Hard contact lens materials and hard contact lenses

Abstract

The present invention provides a hard contact lens that has high oxygen permeability and a large bending deformation capacity, making it resistant to breakage from bending deformation, and a hard contact lens material that can be used to manufacture such a hard contact lens. [Solution] According to one aspect of the present invention, a hard contact lens material is provided, comprising a substituted methacrylate (A) having a molecular structure in which the ratio of the number of fluorine atoms to the number of carbon atoms is 0.6 or more and 0.9 or less, a substituted styrene (B), a methacryloyl group-containing silicone monomer (C), a (meth)acryloyl group-containing monomer (D), an unsaturated double bond-containing hydrophilic monomer (E), and a methacryloyl group-containing monomer (F), wherein the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) is 0.12 or more and 0.2 or less.

Description

[Technical Field]

[0001] This invention relates to hard contact lens materials and hard contact lenses. [Background technology]

[0002] Contact lenses used for refractive correction are classified into soft contact lenses and hard contact lenses. Soft contact lenses, which are made of flexible materials and offer superior comfort, have a higher market share than hard contact lenses. However, hard contact lenses have advantages such as higher visual quality, superior astigmatism correction, and a tendency to make it easier to detect eye problems, due to their rigid material. Recently, hard contact lenses with special shapes are also being used as orthokeratology lenses, which are worn during sleep to change the shape of the cornea and correct nearsightedness and astigmatism.

[0003] Most hard contact lenses are conventional products used in a cycle of "insertion," "removal," "cleaning," and "storage." Therefore, to prevent eye problems, it is necessary to remove any dirt that accumulates during insertion, and thus daily cleaning by rubbing is important. To clean hard contact lenses, apply a cleaning solution to the lens surface, then rub it with your palm or fingertips, followed by rinsing with tap water or a special rinsing solution. However, if excessive force is applied in a direction that bends the lens, it can easily break.

[0004] In particular, with hard contact lenses that have high oxygen permeability, the material itself is soft, making the lens surface more susceptible to scratches during handling and rubbing, thus increasing the rate of breakage. Therefore, there is a need to develop hard contact lenses that have high oxygen permeability and are resistant to breakage due to their large bending deformation when bent. As such hard contact lenses, for example, contact lenses using a poly(organosiloxane) monomer and neopentyl glycol dimethacrylate as crosslinkable monomers have been proposed (see Patent Document 1). Although the physical properties of these contact lenses are said to be improved, their oxygen permeability is not sufficient, and it is difficult to say that the amount of bending deformation in the direction in which the lens bends is sufficient.

[0005] Also, an ophthalmic lens material containing a silicone monomer having a styrene structure, a fluorine-containing monomer, and a crosslinkable monomer having a vinyl group and a methacryloyl group in its molecular structure has been proposed (see Patent Document 2). However, although this ophthalmic lens material has high oxygen permeability and impact strength (strength when a load is applied to a single point of the lens), since the lens breaks with a small amount of deformation, it is difficult to say that the amount of bending deformation is sufficient.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] In view of the above circumstances, the present invention provides a hard contact lens having high oxygen permeability and a large amount of bending deformation, and thus being difficult to break against bending deformation, and a hard contact lens material capable of manufacturing such a hard contact lens.

Means for Solving the Problems

[0008] According to one aspect of the present invention, there is provided a hard contact lens material, 35 mol% or more and 55 mol% or less of a fluoroalkyl methacrylate (A) having a molecular structure in which the ratio of the number of fluorine atoms to the number of carbon atoms is 0.6 or more and 0.9 or less, 4 mol% or more and 15 mol% or less of a styrene (B) having a silicon-containing group, 10 mol% or more and 30 mol% or less of at least one silicone monomer (C) having a methacryloyl group represented by the following general formula (I), [Chemical formula] [Z is one selected from a direct bond, the following linking structure (I-1), and the following linking structure (I-2), R1, R2, R3, and R4 are each independently an alkyl group having 1 to 4 carbon atoms, a is an integer of 1 to 3, and n is 2 or 3.] [Chemical formula] [Chemical formula] The glass transition temperature of the homopolymer is -30°C or lower, and at least one selected from monomers (D) having two (meth)acryloyl groups in the molecular structures represented by the following general formulas (II) to (IV) is 0.6 mol% or more and 1.6 mol% or less, [Chemical formula] [In the formula, X is a methyl group or a hydrogen atom, R5, R6, R7, R8, R9, and R are each independently an alkyl group having 1 to 6 carbon atoms, n1 is 3 or 4, and n2 is an integer of 12 to 40.] [Chemical formula] <0000​​​​​​​[In the formula, n4 is an integer between 4 and 15 (inclusive), and n5 is an integer between 6 and 20 (inclusive).] A hydrophilic monomer (E) having one unsaturated double bond in its molecular structure is present in an amount of 18 mol% to 25 mol%, The homopolymer has a glass transition temperature of 190°C or higher and contains a monomer (F) having two methacryloyl groups in its molecular structure. A hard contact lens material is provided in which the molar ratio of monomer (D) to monomer (F) is 0.12 or more and 0.2 or less.

[0009] According to this embodiment, it is possible to provide a hard contact lens that has high oxygen permeability and a large amount of bending deformation, making it resistant to damage from bending deformation. [Brief explanation of the drawing]

[0010] [Figure 1] This figure shows a hard contact lens set in a mounting fixture for compression bending testing. [Figure 2] This figure shows a hard contact lens compressed to a predetermined distance between mounting fixtures. [Modes for carrying out the invention]

[0011] The following provides a detailed explanation of hard contact lens materials and hard contact lenses. <<Hard contact lens materials and hard contact lenses>> Hard contact lens materials are used to manufacture hard contact lenses. This hard contact lens material comprises a fluoroalkyl methacrylate (A), styrene having a silicon-containing group (B), a silicone monomer containing a methacryloyl group (C), a monomer (D) having a homopolymer glass transition temperature of -30°C or lower and two (meth)acryloyl groups in its molecular structure, a hydrophilic monomer (E) having one unsaturated double bond in its molecular structure, and a monomer (F) having a homopolymer glass transition temperature of 190°C or higher and two methacryloyl groups in its molecular structure.

[0012] Hereinafter, fluoroalkyl methacrylate (A) will also be referred to as "substituted methacrylate (A)", styrene having a silicon-containing group (B) will also be referred to as "substituted styrene (B)", and silicone monomer containing a methacryloyl group (C) will also be referred to as "methacryloyl group-containing silicone monomer (C)". Furthermore, monomers (D) having two (meth)acryloyl groups in their molecular structure are also referred to as "(meth)acryloyl group-containing monomers (D)", hydrophilic monomers (E) having one unsaturated double bond in their molecular structure are also referred to as "unsaturated double bond-containing hydrophilic monomers (E)", and monomers (F) having two methacryloyl groups in their molecular structure are also referred to as "methacryloyl group-containing monomers (F)".

[0013] Such hard contact lens material is a monomer mixture containing a substituted methacrylate (A), a substituted styrene (B), a methacryloyl group-containing silicone monomer (C), a (meth)acryloyl group-containing monomer (D), an unsaturated double bond-containing hydrophilic monomer (E), and a methacryloyl group-containing monomer (F). Therefore, in the following, such hard contact lens material will also be referred to as "monomer mixture." Furthermore, the monomer mixture may optionally contain additional additives such as reactive monomers with UV absorption properties and colorants (see below). The following will explain each component in turn.

