JP4846355B2 - Resin mold - Google Patents

Description

  The present invention relates to a resin mold suitable for producing a cast polymerization product having excellent surface water wettability of a product and excellent mold releasability.

  Since medical devices such as intraocular lenses and contact lenses are required to have surface hydrophilicity, particularly water wettability, they are manufactured by molding in a polypropylene resin mold and then manufacturing the surface of the product to make it hydrophilic. For example, Japanese Patent Application Laid-Open No. 11-502949 discloses an ophthalmic lens in which the surface characteristics are improved by performing cast polymerization in a polypropylene resin mold and then subjecting the surface to plasma polymerization. As a method for producing a contact lens having excellent surface water wettability without performing these surface treatments, a resin having a contact angle of 65 to 80 degrees in WO application JP00 / 08912, which is insoluble in a monomer, For example, there is a description of manufacturing with a resin mold selected from polyamide, polyethylene terephthalate, and ethylene vinyl alcohol copolymer. Japanese Patent Application Laid-Open No. 9-183132 describes a mold obtained by adding a wax-like additive, an adhesion reducing agent such as an antistatic agent, and a wetting improver to a polyolefin resin.

  However, the method of surface treatment after molding a lens requires that the front and back of the lens be uniformly treated, requiring large equipment and strict production process management, resulting in high manufacturing costs. Furthermore, these surface-treated lenses have a problem that the water wettability of the surface easily changes with time. On the other hand, when manufacturing with a resin mold selected from polyamide, polyethylene terephthalate, and ethylene vinyl alcohol copolymer, a special method is required for mold release due to high adhesion between the mold and the product, or resin injection molding. There is a problem that the property is unstable and is insufficient for industrial production. In addition, in the method of adding an additive such as a waxy additive or a low molecular weight antistatic agent to the polyolefin resin in order to prevent adhesion to the mold and improve the wettability of the lens, these additives remain in the lens. On the other hand, when these additives are eluted from the lens, there is a problem that the performance is lowered.

  In order to solve the above-mentioned problems, the present inventors have studied the materials of molds for cast polymerization of medical devices, particularly intraocular lenses and contact lenses that require surface water wettability. It was found that the object can be achieved by using the material of the present invention, and the present invention was completed. That is, the present invention relates to a mold formed from one or more resins selected from a polytrimethylene terephthalate resin, a polytrimethylene terephthalate copolymer resin, and a polymer blend resin containing these as a main component, and a medical treatment using the template The present invention relates to a method for manufacturing an industrial device. Hereinafter, the present invention will be described in detail.

  The resin mold of the present invention is formed from one or more kinds of resins selected from a polytrimethylene terephthalate resin, a polytrimethylene terephthalate copolymer resin, and a polymer blend resin containing these as a main component.

  Polytrimethylene terephthalate and its copolymer (hereinafter abbreviated as PTT) are polyesters mainly composed of trimethylene glycol and terephthalic acid. For example, JP-A-5-262862, JP-A-8-3111177, 2000-159875 and the like. In addition, methods have been developed to increase the degree of polymerization of PTT, improve moldability, increase thermal stability, and suppress the formation of low molecular weight by-products, and have good thermal stability at a high degree of polymerization. A method for producing PTT is described in JP-T-2002-543227, and a composition having a low molecular weight by-product even when remelted and a method for producing the same are disclosed in JP-A No. 2003-119266 and JP-A No. 2003-155335. Described in JP-A-2003-73462, and a composition having high thermal stability and low generation of low-molecular-weight by-products is disclosed in JP-A-2003-160648. JP-A-2004-269571 and JP-A-2003-342356 have disclosed a production method having a high degree of polymerization, excellent color tone and excellent melt moldability. Open 2005-60528 Patent described in Japanese, a method of suppressing the formation of by-products of low molecular weight have been described in publications and Kohyo 2005-520897 Patent JP-T-2005-520896. Further, copolymers of polytrimethylene terephthalate are disclosed in JP-T-2002-543227, column 0036 and 0039, JP-A-2003-73462, column 0014, JP-A-2003-119266, column 0012, and JP-A-2003-155335. Columns 0010 to 0011, JP 2003-160648 A column 0012 to 0013, JP 2003-342356 A column 0017, JP 2004-189977 A column 0009 to 0011, JP 2005-60528 A column 0013, etc. Are listed.

  For example, copolymer monomers of polytrimethylene terephthalate include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2′- Fragrances such as dicarboxylic acid, biphenyl-3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, bis (4,4′-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid Salts such as aliphatic dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 3,5-dicarboxylic acid benzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxylic acid benzenesulfonic acid tributylmethylphosphonium salt, 1 , 4-cyclohexane Aliphatic dicarboxylic acids such as carboxylic acid, 4,4′-dicyclohexyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dimer acid and their ester derivatives, and ethylene glycol, tetramethylene glycol 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanediol, cyclohexanedimethanol, 4,4′-dicyclohexylhydroxymethane, 4,4′-dicyclohexylhydroxy Examples include, but are not limited to, propane, trioxides such as bisphenol A ethylene oxide addition diol, glycerin, and trimethylolpropane.

  Furthermore, the resin mold of the present invention uses a polymer blend in which other thermoplastic resins such as polyethylene terephthalate and ionomer are melt-kneaded within the range in which the properties of these PTTs are not greatly changed, for example, in the range of 5 to 30% by weight. Is possible. PTT is commercially available from Sun Delta, Inc., trade name: Sanvislon, Shell Chemicals, trade name: Cortera. Of these, Sanbislon A0120 is preferable because of its excellent injection moldability.

