N-methyl-3-methylidenepyrrolidone. The transparent gel according to claim 1, wherein a in the general formula (2) is 5 to 80. The transparent gel according to claim 1, wherein the ratio of the transparent polyimide silicone resin to the hydrophilic polymer is 10:90 to 40:60 by weight. Visible light transmittance in a film shape having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (3), soluble in an organic solvent, and having a film thickness of 10 μm. Visible light transmittance (% T) in a film shape having a film thickness of 10 μm, including a step of polymerizing a hydrophilic monomer after dissolving a transparent polyimide silicone resin having a (% T) of 80% or more in a hydrophilic monomer solution Is a method for producing a transparent gel having 80% or more.

[Where X is

Z is a diamine residue represented by the general formula (2)

(In the formula, R ^{9 to} R ¹² are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, and these may be the same or different. A is an integer of 1 to 100. )]

[Where X is

Y is at least one selected from diamine residues represented by the general formula (6)

] The method for producing a transparent gel according to claim 7, further comprising a step of adding a crosslinking agent when the transparent polyimide silicone resin is dissolved in the hydrophilic monomer solution. The method for producing a transparent gel according to claim 8, wherein the crosslinking agent is allyl methacrylate or diethylene glycol diallyl ether. The method for producing a transparent gel according to claim 8 or 9, wherein the amount of the crosslinking agent is 0.1 to 10% by weight in the total mixture. The manufacturing method of the transparent gel as described in any one of Claims 7-10 with which the said superposition | polymerization is performed within a type | mold. The ophthalmic lens material which consists of a transparent gel as described in any one of Claims 1-6.