[0014] <Substituting methacrylate (A)> Substituted methacrylate (A) is a component (fluorine-containing monomer) that is added to monomer mixtures for purposes such as imparting hardness and oxygen permeability to hard contact lenses (polymers of hard contact lens materials). While there are many other fluorine-containing monomers besides this substituted methacrylate (A), substituted methacrylate (A) is preferred because it is readily available and can impart high oxygen permeability.

[0015] In such substituted methacrylate (A), a decrease in the number of fluorine atoms tends to reduce the oxygen permeability of the hard contact lens, while an increase in the number of fluorine atoms inevitably results in a longer chain structure, making the resulting polymer of hard contact lens material softer and less processable. Therefore, there is an appropriate relationship between the number of carbon atoms and the number of fluorine atoms in the substituted methacrylate (A). Specifically, it is preferable that the substituted methacrylate (A) has a molecular structure in which the ratio of fluorine atoms to carbon atoms is approximately 0.6 to 0.9 (i.e., the substituted methacrylate (A) has a molecular structure in which the ratio of fluorine atoms to carbon atoms is approximately 0.6 to 0.9), more preferably approximately 0.7 to 0.86, and even more preferably approximately 0.75 to 0.86. In this case, the oxygen permeability of the hard contact lens can be sufficiently increased while maintaining the good processability of the polymer of the hard contact lens material.

[0016] Examples of substituted methacrylates (A) include 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2-methyl-2,2,2-trifluoro-1-methyl-1-(trifluoromethyl)ethyl methacrylate, and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate. These substituted methacrylates (A) may be used individually or in combination of two or more. Among these, it is preferable that substituted methacrylate (A) includes 1,1,1,3,3,3-hexafluoroisopropyl methacrylate.

[0017] The content of substituted methacrylate (A) in the hard contact lens material is approximately 35 mol% to 55 mol%, but preferably 35 mol% to 50 mol%, and more preferably 40 mol% to 50 mol%. In this case, the oxygen permeability of the hard contact lens and the processability of the hard contact lens material into a lens shape are improved, and a decrease in the amount of bending deformation of the hard contact lens can be prevented or suppressed.

[0018] In this specification, "mol%" means the total amount (100 mol%) of the number of moles of substituted methacrylate (A), the number of moles of substituted styrene (B), the number of moles of methacryloyl group-containing silicone monomer (C), the number of moles of (meth)acryloyl group-containing monomer (D), the number of moles of double bond-containing hydrophilic monomer (E), the number of moles of methacryloyl group-containing monomer (F), the number of moles of an optional UV-absorbing reactive monomer (G), the number of moles of colorant (H), and the number of moles of polymerization initiator (J), that is, the proportion (mol%) of a predetermined component to the entire hard contact lens material (100 mol%).

[0019] <Substituted Styrene (B)> Substituted styrene (B) is an ingredient added to monomer mixtures for purposes such as providing hard contact lenses with high oxygen permeability and, as an auxiliary, stiffness. Substituted styrene (B) has silicon-containing groups, and by adjusting the number of silicon atoms in these silicon-containing groups, it is possible to impart a good balance of oxygen permeability and hardness to hard contact lenses. Specifically, the number of silicon atoms in the silicon-containing group of substituted styrene (B) is preferably 4 to 6, more preferably 4 to 5, and even more preferably 4. In this case, the above effects can be further improved.

[0020] Examples of such substituted styrenes (B) include tris(trimethylsiloxy)silylstyrene, 1-(4-ethenylphenyl)-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, 1-(4-ethenylphenyl)-1,1,5,5,5-pentamethyl-3,3-bis[(trimethylsilyl)oxy]trisiloxane, 3-(4-ethenylphenyl)-1,1,1,3,7,7,7-heptamethyl-5,5-bis[(trimethylsilyl)oxy]tetrasiloxane, and 3-(4-ethenylphenyl)-1,1,1,5,7,7,7-heptamethyl-3,5-bis[(trimethylsilyl)oxy]tetrasiloxane. These substituted styrenes (B) may be used individually or in combination of two or more. Among these, substituted styrene (B) preferably includes tris(trimethylsiloxy)silylstyrene. The content of substituted styrene (B) in the hard contact lens material is approximately 4 mol% to 15 mol%, but preferably 4 mol% to 12 mol%, and more preferably 4 mol% to 10 mol%. In this case, the oxygen permeability of the hard contact lens and the processability of the hard contact lens material into lens shape are improved, and polymerization strain of the hard contact lens can be reduced, and a decrease in bending deformation can be prevented or suppressed.

[0021] <Methacryloyl group-containing silicone monomer (C)> The methacryloyl group-containing silicone monomer (C) is a component added to the monomer mixture for purposes such as supplementing oxygen permeability to hard contact lenses and improving the solubility of the (meth)acryloyl group-containing monomer (D) described later. This methacryloyl group-containing silicone monomer (C) is at least one compound represented by the following general formula (I). [ka] [Z is one selected from direct bonding, the following linkage structure (I-1), and the following linkage structure (I-2); R1, R2, R3, and R4 are each independently alkyl groups having 1 to 4 carbon atoms; a is an integer between 1 and 3; and n is 2 or 3.] [ka] [ka]

[0022] Specific examples of the methacryloyl group-containing silicone monomer (C) represented by this general formula (I) include, for example, 3-methacryloxypropyltris(trimethylsiloxy)silane, (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, and methacryloxymethylphenethyltris(trimethylsiloxy)silane. The content of methacryloyl group-containing silicone monomer (C) in the hard contact lens material is approximately 10 mol% to 30 mol%, more preferably 12 mol% to 25 mol%, and even more preferably 14 mol% to 25 mol%. In this case, it is possible to prevent a decrease in the processability of the hard contact lens material into a lens shape, while also improving the oxygen permeability of the hard contact lens and further improving the solubility of the (meth)acryloyl group-containing monomer (D) described later.

[0023] <(meth)acryloyl group-containing monomer (D)> (Meth)acryloyl group-containing monomer (D) is an ingredient added to monomer mixtures for purposes such as increasing the bending deformation of hard contact lenses. When a homopolymer is synthesized using a (meth)acryloyl group-containing monomer (D), the glass transition temperature of the homopolymer is approximately -30°C or lower, preferably approximately -40°C or lower, and more preferably approximately -50°C or lower. The lower limit of the glass transition temperature of the homopolymer is not particularly limited, but is approximately -130°C. Therefore, the glass transition temperature of the homopolymer can be, for example, between -130°C and -30°C. Although the detailed mechanism is not clear, the inventors have found that by including a (meth)acryloyl group-containing monomer (D) and a methacryloyl group-containing monomer (F) described later, and by appropriately setting their molar ratio (mixing ratio), the amount of bending deformation of hard contact lenses can be increased.

[0024] This (meth)acryloyl group-containing monomer (D) is at least one selected from the compounds represented by the following general formulas (II) to (IV). [ka] [In the formula, X is a methyl group or a hydrogen atom, and R5, R6, R7, R8, R9 and R 10 Each of these is an alkyl group having between 1 and 6 carbon atoms, where n1 is 3 or 4, and n2 is an integer between 12 and 40.