  The reason why the medical device manufactured using the resin mold of the present invention, for example, the contact lens surface is excellent in water wettability and peelability from the mold is not clearly understood, but the chemical composition of the mold surface, molecular structure It is presumed that the chemical structure of the surface of the obtained medical device is made to have a good water wettability and mold releasability due to the interaction between the crystal structure and the monomer for the medical device.

  The resin used for the resin mold of the present invention may be appropriately added with a heat stabilizer, an antioxidant, an antistatic agent, a crystal nucleating agent, a lubricant, a release agent, a pigment, a filler, a reinforcing agent and the like depending on the purpose. I can do it.

  The resin mold of the present invention can be used in various forms of molds depending on the purpose, for example, Japanese Patent Laid-Open Nos. 52-117647, 62-297120, and 9-183132. Or a material for producing a contact lens by one-sided or double-sided cutting as exemplified in JP-A-63-3910 and JP-A-8-505095. It can be used for a polymerization type for polymerization, a mold for polymerizing an intraocular lens exemplified in JP-T-2005-528176.

  The medical device manufactured using the resin mold of the present invention requires that the surface of the product is compatible with water, and is used for artificial heart, artificial heart valve, implantable pacemaker, blood circuit, eye There are inner lenses, contact lenses, catheter guides, etc. In particular, the hydrophilicity and water wettability of the surface of contact lenses are important in preventing dirt adhesion, maintaining visual function, preventing infections, improving wearing comfort, and the like.

  Examples of the contact lens manufactured using the resin mold of the present invention include a hydrous soft contact lens mainly composed of hydroxymethacrylate, n-vinylpyrrolidone and the like, and a silicon hydrous soft contact lens copolymerized with a silicon-containing monomer. included. Examples of the silicon-containing water-containing soft contact lens include a polymer mainly composed of a polysiloxane macromer and a hydrophilic monomer, wherein the polysiloxane macromer is 70 to 30% by weight and the total of the hydrophilic monomers is 30 to 70% by weight. There is a lens consisting of More specifically, as the polysiloxane macromer, a silicon-based macromer having a polymerizable unsaturated group at the molecular terminal, a perfluoro-modified macromer thereof, or a silicon-based macromer such as a polyalkylene glycol-modified macromer can be used. Specific examples thereof include JP-A-3-240021, JP-A-3-257420, JP-A-4-50814, Japanese Patent Application 3-202106, Japanese Patent Application 3-33026, and WO Application JP00 / 08912. It is described in.

  Among these, the hydrophilic polysiloxane macromer represented by the following formula (1) is particularly preferable because of excellent balance of characteristics such as surface water wettability, oxygen permeability, mechanical strength, and elastic modulus.

［ここで、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ炭素数１〜１２の炭化水素基またはトリメチルシロキシ基から選ばれた基であり；Ｘは式（２）で表される重合性置換基であり；

[Wherein R ¹ , R ² , R ³ , R ⁴ are each a group selected from a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group; X is a polymerizable group represented by the formula (2) A substituent;

（Ｒ^５は水素またはメチル基、Ｚ^１は−ＮＨＣＯＯ−、−ＮＨＣＯＮＨ−、
−ＯＣＯＮＨ−Ｒ^６−ＮＨＣＯＯ−、−ＮＨＣＯＮＨ−Ｒ^７−ＮＨＣＯＮＨ−
および−ＯＣＯＮＨ−Ｒ^８−ＮＨＣＯＮＨ−から選ばれた基（Ｒ^６、Ｒ^７、Ｒ^８は炭素数２〜１３の炭化水素基）であり、ｍは０〜１０、ｎは３〜１０、
ｐはｍが０のとき０であり、ｍが１以上のとき１である。ｑは０〜２０の整数である。）

(R ⁵ is hydrogen or a methyl group, Z ¹ is —NHCOO—, —NHCONH—,
^{-OCONH-R 6 -NHCOO -, -} NHCONH-R 7 -NHCONH-
And —OCONH—R ⁸ —NHCONH— (R ⁶ , R ⁷ , R ⁸ are hydrocarbon groups having 2 to 13 carbon atoms), m is 0 to 10, n is 3 to 10,
p is 0 when m is 0, and 1 when m is 1 or more. q is an integer of 0-20. )

Structure Y is formed by combining structural units [I] and [II] represented by the following formula:
The ratio of the number of bonds between the structural units [I] and [II] is [I] / [II] = 0.1 to 200
The total number of [I] and [II] is 10 to 1000.

（ここで、Ｒ^９及びＲ^１０はそれぞれ炭素数１〜１２の炭化水素基、炭素数１〜１２のフッ素置換炭化水素基およびトリメチルシロキシ基から選択された基であって、同一でも異なっていてもよい。Ｒ^１１およびＲ^１２はそれぞれ炭素数１〜１２の炭化水素基、トリメチルシロキシ基または親水性置換基からなる基であって、Ｒ^１１またはＲ^１２の少なくとも一方は親水性置換基である。ここでいう親水性置換基とは水酸基またはオキシアルキレン基から選ばれた置換基が少なくとも１個結合してなる鎖状または環状の炭化水素基である。）]

(Here, R ⁹ and R ¹⁰ are groups selected from a hydrocarbon group having 1 to 12 carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 12 carbon atoms, and a trimethylsiloxy group, and they may be the same or different. R ¹¹ and R ¹² are each a group consisting of a hydrocarbon group having 1 to 12 carbon atoms, a trimethylsiloxy group or a hydrophilic substituent, and at least one of R ¹¹ or R ¹² is a hydrophilic substituent. Here, the hydrophilic substituent is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group or an oxyalkylene group.]]