[0025] In the above general formula (II), n2 is preferably an integer between 12 and 38, more preferably an integer between 15 and 30, and even more preferably an integer between 18 and 28. In this case, it is possible to increase the bending deformation of the hard contact lens while improving oxygen permeability. Furthermore, it is possible to prevent a decrease in the solubility of the component in the monomer mixture solution and a decrease in the processability of the hard contact lens material into a lens shape. Furthermore, urethane bonds or urea bonds, etc., are preferable not to be included in the molecular structure of the compound represented by general formula (II) because they induce a decrease in the strength of hard contact lenses through hydrolysis and reduce solubility in fluorine-containing monomers, which are substituted methacrylates (A).

[0026] [ka] [In the formula, X1 is a methyl group or a hydrogen atom, and n3 is an integer between 12 and 30.] In the above general formula (III), n3 is preferably an integer between 12 and 28, more preferably an integer between 12 and 25, and even more preferably an integer between 14 and 25.

[0027] [ka] [In the formula, n4 is an integer between 4 and 15 (inclusive), and n5 is an integer between 6 and 20 (inclusive).] In the above general formula (IV), n4 is preferably an integer between 5 and 12, more preferably an integer between 5 and 10, and even more preferably an integer between 6 and 10. Also, n5 is preferably an integer between 8 and 20, more preferably an integer between 10 and 20, and even more preferably an integer between 12 and 20.

[0028] In the general formulas (II) to (IV) above, the values ​​of n1, n2, n3, n4, and n5 may or may not have a distribution. Note that "the values ​​of n1, n2, n3, n4, and n5 do not have a distribution" means, for example, that if the value of n1 is 3, it is a single repeating number that does not include other values ​​(2, 4, etc.). Furthermore, in this specification, the term "average value" applies when there is a distribution in the number of repetitions in the dialkylsiloxane structure of general formula (II), the ethylene oxide group of general formula (III), the ethylene oxide group of general formula (IV), and the propylene oxide group. Specifically, the "average value" is calculated using (meth)acryloyl group-containing monomer (D) 1 This refers to the value obtained by performing 1H-NMR analysis, calculating the number of repetitions using the peak integral intensity ratio of the dialkylsiloxane structure, ethylene oxide group, and propylene oxide group, and rounding the result to the first decimal place.

[0029] The compounds represented by the above general formulas (III) and (IV) have the function of increasing the bending deformation of hard contact lenses, as well as the function of supplementarily improving the water wettability of the surface of hard contact lenses. The content of (meth)acryloyl group-containing monomer (D) in the hard contact lens material is approximately 0.6 mol% to 1.6 mol%, but preferably approximately 0.8 mol% to 1.4 mol%, and more preferably approximately 1 mol% to 1.4 mol%. In this specification, compounds with a molecular weight of less than 800 are referred to as "monomers," and compounds with a molecular weight of 800 or more are also referred to as "macromonomers." Furthermore, in this specification, "(meth)acryloyl group" means either a methacryloyl group or an acryloyl group.

[0030] <Unsaturated double bond-containing hydrophilic monomer (E)> Unsaturated double-bond-containing hydrophilic monomer (E) is a component added to monomer mixtures for purposes such as improving the water wettability of the hard contact lens surface and improving the processability of hard contact lens materials into lens shapes. These components may include at least one of the following: unsaturated carboxylic acids, unsaturated amides, etc. Examples of unsaturated carboxylic acids include acrylic acid and methacrylic acid. Examples of unsaturated amides include acrylamide, methacrylamide, and N,N-dimethylacrylamide. The content of unsaturated double-bond-containing hydrophilic monomer (E) in the hard contact lens material is approximately 18 mol% to 25 mol%, but preferably 18 mol% to 24 mol%, and more preferably 20 mol% to 24 mol%. In this case, the water wettability of the hard contact lens surface is improved, the processability of the hard contact lens material into a lens shape is improved, and a decrease in oxygen permeability and transparency of the hard contact lens can be prevented.

[0031] <Methacryloyl group-containing monomer (F)> The methacryloyl group-containing monomer (F) is a component added to the monomer mixture for purposes such as increasing the bending deformation of hard contact lenses and improving the processability of hard contact lens materials into lens shapes. When a homopolymer is synthesized using a methacryloyl group-containing monomer (F), the glass transition temperature of the homopolymer is approximately 190°C or higher, preferably 195°C or higher, and more preferably 200°C or higher. The upper limit of the glass transition temperature of the homopolymer is not particularly limited, but is approximately 300°C. Therefore, the glass transition temperature of the homopolymer can be, for example, between 190°C and 300°C.

[0032] These components preferably do not contain urethane bonds or urea bonds in their molecular structure, from the viewpoint of preventing a decrease in the strength of hard contact lenses due to hydrolysis and a decrease in solubility to fluorine-containing monomers such as substituted methacrylate (A). Examples of such methacryloyl group-containing monomers (F) include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol dimethacrylate, and the like.

[0033] The content of methacryloyl group-containing monomer (F) in the hard contact lens material is set in relation to the amount of (meth)acryloyl group-containing monomer (D) used. Specifically, the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) is approximately 0.12 to 0.2. Here, a molar ratio of approximately 0.12 to 0.2 means, for example, that when the amount of (meth)acryloyl group-containing monomer (D) used is 1.2 mol%, the amount of methacryloyl group-containing monomer (F) used is approximately 6 mol% to 10 mol%. Furthermore, the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) is preferably approximately 0.13 to 0.19, and more preferably approximately 0.14 to 0.18. In this case, the amount of bending deformation of the hard contact lens can be increased, and a decrease in the processability of the hard contact lens material into a lens shape, as well as deformation of the lens shape of the hard contact lens after rubbing and cleaning (for example, a change in the base curve), can be prevented or suppressed.

[0034] <Other ingredients> • Reactive monomer (G) that absorbs ultraviolet light Reactive monomers (G) having ultraviolet-absorbing properties (hereinafter also simply referred to as "reactive monomers (G)") are optional components that have a structure capable of absorbing ultraviolet light and are added to monomer mixtures for purposes such as imparting ultraviolet light absorption capabilities to hard contact lenses. Specific examples of reactive monomers (G) include, for example, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, 2-hydroxy-4-(methacryloyloxy)benzophenone, 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-3-(methacryloxyaminomethyl)-5-tert-octylphenyl)-2H-benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, and 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole.

[0035] Among these, the reactive monomer (G) is preferably 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, or 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole. These compounds may be used individually or in combination of two or more. The content of reactive monomer (G) in the hard contact lens material is preferably about 0.6 mol% or less, and more preferably about 0.2 mol% to 0.5 mol%.

[0036] • Coloring agent (H) The coloring agent (H) is an optional component added to the monomer mixture for purposes such as improving the visibility of hard contact lenses by coloring them. These colorants (H) are classified into two types: reactive colorants that contain at least one unsaturated double bond in their molecular structure and chemically bond with the components that make up the hard contact lens, and non-reactive colorants that do not contain an unsaturated double bond and whose colorant molecules are fixed within the three-dimensional network structure of the polymer that makes up the hard contact lens.

[0037] Reactive colorants that can be used include, for example, azo colorants, pyrazolone colorants, anthraquinone colorants, and cyanine colorants. Specific examples include, for instance, 1-(4-vinylbenzylamino)-4-phenylaminoanthraquinone, 1,4-bis(4-methylphenylamino)anthraquinone, 1,4-bis[4-(2-methacryloxyethyl)phenylamino]-9,10-anthraquinone, 1,5-bis((meth)acryloylamino)-9,10-anthraquinone, (meth)acryloylated tetraaminocopper phthalocyanine, and (meth)acryloylated (dodecanoylated tetraaminocopper phthalocyanine).

[0038] Specific examples of non-reactive colorants include, for example, Solvent Green 3, Solvent Green 7, Solvent Green 28, Solvent Yellow 18, Solvent Red 17, Solvent Red 23, Solvent Red 72, Solvent Blue 63, and Solvent Violet 13. The content of the coloring agent (H) in the hard contact lens material is preferably about 0.001 mol% or more and 0.01 mol% or less.

[0039] • Polymerization initiator (J) The polymerization initiator (J) can be either a thermal polymerization initiator or a photopolymerization initiator. Examples of thermal polymerization initiators include di(4-tert-butylcyclohexyl)peroxydicarbonate, di(3,5,5-trimethylhexanoyl)peroxide, dilauroyl peroxide, benzoyl peroxide, tert-hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2, Examples include peroxides such as 5-bis(2-ethylhexanoylperoxy)hexane, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), dimethyl-1,1'-azobis(1-cyclohexanecarboxylate), and 1,1'-azobis(cyclohexane-1-carbonitride).

[0040] Examples of photopolymerization initiators include benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. The content of the polymerization initiator (J) in the hard contact lens material is appropriately selected based on the polymerization temperature in thermal polymerization, the wavelength and intensity of light irradiation in photopolymerization, etc., but it is preferably about 0.1 mol% to 1 mol%.

[0041] <<Manufacturing Method for Hard Contact Lenses>> Hard contact lenses can be manufactured from the monomer mixture solution used as a hard contact lens material as described above. In other words, the hard contact lens of this embodiment includes a polymer (cured product) of the hard contact lens material, or a processed product of this polymer. There are no limitations on the manufacturing of hard contact lenses, but for example, the following method can be used. First, the above components are homogeneously mixed to prepare a monomer mixture, which is then poured into a container made of a material such as metal, glass, or plastic. Subsequently, the monomer mixture is polymerized by heat to produce a polymer of the monomer mixture in a predetermined shape (e.g., rod, block, plate, etc.). This thermal polymerization is preferably carried out continuously in a constant temperature bath at a temperature range of approximately 30°C to 50°C for approximately 72 to 200 hours.

[0042] After polymerization, it is preferable to perform a reheating treatment for purposes such as further reducing the amount of unpolymerized monomers in the polymer. In this reheating process, first, the lid of the container in which polymerization has been completed is removed to open the container, and then the container with the polymer inside is placed in the heat treatment apparatus. Next, the temperature is gradually increased in a range from room temperature to approximately 90°C or less, and the polymer is heated continuously for approximately 24 hours to 100 hours, after which it is cooled to room temperature. By performing this reheating process, it is possible to reduce the amount of unpolymerized monomers and oligomers remaining in the polymer.

[0043] When performing this reheating treatment, it is preferable to continuously supply (inflow) and discharge (outflow) a constant flow rate of air or nitrogen gas into the heating device. This allows for efficient removal of unpolymerized monomers from the polymer. The higher the flow rate of the gas supplied into the heating device, the more efficient the removal of unpolymerized monomers will be, but a flow rate of approximately 10 L / min to 100 L / min is sufficient. After reheating, the polymer is removed from the polymerization container and then processed into the desired shape (for example, the shape of the hard contact lens itself) by cutting and polishing. This process is called the lace-cut method.

[0044] Separately, hard contact lenses can also be manufactured by methods such as the cast molding method, in which a monomer mixture is injected into a mold having a predetermined curvature to directly form the lens shape. When this mold is used as a container, thermal polymerization can be carried out by placing the mold in the polymerization apparatus and gradually raising the temperature in a range of room temperature to approximately 90°C for 10 to 72 hours, or by placing the mold in a polymerization apparatus that has been pre-set to a constant temperature (approximately 90°C or lower) and heating for 1 to 48 hours. The atmosphere used for thermal polymerization is preferably an inert gas atmosphere such as nitrogen or argon gas. By performing thermal polymerization in such an atmosphere, the polymerization rate of monomers can be improved and the amount of unpolymerized monomers can be reduced.

[0045] When polymerization is carried out using light, the wavelength of the light used for irradiation is not particularly limited, as it is appropriately selected according to the characteristics of the photopolymerization initiator used. Specific examples of lamps used for light irradiation include, for example, lamps with strong peaks in the 200nm to 280nm range and at 350nm wavelength, lamps that emphasize wavelengths in the 350nm to 400nm range, lamps that emphasize wavelengths in the 400nm to 425nm range centered around 420nm wavelength, and lamps that emphasize wavelengths in the 400nm to 450nm range. The light irradiation intensity varies depending on the area of ​​the light-receiving part of the measuring instrument, but for example, 1 mW / cm² 2 More than 100mW / cm 2 It is preferable that it be within the following range.

[0046] The light irradiation time (polymerization time) is set appropriately according to the light irradiation intensity and is therefore not particularly limited. For example, if the light irradiation intensity is 1 mW / cm² 2 More than 100mW / cm 2 If the conditions are as follows, the irradiation time is preferably between 15 minutes and 120 minutes. In this photopolymerization, the atmosphere during polymerization is preferably an inert gas atmosphere such as nitrogen or argon gas, and the reheating treatment described above is preferable for the purpose of further reducing the amount of unpolymerized monomer in the polymer. The surface of the hard contact lens obtained in this manner may be further subjected to treatments to improve water wettability, such as low-temperature plasma treatment or atmospheric pressure plasma treatment, as needed.

[0047] <<Hard contact lenses>> The amount of flexural deformation at the time of fracture of a hard contact lens (polymer of hard contact lens material) is preferably 70% or more, more preferably 72% or more, and even more preferably 75% or more, when measured according to the test method described in ISO 18369-4:2017 (4.3 Rigid lens flexural deformation and rupture). The upper limit of the amount of flexural deformation at the time of fracture is not particularly limited, but is usually around 90%. Therefore, the amount of flexural deformation at the time of fracture can be, for example, between 70% and 90%. A hard contact lens exhibiting such an amount of flexural deformation at the time of fracture can be judged to have excellent mechanical strength.