Here, the structural unit [I] of the hydrophilic polysiloxane macromer is such that R ⁹ and R ¹⁰ are only hydrocarbon groups [Ia], at least one is a trimethylsiloxy group [Ib], and at least one is fluorine-substituted carbonized It may be a hydrogen group [Ic] or a structure containing two or more selected from these, and the structural units [I] and [II] are connected in block form , Randomly bonded ones, or a mixture of them may be included. The hydrophilic substituent in the structural unit [II] of the polysiloxane macromer is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group and an oxyalkylene group. ) Or a group represented by the formula (4) is preferable.

（ここでＲ^１３は炭素数３〜１２の炭化水素基であって、炭素炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−からなる基を挟んでいてもよく、ＯＨ基は同一炭素原子上には１個のみ置換され、ａは１よりも大きい数である）

(Here, R ¹³ is a hydrocarbon group having 3 to 12 carbon atoms, and a group consisting of —O—, —CO—, and —COO— may be sandwiched between carbon and carbon atoms, and the OH group is the same carbon atom. Only one is substituted above, and a is a number greater than 1)

（ここで、Ｒ^１４は炭素数３〜１２の炭化水素基であって、炭素炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−からなる基を挟んでいてもよい。Ｒ^１５は炭素数２〜４の炭化水素であって、ｂが２以上の場合、異なる炭素数であっても良い。ｂは１〜２００であり、Ｚ^２は水素原子、炭素数１〜１２の炭化水素または−ＯＣＯＲ^１６（Ｒ^１６は炭素数１〜１２の炭化水素基）から選ばれた基を示す）

(Here, R ¹⁴ is a hydrocarbon group having 3 to 12 carbon atoms, and a group consisting of —O—, —CO—, and —COO— may be sandwiched between carbon and carbon atoms. R ¹⁵ is carbon number. 2 to 4 hydrocarbons, and when b is 2 or more, they may have different carbon numbers, b is 1 to 200, Z ² is a hydrogen atom, a hydrocarbon having 1 to 12 carbon atoms, or- OCOR ¹⁶ (R ¹⁶ represents a group selected from hydrocarbon groups having 1 to 12 carbon atoms)

More preferably the hydrophilic _{group, -C 3 H 6 OH, -C} 8 H 16 OH, -C 3 H 6 OC 2 H 4 OH, -C 3 H 6 OCH 2 CH (OH) CH 3, -C 2 _{H 4 COOC 2 H 4 OH,} -C 2 H 4 COOCH 2 CH (OH) 1 monohydric alcohol substituent, such as _{C 2 H 5, -C 3 H} 6 OCH 2 CH (OH) CH 2 OH, -C 2 H _{4 COOCH 2 CH (OH) CH} 2 OH, -C 3 H 6 OCH 2 C (CH 2 OH) 3 polyhydric alcohol substituent, such _{as, -C 3 H 6 (OC 2} H 4) 4 OH, -C 3 _{H 6 (OC 2 H 4)} 3 0OH, -C 3 H 6 (OC 2 H 4) 10 OCH 3, -C 3 H 6 (OC 2 H 4) 10 - (OC 3 H 6) 10 OC 4 H 9 Selected from polyoxyalkylene groups such as . Among these, alcohol substituents such as —C ₃ H ₆ OH, —C ₃ H ₆ OCH ₂ CH (OH) CH ₂ OH, —C ₃ H ₆ OC ₂ H ₄ OH, —C ₃ H ₆ ( _{OC 2 H 4) c OH-} C 3 H 6 (OC 2 H 4) d OCH 3 (c, d is 2 to 40 out) as hydrophilic polyoxyethylene groups, such as, oxygen permeability of the balance It is excellent in that it is taken.

The fluorine-substituted hydrocarbon group as R ⁹ or R ¹⁰ imparts contamination resistance to the material. However, when too many fluorine atoms are present, the hydrophilicity is lowered. Therefore, 40 to 85% of hydrocarbon hydrogen atoms are converted to fluorine atoms. Substituted substituents having 1 to 12 carbon atoms are preferable, for example, 3,3,3-trifluoropropyl group, 1,1,2,2-tetrahydroperfluorooctyl group, 1,1,2,2-tetrahydroper There are fluorodecyl groups and the like, and among these, 3,3,3-trifluoropropyl group is preferable in terms of excellent balance between hydrophilicity and oxygen permeability. In addition to the hydrophilic substituent and the fluorine-substituted hydrocarbon group, R ⁹ or R ¹⁰ may be bonded to an Si atom or R ¹¹ or R ¹² may be bonded to an Si atom as a substituent having 1 to 1 carbon atoms. 12 hydrocarbon groups or trimethylsiloxy groups, which may be the same as or different from each other, preferably an alkyl group having 1 to 3 carbon atoms, which has high flexibility and good oxygen permeability. The group is particularly preferred.