[0048] The amount of bending deformation at the time of fracture is a value that can be determined by the following formula. For example, "the amount of bending deformation at the time of fracture is 70%" means that when a hard contact lens with a diameter (initial diameter) of 9.5 mm is compressed at a test speed of 200 mm / min in a test environment of 23°C and 50% humidity, the distance between the mounting fixtures at the time of fracture of the hard contact lens is 2.85 mm (see Figures 1 and 2).

number

[0049] Furthermore, the oxygen permeability coefficient of hard contact lenses (polymers of hard contact lens materials) was measured using the test methods described in ISO 18369-4:2017 (4.4 Oxygen permeability, 4.4.3 Polarographic method), and was 120 × 10⁻¹⁰.-11 (cm 2 / sec)·(mL O₂ / (mL×mmHg)) or more is preferable, and 130×10 -11 (cm 2 / sec)·(mL O₂ / (mL×mmHg)) or more is more preferable, and 140×10 -11 (cm 2 / sec)·(mL O₂ / (mL×mmHg)) or more is even more preferable. The upper limit of the oxygen permeability coefficient is not particularly limited, but is usually about 200×10 -11 (cm 2 / sec)·(mL O₂ / (mL×mmHg)). Therefore, the oxygen permeability coefficient can be, for example, 120×10 -11 (cm 2 / sec)·(mL O₂ / (mL×mmHg)) or more and 200×10 -11 (cm 2 / sec)·(mL O₂ / (mL×mmHg)) or less. A hard contact lens having such an oxygen permeability coefficient can be judged to have extremely high oxygen permeability.

[0050] Also, the durometer hardness (Type D) measured under the test environment of 23°C and 5% humidity of the hard contact lens (polymer of the hard contact lens material) is preferably about 74 or more and 78 or less, more preferably about 75 or more and 78 or less, and even more preferably about 76 or more and 78 or less. A hard contact lens having such a durometer hardness (Shore D hardness) can also be judged to have excellent mechanical strength. Furthermore, it may be provided in each of the following aspects.

[0051] (1) A hard contact lens material, 35 mol% or more and 55 mol% or less of fluoroalkyl methacrylate (A) having a molecular structure in which the ratio of the number of fluorine atoms to the number of carbon atoms is 0.6 or more and 0.9 or less, 4 mol% or more and 15 mol% or less of styrene (B) having a silicon-containing group, At least one silicone monomer (C) having a methacryloyl group represented by the following general formula (I) is included in an amount of 10 mol% to 30 mol%, [ka] [Z is one selected from direct bonding, the following linkage structure (I-1), and the following linkage structure (I-2); R1, R2, R3, and R4 are each independently alkyl groups having 1 to 4 carbon atoms; a is an integer between 1 and 3; and n is 2 or 3.] [ka] [ka] The homopolymer has a glass transition temperature of -30°C or lower, and contains at least one monomer (D) selected from those having two (meth)acryloyl groups in the molecular structure represented by the following general formulas (II) to (IV), in an amount of 0.6 mol% to 1.6 mol%, [ka] [In the formula, X is a methyl group or a hydrogen atom, and R5, R6, R7, R8, R9 and R 10 Each of these is an alkyl group having between 1 and 6 carbon atoms, where n1 is 3 or 4, and n2 is an integer between 12 and 40. [ka] [In the formula, X1 is a methyl group or a hydrogen atom, and n3 is an integer between 12 and 30.] [ka] [In the formula, n4 is an integer between 4 and 15 (inclusive), and n5 is an integer between 6 and 20 (inclusive).] A hydrophilic monomer (E) having one unsaturated double bond in its molecular structure is present in an amount of 18 mol% to 25 mol%, The homopolymer has a glass transition temperature of 190°C or higher and contains a monomer (F) having two methacryloyl groups in its molecular structure. A hard contact lens material in which the molar ratio of monomer (D) to monomer (F) is 0.12 or more and 0.2 or less.

[0052] (2) The hard contact lens material described in (1) above, wherein the fluoroalkyl methacrylate (A) comprises 1,1,1,3,3,3-hexafluoroisopropyl methacrylate.

[0053] (3) A hard contact lens material according to (1) or (2) above, wherein the styrene (B) having a silicon-containing group has a number of silicon atoms in the silicon-containing group of 4 or more and 6 or less.

[0054] (4) A hard contact lens material according to any one of (1) to (3) above, wherein the silicon-containing styrene (B) comprises tris(trimethylsiloxy)silylstyrene.

[0055] (5) A hard contact lens comprising a polymer of the hard contact lens material described in any one of (1) to (4) above, or a processed product of the polymer.

[0056] (6) A hard contact lens as described in (5) above, wherein the amount of bending deformation of the hard contact lens at the time of breakage is 70% or more.

[0057] (7) In the hard contact lens described in (5) or (6) above, the oxygen permeability coefficient of the hard contact lens is 120 × 10 -11 (cm 2 Hard contact lenses with a pH of 1 / sec)·(mLO2 / (mL×mmHg)) or higher.

[0058] (8) A hard contact lens as described in any one of (5) to (7) above, wherein the durometer hardness (Type D) of the hard contact lens measured under a test environment of 23°C and 50% humidity is 74 or more and 78 or less. Of course, this is not always the case.

[0059] As previously described, various embodiments of the present invention have been explained, but these are merely examples and do not limit the scope of the invention in any way. These novel embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents. [Examples]

[0060] The hard contact lens material and hard contact lens will be described in more detail below with reference to examples, but the invention is not limited to these examples. 1.Ingredients used The names and abbreviations of the compounds used in the following examples and comparative examples are shown.

[0061] 1-1. Substituted methacrylate (A) 6F: 1,1,1,3,3,3-Hexafluoroisopropyl methacrylate [CAS: 3063-94-3, Molecular weight: 236, Ratio of fluorine atoms to carbon atoms: 0.857] • 5F: 2,2,3,3,3-Pentafluoropropyl methacrylate [CAS: 45115-53-5, Molecular weight: 218, Ratio of fluorine atoms to carbon atoms: 0.714] • 7F: 2,2,3,3,4,4,4-heptafluorobutyl methacrylate [CAS: 13695-31-3, Molecular weight: 268, Ratio of fluorine atoms to carbon atoms: 0.875]

[0062] 1-2. Substituted styrene (B) • TTMS: Tris(trimethylsiloxy)silylstyrene [CAS:18547-54-1, molecular weight: 399]

[0063] 1-3. Methacryloyl group-containing silicone monomer (C) TRIS: 3-Methacryloxypropyltris(trimethylsiloxy)silane [CAS: 17096-07-0, Molecular weight: 423, Compound in which Z is directly bonded, n is 3, R2, R3 and R4 are methyl groups, and a is 3 in the above general formula (I)] SiGMA: (3-methacrylateoxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane [CAS: 69861-02-5, Molecular weight: 423, Compound in which, in the above general formula (I), Z is the above linkage structure (I-1), n ​​is 3, R1, R2, R3 and R4 are methyl groups, and a is 2] MP-TRIS: Methacrylateoxymethylphenethyltris(trimethylsiloxy)silane [CAS: 108587-59-3, Molecular weight: 499, Compound in which, in the above general formula (I), Z is the above linkage structure (I-2), n is 2, R2, R3 and R4 are methyl groups, and a is 3]

[0064] 1-4. (Meth)acryloyl group-containing monomer (D) M2D17 [CAS: 70877-62-2, Molecular weight: 1672, In the above general formula (II), X is a methyl group, R5, R6, R7, R8, R9 and R 10 [A compound in which each of the following is a methyl group, n1 is 4, and n2 (average value) is 17] PDMS23 [CAS: 58130-03-3, Molecular weight: 2088, In the above general formula (II), X is a methyl group, R5, R6, R7, R8, R9 and R 10 [A compound in which each of the following is a methyl group, n1 is 3, and n2 (average value) is 23] PDMS37 [CAS: 58130-03-3, Molecular weight: 3124, In the above general formula (II), X is a methyl group, R5, R6, R7, R8, R9 and R 10 [A compound in which each of the following is a methyl group, n1 is 3, and n2 (average value) is 37]

[0065] M2D25 [CAS: 70877-62-2, Molecular weight: 2264, In the above general formula (II), X is a methyl group, R5, R6, R7, R8, R9 and R 10 [A compound in which each of the following is a methyl group, n1 is 4, and n2 (average value) is 25] P600-DMA [CAS: 25852-47-5, Molecular weight: 770, Compound in which X1 is a methyl group and n3 (average value) is 14 in the above general formula (III)] · P1000-DMA [CAS: 25852-47-5, Molecular weight: 1166, Compound in which X1 is a methyl group and n3 (average value) is 23 in the above general formula (III)] 1700B [CAS: 87003-89-2, Molecular weight: 1756, Compound in which n4 (mean value) is 7 and n5 (mean value) is 17 in the above general formula (IV)]

[0066] 1-5. Unsaturated double bond-containing hydrophilic monomers (E) • MAA: Methacrylic acid [CAS:79-41-4, molecular weight:86]

[0067] 1-6. Methacryloyl group-containing monomer (F) NPG-DMA: Neopentyl glycol dimethacrylate [CAS:1985-51-9, molecular weight:240] • EDMA: Ethylene glycol dimethacrylate [CAS:97-90-5, molecular weight: 198] • DEGDMA: Diethylene glycol dimethacrylate [CAS:2358-84-1, molecular weight: 242] TEGDMA: Triethylene glycol dimethacrylate [CAS:109-16-0, molecular weight:286] • HDDMA: 1,6-Hexanediol dimethacrylate [CAS:6606-59-3, molecular weight: 254]

[0068] 1-7. Reactive monomers (G) RUVA-93:2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole [CAS:96478-09-0, molecular weight: 323]

[0069] 1-8. Polymerization initiator (J) AIBN: 2,2'-Azobis(isobutyronitrile) [CAS:78-67-1, molecular weight: 164] • Darocur1173: 2-Hydroxy-2-methylpropiophenone [CAS:7473-98-5, molecular weight: 164] PX431: 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane [CAS:13052-09-0, molecular weight: 431] V-65: 2,2'-Azobis(2,4-dimethylvaleronitrile) [CAS:4419-11-8, molecular weight:248]

[0070] 1-9. Ingredients (R) that do not fall under (A) to (H) and (J) above. • 3F: 2,2,2-trifluoroethyl methacrylate [CAS: 352-87-4, Molecular weight: 168, Ratio of fluorine atoms to carbon atoms: 0.5] • 13F: 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate [CAS: 2144-53-8, Molecular weight: 432, Ratio of fluorine atoms to carbon atoms: 1.08] ·PDMS07 [CAS: 58130-03-3, Molecular weight: 904, In the above general formula (II), X is a methyl group, R5, R6, R7, R8, R9 and R 10 [A compound in which each of the following is a methyl group, n1 is 3, and n2 (average value) is 7] M2D10 [CAS: 70877-62-2, Molecular weight: 1154, In the above general formula (II), X is a methyl group, R5, R6, R7, R8, R9 and R 10 [A compound in which each of the following is a methyl group, n1 is 4, and n2 (average value) is 10] M2D50 [CAS: 70877-62-2, Molecular weight: 4114, In the above general formula (II), X is a methyl group, R5, R6, R7, R8, R9 and R 10 [A compound in which each of the following is a methyl group, n1 is 4, and n2 (average value) is 50] PEG-DA [CAS: 26570-48-9, Molecular weight: 522, Compound in which X1 is a hydrogen atom and n3 (average value) is 9 in the above general formula (III)]

[0071] UDMA: Urethane dimethacrylate [CAS: 72869-86-4, Molecular weight: 471, Compound represented by the following formula] [ka] NVP: N-vinyl-2-pyrrolidone [CAS:88-12-0, molecular weight: 111] VBMA: 4-vinylbenzyl methacrylate [CAS:99413-45-3, molecular weight:202]

[0072] 2. Preparation of homopolymers of (meth)acryloyl group-containing monomer (D) (Homopolymer 1) First, 10 g of PDMS23 and 0.06 g of Darocur1173 were placed in a 20 mL glass bottle and stirred at room temperature for approximately 18 hours. Next, this monomer mixture was poured into a mold (made of polypropylene) to produce a disc-shaped polymer with a final shape of 16 mm in diameter and 0.6 mm in thickness, and the upper and lower molds were assembled. After that, approximately 35 mW / cm² was generated. 2 Polymerization was completed by irradiating the sample with ultraviolet light (wavelength between 300nm and 400nm) for 20 minutes. After polymerization, only the upper mold was removed, leaving the polymer contained in the lower mold. Next, the mold was placed in the heat treatment apparatus and reheated according to the following schedule to obtain a disc-shaped polymer.

[0073] [Table 1]

[0074] (Homopolymers 2-11) Similarly, 10 g each of PDMS07, PDMS37, M2D10, M2D17, M2D25, M2D50, P600-DMA, P1000-DMA, 1700B, and PEG-DA were weighed out, along with 0.06 g of Darocur1173, and disc-shaped polymers were prepared in the same manner as homopolymer 1.

[0075] 3. Preparation of homopolymers of methacryloyl group-containing monomers (F) (Homopolymer 12-17) 10 g each of NPG-DMA, EDMA, DEGDMA, TEGDMA, HDDMA, and UDMA were weighed out, along with 0.06 g of Darocur 1173, and disc-shaped polymers were prepared in the same manner as for homopolymer 1.

[0076] 4. Measurement of glass transition temperature (Tg) First, from the disc-shaped polymers obtained above, test specimens of homopolymers 2-11 were extracted using a φ5 mm biopsy trephine. Homopolymers 12-17 were pulverized using a small pulverizer to prepare test specimens. Next, these test specimens were placed in aluminum containers used for differential scanning calorimetry and sealed. At this time, the mass of the test specimens was approximately 10 mg to 13 mg. Next, using an empty aluminum container as the reference material, the glass transition temperatures of homopolymers 2-11 were measured using a differential scanning calorimeter (NETZSCH, "DSC3500 Sirius") according to the schedule shown in Table 2, and those of homopolymers 12-17 according to the schedule shown in Table 3.

[0077] [Table 2]

[0078] [Table 3]

[0079] From the obtained DSC chart, the midpoint glass transition temperature was defined as the glass transition temperature of the homopolymer. As a result, the glass transition temperatures of each homopolymer were as shown in Tables 4 and 5 below.

[0080] [Table 4]

[0081] [Table 5]

[0082] 5. Fabrication of hard contact lenses (Example 1) In a 30 mL glass bottle, the following amounts of 6F, TTMS, TRIS, M2D17, MAA, NPG-DMA, RUVA-93, and AIBN were weighed out and stirred at room temperature for approximately 18 hours. This prepared a monomer mixture (hard contact lens material).