  The ratio of the siloxane structural unit [I] and the siloxane structural unit [II] to which the hydrophilic substituent is bonded is 0.1 to 200 in terms of [I] / [II], and the ratio of the siloxane structural unit [I] is small. While the flexibility and oxygen permeability of the siloxane chain are reduced, if the hydrophilic substituent is too small, the hydrophilicity is reduced and the surface wettability is deteriorated. Furthermore, the total number of the siloxane structural units [I] and [II] is preferably 10 to 1000, more preferably 20 to 500. When the polysiloxane chain is short, the flexibility and oxygen permeability of the polymer are lowered. On the other hand, if the siloxane chain is too long, the viscosity of the monomer itself is remarkably increased, making it difficult to produce and handle the monomer, and decreasing the polymerizability.

The polymerizable substituent (X) containing a polymerizable unsaturated part is bonded to the terminal of the siloxane chain, and the structure of the unsaturated part is preferably an acrylate group or a methacrylate group from the viewpoint of polymerizability. The unsaturated moiety may be bonded to a linking moiety group with an Si atom via a hydrocarbon bridge having 0 to 10 carbon atoms. As the linking moiety group with the Si atom, a hydrocarbon group containing a urethane bond or a urea bond is preferable, and the urethane bond or urea bond (Z ¹ ) is further bonded to a hydrocarbon via an oxyethylene group and contained therein. It may be. Urethane bonds and urea bonds are highly polar, increasing the hydrophilicity of the polymer and increasing the strength. Two urethane bonds or urea bonds may be present as a linking moiety group with an Si atom. For example, —OCONH—R ⁶ —NHCOO—, —NHCONH—R ⁷ —NHCONH— and —OCONH—R ⁸ —NHCONH— (wherein R ⁶ , R ⁷ and R ⁸ are hydrocarbon groups having 2 to 13 carbon atoms) are exemplified. it can. These structures are introduced by a reaction with a diisocyanate compound, and both isocyanates can be connected to each other by a hydrocarbon group having 2 to 13 carbon atoms, and the hydrocarbon group is a chain, cyclic or aromatized hydrocarbon. It may be a group. More preferred is an aliphatic hydrocarbon group having good light resistance. Examples of diisocyanate compounds that can be used include trimethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate, and the like.

  3 to 10 hydrocarbons in a hydrocarbon group containing a urethane bond or a urea bond, that is, a urethane bond or a urea bond to which a urethane bond or a urea bond may be bonded via an oxyethylene group in a connecting partial group with an Si atom. Of carbon atoms may be included.

  There are various methods for synthesizing the hydrophilic polysiloxane macromer disclosed in the present invention. For example, a cyclic siloxane having hydrosilane (Si-H), a cyclic siloxane having a hydrocarbon group, and a disiloxane having a hydroxyalkyl group at both ends, In some cases, a mixture containing a cyclic siloxane having a fluorine-substituted hydrocarbon group is subjected to ring-opening polymerization using an acidic catalyst such as sulfuric acid, trifluoromethanesulfonic acid, acidic clay, etc. A compound is obtained. In this case, siloxane compounds having different degrees of polymerization and introduction ratios of fluorine substituents and hydrosilyl groups can be obtained by changing the charging ratio of each cyclic siloxane and disiloxane compound. Next, an isocyanate group-containing acrylate or an isocyanate group-containing methacrylate is reacted with a hydroxyl group at the siloxane end to obtain a hydrosilane-containing fluorine-containing siloxane compound having a polymerizable substituent at both ends. Here, examples of the isocyanate group-containing methacrylate compound include methacryloxyethyl isocyanate, methacryloyl isocyanate, etc., and further obtained by reacting a hydroxyl group-containing acrylate such as hydroxyethyl methacrylate or hydroxybutyl acrylate or a hydroxyl group-containing methacrylate with various diisocyanate compounds. An acrylate group or methacrylate group-containing isocyanate compound can also be used. Next, a hydrophilic polysiloxane macromer can be obtained by utilizing a so-called hydrosilylation reaction in which a hydrophilic compound having an unsaturated hydrocarbon group is subjected to an addition reaction with hydrosilane using a transition metal catalyst such as chloroplatinic acid. Here, in the hydrosilylation reaction, if an active hydrogen compound such as a hydroxyl group or carboxylic acid is present, it is known to cause a dehydrogenation reaction as a side reaction, and the active hydrogen is protected in advance or a buffer agent is added, Methods for suppressing side reactions are described, for example, in US Pat. No. 3,907,851 and JP-A-62-195389. As another synthesis route, after synthesizing a hydrosilyl group-containing polysiloxane compound having hydroxyl groups at both ends, a hydrophilic compound is first introduced by hydrosilylation, and then reacted with an isocyanate group-containing methacrylate, etc. There is also a method of introducing a polymerizable substituent. Also in this case, there is known a method for preventing a reaction with an isocyanate by introducing a protective group when an active hydrogen capable of reacting with an isocyanate is present in the hydrophilic compound. Further, in place of the cyclic siloxane, a silicate derivative such as a dimethoxysilane compound or a diethoxysilane compound can be used as a starting material. Two or more kinds of hydrophilic polysiloxane macromers obtained in this manner can be mixed and used.

  Specific examples of these hydrophilic polysiloxane macromers include the following.