[0083] • 6F: 6.7672g (36.08 mol%, 30.76 mass%) • TTMS: 1.6918g (5.34 mol%, 7.69 mass%) TRIS: 8.4590g (25.19 mol%, 38.45 mass%) • M2D17: 1.7160g (1.29 mol%, 7.80 mass%) MAA: 1.5400g (22.52 mol%, 7.00 mass%) • NPG-DMA: 1.6500g (8.64 mol%, 7.50 mass%) RUVA-93: 0.1100g (0.43 mol%, 0.50 mass%) AIBN: 0.0660g (0.51 mol%, 0.30 mass%)

[0084] Next, this monomer mixture was filled into a polyethylene container with an inner diameter of 13.0 mm, an outer diameter of 15.0 mm, and a length of 200 mm, and sealed tightly with a polyethylene cap. Then, it was immersed in a water bath pre-set to 38.5°C and polymerized for 144 hours. Subsequently, the cap was removed from the container, and the mixture was reheated under the conditions shown in Table 6 to obtain a rod-shaped polymer of the monomer mixture. A button shape with a diameter of 12.0 mm and a thickness of 5.0 mm was cut from this polymer of the monomer mixture, and this button-shaped polymer was then cut and processed into a lens shape to obtain a hard contact lens.

[0085] [Table 6]

[0086] (Examples 2-5, Comparative Examples 1-4) A monomer mixture (hard contact lens material) and a hard contact lens were prepared in the same manner as in Example 1, except for the composition shown in Table 7.

[0087] (Examples 6-9) A monomer mixture (hard contact lens material) and a hard contact lens were prepared in the same manner as in Example 1, except for the composition shown in Table 8.

[0088] (Comparative Examples 5-7) A monomer mixture (hard contact lens material) was prepared in the same manner as in Example 1, except for the composition shown in Table 8, and degassed by freezing and thawing with liquid nitrogen. Next, the monomer mixture was placed in a polymerization container consisting of two Teflon® sheets separated by an elastomer and held together by a double clip. After filling, the container was purged with nitrogen gas and sealed tightly. This container was heated at 70°C for 4 hours, then at 80°C for 3 hours and at 110°C for 1 hour. The resulting sheet-like monomer mixture polymer was further heated at 120°C for 1 hour, and after cooling, a button shape with a diameter of 12.0 mm and a thickness of 5.0 mm was cut from the sheet. This button-shaped polymer was then cut and processed into a lens shape to obtain a hard contact lens.

[0089] (Comparative Examples 8 and 9) A monomer mixture (hard contact lens material) was prepared in the same manner as in Example 1, except for the composition shown in Table 8, and was placed in a borosilicate glass test tube with a diameter of 15.0 mm and a length of 150 mm, and sealed tightly. This container was polymerized in a constant temperature water bath at 35°C for 40 hours. Then, the test tube was transferred to a circulating dryer and heated at 50°C for 6 hours, followed by a heating rate of 10°C per hour up to 130°C to heat polymerize the components and obtain a polymer of a rod-shaped monomer mixture. From this polymer, a button shape with a diameter of 12.0 mm and a thickness of 5.0 mm was cut out, and this button-shaped polymer was then cut and processed into a lens shape to obtain a hard contact lens.

[0090] (Examples 10-17, Comparative Example 10) A monomer mixture (hard contact lens material) and a hard contact lens were prepared in the same manner as in Example 1, except for the composition shown in Table 9.

[0091] (Examples 18, 19 and Comparative Examples 11, 12) A monomer mixture (hard contact lens material) and a hard contact lens were prepared in the same manner as in Example 1, except for the composition shown in Table 10.

[0092] 6. Measurement and Evaluation The polymers of the monomer mixtures obtained in each example and comparative example, as well as the hard contact lenses, were evaluated for machinability, hardness, oxygen permeability coefficient, and compression bending properties.

[0093] 6-1. Evaluation of machinability When hard contact lenses were processed from a polymer of a button-shaped monomer mixture with a diameter of 12.0 mm and a thickness of 5.0 mm using the lace-cutting method, the surface condition of the hard contact lenses after cutting and polishing was evaluated according to the following criteria. <Evaluation Criteria> G (Good): The surface of the hard contact lens after polishing showed excellent transparency, and no lace marks from the cutting process were observed. B (Bad): The polymer in the monomer mixture was soft, resulting in high cutting resistance, and the cut surface and subsequent polished surface became rough and white.

[0094] 6-2. Measurement of Hardness Button-shaped test specimens with a diameter of 12.0 mm and a thickness of 5.0 mm were cut from the monomer mixture polymer and their surfaces were polished. Next, after conditioning for 96 hours at 23°C and 50% humidity, the hardness of the test specimens was measured using a durometer (Type D) (GSD-720J-R, manufactured by Teclock Co., Ltd.). The number of tests was set to 3, and the average value (rounded to the first decimal place) was used as the hardness rating.

[0095] 6-3. Measurement of Oxygen Permeability Coefficient From a button-shaped monomer mixture polymer with a diameter of 12.0 mm and a thickness of 5.0 mm, flat test pieces with thicknesses of 0.14 mm, 0.18 mm, 0.25 mm, 0.32 mm, and 0.40 mm were cut out, and their surfaces were polished. Next, the oxygen permeability coefficient was measured according to the polarography method described in ISO 18369-4:2017. An oxygen permeability analyzer (Createch Rehder Development Company, "201T") was used for the measurement.

[0096] 6-4. Compression bending test (calculation of bending deformation at the time of failure) Hard contact lenses of the following shapes were fabricated from polymers of a button-shaped monomer mixture with a diameter of 12.0 mm and a thickness of 5.0 mm. Front: Single cut (radius of curvature 8.00mm ± 0.025mm) Rear: Single cut (radius of curvature 7.80mm ± 0.025mm) Total diameter: 9.5mm±0.1mm Center thickness: 0.20mm ± 0.01mm Edge thickness: 0.24mm ± 0.01mm (edge ​​shape is rounded) Maximum prism error: 0.5 cm / m Next, the hard contact lens was tested according to the method described in ISO 18369-4:2017 to determine the amount of bending deformation at the time of fracture. The number of tests was set to 5, and the average value (rounded to two decimal places) was used as the amount of bending deformation at the time of fracture.

[0097] These results are shown in Tables 7 to 10 below. [Table 7]

[0098] In Table 7, the units of composition are shown in mole percent in the upper row and in mass percent in the lower row (in parentheses). As shown in Table 7, the hard contact lenses of Examples 1 to 5 have good processability and an oxygen permeability coefficient of 130 × 10⁻⁶. -11 (cm 2 / sec)·(mLO2 / (mL×mmHg)) or more 156×10 -11 (cm 2The bending deformation was between 75.0% and 83.0% when the ratio was less than or equal to (mLO2 / (mL×mmHg)). In contrast, the hard contact lenses of Comparative Examples 1-3 were made from monomer mixtures using monomers (PDMS07, M2D50, or PEG-DA) that deviated from the molecular structural range of (meth)acryloyl group-containing monomer (D). As a result, the bending deformation of the hard contact lenses of Comparative Examples 1 and 3 was small, at 68.4% and 67.1%, respectively. Furthermore, the polymer of the monomer mixture in Comparative Example 2 was soft, making it difficult to cut and polish into a lens shape, and therefore unsuitable for hard contact lenses.