ここで、Ｙ：

Where Y:

若しくは、式（５）において、Ｙ：

Or in Formula (5), Y:

または、

Or

ここで、Ｙ：

Where Y:

または、

Or

ここで、Ｙ：

Where Y:

または、

Or

ここで、Ｙ：

Where Y:

若しくは、式（９）において、Ｙ：

Or in Formula (9), Y:

または、

Or

ここで、Ｙ：

Where Y:

  For medical devices, particularly contact lenses, at least one selected from the above polysiloxane macromers is used in an amount of 70 to 30% by weight, and hydrophilic monomers are used in an amount of 30 to 70% by weight. The polysiloxane macromer is 65 to 40% by weight. %, And a total of 35 to 60% by weight of the hydrophilic monomers is preferable because the above properties are balanced.

  If the polysiloxane macromer is less than 30% by weight, the required oxygen permeability cannot be obtained, which is not preferable. If the hydrophilic monomer is less than 30% by weight, the required water wettability is lowered, and if it exceeds 70% by weight, the oxygen permeability is lowered.

  Hydrophilic monomers that can be used in the present invention include (meth) acrylates containing hydroxy groups such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, glyceryl methacrylate, N-vinyl-N- Methylacetamide, N-vinylacetamide, N-vinylformamide, acrylamide, N-methylacrylamide, N-methylolacrylamide, 2-vinylpyridine, N-methylitaconimide, N-vinylpyrrolidone, N, N-dimethylacrylamide, Contains N atoms such as N-vinylimidazole, N-octadecylacrylamide, 1-vinyl-2-methylimidazole, N-vinylcarbazole, N-vinyloxazolidone, N-vinylsuccinimide Preferably 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-vinyl-N-methyl from the standpoint of solubility with polysiloxane macromer, balance of physical properties of the obtained polymer, etc. One or more selected from acetamide, N-vinylacetamide, N-vinylformamide, acrylamide, N-methylacrylamide, N-vinylpyrrolidone, and N, N-dimethylacrylamide are used.

  The above contact lens can use a copolymerizable monomer for the purpose of maintaining its practical performance. The composition is not limited, but for example, acrylic monomers such as methyl acrylate, ethyl acrylate and acrylic acid, methacrylic monomers such as methyl methacrylate and ethyl methacrylate, tris (trimethylsiloxy) silylpropyl methacrylate, bis Silicon monomers such as (trimethylsiloxy) methylsilylpropyl methacrylate, pentamethyldisiloxanepropyl methacrylate, tris (trimethylsiloxy) silylpropyloxyethyl methacrylate, tris (polydimethylsiloxy) silylpropyl methacrylate, siloxanyl group and meta Those having a hydrophilic group such as urethane bond, glyceryl group, polyalkylene glycol group between acrylate groups, or part of siloxanyl group Fluorosilicone monomers such as hydrophilic siloxanyl methacrylate substituted with terminal hydroxy group or polyalkylene glycol group, tris (dimethyltrifluoropropylsiloxy) silylpropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, Perfluoroalkyl monomers such as 2,2,3,3,3-pentafluoropropyl methacrylate and hexafluoroisopropyl methacrylate and hydroxyl groups such as 1,1,2,2-tetrafluoroethoxy-2-hydroxypropyl methacrylate Fluoroalkyl and fluoroalkyl ether monomers, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetramethyldisiloxane bis (propyl methacrylate) Over G) is a copolymer of such copolymerizable compounds crosslinking monomers, such as.

  The contact lens is produced from a polymer obtained by adding a polymerization initiator that initiates polymerization by heat, UV, electron beam, radiation, or the like to a mixture selected from the monomer and macromer. It is also possible to add additives such as dyes, pigments and UV absorbers depending on the purpose.

In order to control the microstructure and macrostructure of the polymer so as to meet the object of the present invention, the above contact lens is further soluble in a monomer mixture in a mixture selected from the above monomers and macromers, and is made of a lower alcohol or water. Soluble organic solvent can be added in the range of 0.2 to 50% by weight. As these organic solvents, methanol, ethanol, isopropyl alcohol, butyl alcohol, ethylene glycol, ethoxyethanol, glycerin, dimethylacetamide, dimethylformamide, tetrahydrofuran, alkyl phosphate ester, pyrrolidone and the like can be used.

  The above contact lens can be manufactured by a conventional lens manufacturing method except that the mold of the present invention is used. For example, a cast method in which a monomer mixture is injected into a polymerization mold corresponding to the shape of the lens and polymerized. Can be manufactured. It is also possible to further improve the surface characteristics, particularly water wettability, by subjecting the lens surface to ozone treatment and plasma irradiation treatment after production by cast polymerization. For example, as one specific example, it can be produced by adding a polymerization initiator to the mixture containing the polysiloxane macromer and the hydrophilic monomer, and injecting the mixture into the mold of the present invention to heat polymerization.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, it cannot be overemphasized that this invention is not limited by an Example.

  Unless otherwise specified, all numerical values used individually are expressed as significant figures.

(Example)
The evaluation method of the mold in the examples is as follows.

1. Kyowa Interface Science Co., Ltd. is a mold material that is injection-molded under appropriate injection molding conditions based on the technical data of each resin, using a mold that molds a plate-shaped cast polymerization mold with a water contact angle of 1 mm thickness and 40 × 60 mm square. It measured at 23 degreeC using the company make Contact Angle Meter CA-A. Before the measurement, the sample piece is kept in a thermostatic chamber at 23 ° C. for 24 hours in a packaged state with a moisture-proof film, taken out from the package at the time of measurement, and pure water having a diameter of about 1.8 mm is brought into contact with the sample piece with a syringe. The angle formed between the droplet and the sample piece was read and calculated.

  The evaluation method of the cast polymerized sample in the examples is as follows.

2-1. Moisture content After placing the sample piece in purified water and allowing to stand at 37 ° C. for 72 hours, take out the sample piece, quickly wipe off the water adhering to the surface, accurately weigh its weight, and then dry to a constant weight with a vacuum dryer. It was obtained from the weight change.
Water content = (weight change / weight before drying) × 100 (%)

2-2. Water wettability The water wettability was evaluated by observing the maintenance of the water layer on the lens surface when the sample piece was pulled up from the preservation solution.

2-3. Oxygen transmission coefficient (Dk value)
According to the contact lens society standard Dk value measuring method, it measured by the electrode method using the K316 IPI type | mold film oxygen permeation measuring device by the Rika Seiki Co., Ltd. company.
The display of the Dk value was indicated by × 10 ¹¹ (cm ² / sec) · (mlO ₂ / ml × mmHg).

2-4. Tensile elastic modulus A sample having a width of about 3 mm was cut out from the specimen, and a tensile test was performed at a speed of 100 mm / min with a universal testing machine (AGS-50B model, manufactured by Shimadzu Corporation). The value was indicated in dyne / cm ² .

2-5. Protein adhesion A model soil aqueous solution having the following composition was prepared.

  A sample piece having a thickness of about 0.2 mm and a diameter of about 15 mm is placed in 2 ml of this liquid, immersed in a temperature of 37 ° C. for 24 hours, and the sample piece is placed in purified water and shaken for 30 minutes for washing. Remove the sample piece and gently wipe off the surface water.

  The sample piece was immersed in an SDS / sodium carbonate solution at 60 ° C. for 15 hours, the immersion solution was added to a protein analysis reagent (BCA solution) solution, reacted at 60 ° C. for 1 hour, and then a spectrophotometer at UV562 nm (Japan) Spectroscopic Co., Ltd. V-550 type).

  From the separately obtained calibration curve, the amount of attached protein per 1 cm square of the sample piece was determined.

2-6. Lipid Adhesive Phosphate buffer solution of olive oil 0.1% was stirred and mixed, and a sample piece having a thickness of about 0.2 mm and a diameter of about 15 mm was placed and immersed in a constant temperature bath at 40 ° C. for 20 hours. A sample piece was placed in a container containing 5 ml of purified water, shaken for 30 seconds, and this was repeated 5 times for washing.

  The sample piece was vacuum dried, extracted with a chloroform / methanol 2/1 mixed solvent, colored with a triglyceride G test solution, and the absorbance was measured with a spectrophotometer (V-550, manufactured by JASCO Corporation). . From the separately obtained calibration curve, the lipid adhesion amount per 1 cm square of the sample piece was determined.

  A plate-shaped cast polymerization mold was prepared with an injection molding machine using PTT resin (Sun Delta® A0120 manufactured by Sun Delta Co., Ltd.) and stored in a room (25 ° C., 65% RH). The water contact angle of this mold measured before use was 61 degrees.

50 parts by weight of a polydimethylsiloxane macromer having a methacryloxypropyl group at both ends having an average molecular weight of about 6000, 40 parts by weight of hexafluoroisopropyl acrylate, 10 parts by weight of N-butyl acrylate, 5 parts by weight of methacrylic acid, 5 parts by weight of ethylene glycol dimethacrylate 0.12 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added to the monomer mixture of one part, and the mixture was poured into the PTT resin mold obtained in Example 1 and heated at 80 ° C. for 1 hour. And polymerized. The mold immediately after polymerization could be easily peeled off by placing it in water at 70 ° C. for 1 hour, and the polymer sheet could be easily peeled off from the mold. As a result of evaluating the physical properties, the water content was 3%, the Dk value was 226, the water wettability was rank 3, and the adhesion of proteins and lipids was 5 μg / cm square and 50 μg / cm square, respectively. . Moreover, the tensile elastic modulus was 1.2 × 10 ⁷ dyne / cm ² .

  Polydimethylsiloxane having a methyl group-terminated polyethylene glycol group having a polymerization degree of 10 in the molecular side chain and a trifluoropropyl group having both terminal hydroxyethoxypropyl groups having an average molecular weight of about 6000 (in the siloxane skeleton, a polyethylene glycol group-substituted siloxane unit, Hydrophilic siloxanyl macromers were synthesized by reaction of trifluoropropyl group-substituted siloxane units with a content ratio of about 3.9 mol% and 6.4 mol%, respectively, and 2-isocyanatoethyl methacrylate.

Monomer of 55 parts by weight of the above hydrophilic siloxanyl macromer, 15 parts by weight of N-vinylpyrrolidone, 20 parts by weight of N-vinyl-N-methylacetamide, 9 parts by weight of trifluoroethyl methacrylate, and 1 part by weight of ethylene glycol dimethacrylate To the mixture, 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator, and the mixture was poured into a cast polymerization mold made of PTT resin prepared in Example 1 at 80 ° C. And polymerized by heating for 1 hour. The mold immediately after polymerization was easily peeled off by being immersed in water at 70 ° C., and the polymer sheet was also easily peeled off from the mold. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties, the water content was 39%, the Dk value was 125, and the adhesion of protein and lipid was as small as 33 μg / cm 2 and 9 μg / cm 2 respectively. Water wettability was excellent at rank 3. Moreover, the tensile elastic modulus was 1.1 × 10 ⁷ dyne / cm ² .

  Polydimethylsiloxane having both molecular end chain hydroxyethylenepropyl groups having an average molecular weight of about 10,000 having a polyethylene glycol group having a polymerization degree of 7 in the molecular side chain and a trifluoropropyl group (in the siloxane skeleton, a polyethylene glycol group-substituted siloxane unit, Hydrophilic siloxanyl macromers were synthesized by reaction of trifluoropropyl group-substituted siloxane units with a content ratio of about 3.9 mol% and 6.4 mol%, respectively, and 2-isocyanatoethyl methacrylate.

  49 parts by weight of the above hydrophilic siloxanyl macromer, 22 parts by weight of N-vinylpyrrolidone, 11 parts by weight of N-vinyl-formamide, 11 parts by weight of hydroxybutyl methacrylate, 6.7 parts by weight of isobornyl methacrylate, triallyl 30 parts by weight of ethoxyethanol was added to a monomer mixture of 0.7 parts by weight of isocyanurate, and 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator to the monomer mixture. The polymer was poured into a casting polymerization mold made of PTT resin prepared in Example 1, and polymerized by heating at 80 ° C. for 1 hour. The mold immediately after polymerization was peelable, and the polymer sheet was easily peeled from the mold. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties of the obtained water-containing polymer sheet, the water content was 41% and the water wettability was excellent at rank 3. Moreover, the wettability after the water-containing polymer sheet was autoclaved at 121 ° C. for 60 minutes was the same as that before the treatment.

  Polydimethylsiloxane having both molecular weights of about 9 000 having an average molecular weight of about 9000 having a polyethylene glycol group having a polymerization degree of 7 in the molecular side chain and a trifluoropropyl group (in the siloxane skeleton, a polyethylene glycol group-substituted siloxane unit, Hydrophilic siloxanyl macromers were synthesized by reaction of trifluoropropyl group-substituted siloxane units with a content ratio of about 3.9 mol% and 6.4 mol%, respectively, and 2-isocyanatoethyl methacrylate.

  48 parts by weight of the above hydrophilic siloxanyl macromer, 23 parts by weight of N-vinylpyrrolidone, 11 parts by weight of N-vinylformamide, 11 parts by weight of hydroxybutyl methacrylate, 6.8 parts by weight of isobornyl methacrylate, triallyl PTT resin (Sun Delta stock) prepared in Example 1 was prepared by adding 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator to a monomer mixture of 0.7 part by weight of isocyanurate. It was poured into a cast polymerization mold manufactured by Sanvislon ™ A0120) manufactured by the company and polymerized by heating at 80 ° C. for 1 hour. The mold immediately after polymerization was peelable, and the polymer sheet was easily peeled from the mold. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties of the obtained water-containing polymer sheet, the water content was 48% and the water wettability was excellent at rank 3.

(Comparative Example 1)
In Example 2, a cast polymerization mold made of an ethylene vinyl alcohol copolymer (manufactured by Nippon Gosei Kagaku, trade name: Soarite M) was used as a resin mold, and polymerization was carried out by heating at 80 ° C. for 1 hour. After polymerization, the mold could not be easily peeled off, and after being immersed in 90 ° C. hot water, the mold and the sample piece were finally peeled off. The sample piece was swollen with a phosphate buffer contact lens preservation solution to obtain a water-containing polymer sheet. As a result of evaluating the physical properties, the water content was 3%, the Dk value was 225, and the water wettability was rank 3. Moreover, the tensile elastic modulus was 1.3 × 10 ⁷ dyne / cm ² .

(Comparative Example 2)
In Example 2, a cast polymerization mold made of an ethylene vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Soarlite S) was used as a resin mold, and polymerization was carried out by heating at 80 ° C. for 1 hour. After the polymerization, the mold could not be easily peeled off, and after being immersed in hot water at 90 ° C., the mold and the sample piece were finally peeled to obtain a polymer sheet. As a result of evaluating the physical properties, the water content was 2%, the Dk value was 226, the water wettability was rank 3, and the adhesion of proteins and lipids was 5 μg / cm 2 and 55 μg / cm 2 respectively. Moreover, the tensile elastic modulus was 1.3 × 10 ⁷ dyne / cm ² .

(Comparative Example 3)
In Example 2, a cast polymerization mold made of polyethylene terephthalate (Mitsubishi Rayon, Dianite) was used as a resin mold, and polymerization was carried out by heating at 80 ° C. for 1 hour. After the polymerization, the mold was peelable by hand, and the mold and the sample piece were peeled to obtain a polymer sheet. As a result of evaluating the physical properties, the water content was 2%, the Dk value was 225, and the water wettability was slightly inferior in rank 2. The adhesion of protein and lipid was 5 μg / cm 2 and 60 μg / cm 2 respectively. Moreover, the tensile elastic modulus was 1.3 × 10 ⁷ dyne / cm ² . However, when a mold for obtaining a contact lens of P-3.0, S14.0 mm, and Tc 0.07 mm is injection-molded as the mold, the thermal stability of the resin changes with time, so that the lens peripheral portion changes. A stable fitting part could not be obtained.

(Comparative Example 4)
The monomer mixture of Example 2 was poured into a cast polymerization mold made into a lens shape (P-3.0, S14.0, Tc0.12) made of polypropylene (manufactured by Chisso Corporation, homopolymer), and 1 at 80 ° C. Polymerized by heating for a period of time. After polymerization, the mold was peelable by hand, and the mold and sample piece were peeled to obtain a soft contact lens. As a result of evaluating the physical properties, the water content was 3%, the Dk value was 226, and the adhesion of protein and lipid was 18 μg / cm 2 and 103 μg / cm 2 respectively. The wettability of the storage solution immersion lens was rank 1, and when the test was conducted after wiping off the water on the lens surface, the water wettability of the surface was greatly reduced by drying at rank 0. Moreover, the tensile elastic modulus was 1.2 × 10 ⁷ dyne / cm ² .

(The invention's effect)
The present invention provides a mold having excellent surface hydrophilicity of a product and simple mold releasability, and a resin useful as a mold for cast polymerization of medical devices such as intraocular lenses and contact lenses that require surface hydrophilicity. A mold and a method for producing a medical device using the mold are provided.

Claims (8)

A mold for cast polymerization of a silicon-containing water-containing soft contact lens, one selected from the group consisting of a polytrimethylene terephthalate resin, a polytrimethylene terephthalate copolymer resin, and a polymer blend resin based on these A mold formed from the above resin. 2. The lens according to claim 1, wherein the silicon-based soft contact lens is a lens made of a polymer containing 70 wt% to 30 wt% of a polysiloxane macromer and 30 wt% to 70 wt% of a hydrophilic monomer . template. The polysiloxane macromer has a silicon-based macromer having a polymerizable unsaturated group at a molecular end, or a perfluoro-modified or polyalkylene glycol-modified silicon-based macromer having a polymerizable unsaturated group at a molecular end. Item 3. The mold according to Item 2. A method for producing a silicon-based hydrous soft contact lens molded by cast polymerization, wherein the method is selected from a polytrimethylene terephthalate resin, a polytrimethylene terephthalate copolymer resin, and a polymer blend resin based on these. The method is characterized in that the polymerization is performed in a mold formed from one or more kinds of resins. 5. The lens according to claim 4, wherein the silicon-containing water-containing soft contact lens is a lens made of a polymer containing 70 wt% to 30 wt% of a polysiloxane macromer and 30 wt% to 70 wt% of a hydrophilic monomer. the method of. The said polysiloxane macromer is a hydrophilic polysiloxane macromer shown by Formula (1), The casting_mold | template of Claim 3 characterized by the above-mentioned.

Here, R ¹ , R ² , R ³ and R ⁴ are each a group selected from a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group; X is a polymerizable substituent represented by the formula (2) A group;

R ⁵ is hydrogen or a methyl group, Z ¹ is —NHCOO—, —NHCONH—,
^{-OCONH-R 6 -NHCOO -, -} NHCONH-R 7 -NHCONH-
And —OCONH—R ⁸ —NHCONH— (R ⁶ , R ⁷ , R ⁸ are hydrocarbon groups having 2 to 13 carbon atoms), m is 0 to 10, n is 3 to 10,
p is 0 when m is 0, and 1 when m is 1 or more. q is an integer from 0 to 20,
Structure Y is formed by combining structural units [I] and [II] represented by the following formula:
The ratio of the number of bonds between the structural units [I] and [II] is [I] / [II] = 0.1 to 200
And the total number of [I] and [II] is 10 to 1000,

Here, R ⁹ and R ¹⁰ are groups selected from a hydrocarbon group having 1 to 12 carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 12 carbon atoms, and a trimethylsiloxy group, which may be the same or different. Good. R ¹¹ and R ¹² are each a group consisting of a hydrocarbon group having 1 to 12 carbon atoms, a trimethylsiloxy group or a hydrophilic substituent , and at least one of R ¹¹ or R ¹² is a hydrophilic substituent. The hydrophilic substituent here is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group or an oxyalkylene group. The polysiloxane macromer has a silicon-based macromer having a polymerizable unsaturated group at a molecular end, or a perfluoro-modified or polyalkylene glycol-modified silicon-based macromer having a polymerizable unsaturated group at a molecular end. Item 6. The method according to Item 5. The method according to claim 7, wherein the polysiloxane macromer is a hydrophilic polysiloxane macromer represented by the formula (1).

Here, R ¹ , R ² , R ³ and R ⁴ are each a group selected from a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group; X is a polymerizable substituent represented by the formula (2) A group;

R ⁵ is hydrogen or a methyl group, Z ¹ is —NHCOO—, —NHCONH—,
^{-OCONH-R 6 -NHCOO -, -} NHCONH-R 7 -NHCONH-
And —OCONH—R ⁸ —NHCONH— (R ⁶ , R ⁷ , R ⁸ are hydrocarbon groups having 2 to 13 carbon atoms), m is 0 to 10, n is 3 to 10,
p is 0 when m is 0, and 1 when m is 1 or more. q is an integer from 0 to 20,
Structure Y is formed by combining structural units [I] and [II] represented by the following formula:
The ratio of the number of bonds between the structural units [I] and [II] is [I] / [II] = 0.1 to 200
And the total number of [I] and [II] is 10 to 1000,

Here, R ⁹ and R ¹⁰ are groups selected from a hydrocarbon group having 1 to 12 carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 12 carbon atoms, and a trimethylsiloxy group, which may be the same or different. Good. R ¹¹ and R ¹² are each a group consisting of a hydrocarbon group having 1 to 12 carbon atoms, a trimethylsiloxy group or a hydrophilic substituent , and at least one of R ¹¹ or R ¹² is a hydrophilic substituent. The hydrophilic substituent here is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group or an oxyalkylene group.