[0099] The hard contact lens of Comparative Example 4 was made from a monomer mixture using two types of crosslinkable monomers (NPG-DMA and UDMA) without using the (meth)acryloyl group-containing monomer (D). As a result, the bending deformation of the hard contact lens of Comparative Example 4 was small, at 66.9%. The hard contact lenses of Examples 1 to 5, obtained using a monomer mixture containing (meth)acryloyl group-containing monomer (D) in a molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) in the range of 0.12 to 0.2, exhibit high oxygen permeability and bending deformation. Therefore, while maintaining excellent oxygen permeability, they are considered to be more resistant to bending deformation and less prone to breakage than conventional hard contact lenses.

[0100] [Table 8]

[0101] In Table 8, the units of composition are shown in mole percent in the upper row and mass percent in the lower row (in parentheses). As shown in Table 8, the hard contact lenses of Examples 6-9 have good processability and an oxygen permeability coefficient of 131 × 10⁻⁶. -11 (cm 2 / sec)·(mLO2 / (mL×mmHg)) or more 183×10 -11 (cm2 When the ratio was less than or equal to (mLO2 / (mL×mmHg)), the bending deformation was between 73.1% and 82.0%. In contrast, the hard contact lens of Comparative Example 5 was manufactured using a monomer (M2D50) that deviated from the molecular structural range of the (meth)acryloyl group-containing monomer (D), and using a monomer mixture in which the molar ratio of monomer (M2D50) to methacryloyl group-containing monomer (F) was less than 0.12. As a result, the bending deformation of the hard contact lens of Comparative Example 5 was small, at 63.3%.

[0102] Although the hard contact lens of Comparative Example 6 used a (meth)acryloyl group-containing monomer (D), it was manufactured using a monomer mixture in which the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) was less than 0.12. As a result, the bending deformation of the hard contact lens of Comparative Example 6 was small, at 58.4%. The hard contact lens of Comparative Example 7 was manufactured using a monomer (M2D10) that deviates from the molecular structural range of the (meth)acryloyl group-containing monomer (D), and using a monomer mixture in which the molar ratio of monomer (M2D10) to methacryloyl group-containing monomer (F) was greater than 0.2. As a result, the bending deformation of the hard contact lens of Comparative Example 7 was small, at 53.9%.

[0103] The hard contact lenses of Comparative Examples 8 and 9 were made from contact lens material that did not contain (meth)acryloyl group-containing monomer (D). As a result, the bending deformation of the hard contact lenses of Comparative Examples 8 and 9 was low, at 58.9% and 65.6%, respectively. The hard contact lenses of Examples 6 to 9, obtained using a monomer mixture containing (meth)acryloyl group-containing monomer (D) in a molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) in the range of 0.12 to 0.2, exhibit high oxygen permeability and bending deformation. Therefore, while maintaining excellent oxygen permeability, they are considered to be more resistant to bending deformation and less prone to breakage than conventional hard contact lenses.

[0104] [Table 9]

[0105] In Table 9, the units of composition are shown in mole percent in the upper row and in mass percent in the lower row (in parentheses). As shown in Table 9, the hard contact lenses of Examples 10-17 have good processability and an oxygen permeability coefficient of 158 × 10⁻⁶. -11 (cm 2 / sec)·(mLO2 / (mL×mmHg)) or more 198×10 -11 (cm 2 When the ratio was less than or equal to (mLO2 / (mL×mmHg)), the bending deformation was between 77.0% and 82.8%. Thus, the hard contact lenses of Examples 10 to 17, obtained using a monomer mixture containing (meth)acryloyl group-containing monomer (D) in a molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) in the range of 0.12 to 0.2, have high oxygen permeability and bending deformation capacity. Therefore, while maintaining excellent oxygen permeability, they are considered to be more resistant to bending deformation and less prone to breakage than conventional hard contact lenses.

[0106] In contrast, the hard contact lens of Comparative Example 10 was manufactured using a monomer mixture in which the amount of (meth)acryloyl group-containing monomer (D) exceeded 1.6 mol%, and the molar ratio of (meth)acryloyl group-containing monomer (D) to methacryloyl group-containing monomer (F) also exceeded 0.2. As a result, the polymer of the monomer mixture of Comparative Example 10 was soft, making it difficult to cut and polish into a lens shape, and therefore unsuitable for hard contact lenses.

[0107] [Table 10]

[0108] In Table 10, the units of composition are shown in mole percent in the upper row and mass percent in the lower row (in parentheses). As shown in Table 10, the hard contact lenses of Examples 18 and 19 have good processability and an oxygen permeability of 131 × 10 -11 (cm 2 / sec)·(mLO2 / (mL×mmHg)) and 149×10 -11 (cm 2 The bending deformation was 77.8% and 80.6% at (mLO2 / (mL×mmHg))·(mLO2 / (mL×mmHg)). The hard contact lenses of Examples 18 and 19, and the hard contact lens of Example 2, which has a similar composition, were fabricated using substituted methacrylate (A) having a molecular structure in which the ratio of fluorine atoms to carbon atoms is 0.6 or more and 0.9 or less. Since all of these hard contact lenses have high oxygen permeability and bending deformation capacity, they are considered to be stronger against bending deformation and less prone to breakage than conventional hard contact lenses while maintaining excellent oxygen permeability.

[0109] In contrast, the hard contact lens of Comparative Example 11 was manufactured using substituted methacrylate (A) having a molecular structure in which the ratio of fluorine atoms to carbon atoms is less than 0.6 (specifically 0.5). Therefore, the oxygen permeability coefficient of the hard contact lens of Comparative Example 11 was 83 × 10⁻¹⁰. -11 (cm2 The values ​​were low ( / sec)·(mLO2 / (mL×mmHg)). Furthermore, the hard contact lens of Comparative Example 12 was manufactured using substituted methacrylate (A) having a molecular structure in which the ratio of fluorine atoms to carbon atoms was greater than 0.9 (specifically 1.08). As a result, the hard contact lens material of Comparative Example 12 was soft and sticky, and could not be removed from the polyethylene container used for polymerization.

[0110] Furthermore, if you use another substituted styrene (B) (styrene (B) having a silicon-containing group) instead of tris(trimethylsiloxy)silylstyrene and prepare a monomer mixture (hard contact lens material) and manufacture a hard contact lens in the same manner as in the above example, and then measure and evaluate it in the same manner as above, you will get the same effects as in the above example. [Explanation of Symbols]

[0111] 1: Hard contact lens placement jig, 2: Hard contact lens, d: Initial diameter, D T : Distance between installation fixtures

Claims

1. A hard contact lens material, A fluoroalkyl methacrylate (A) having a molecular structure in which the ratio of fluorine atoms to carbon atoms is 0.6 or more and 0.9 or less is used in a quantity of 35 mol% or more and 55 mol% or less. Styrene (B) containing a silicon-containing group, including tris(trimethylsiloxy)silylstyrene, is present in an amount of 4 mol% to 15 mol%, At least one silicone monomer (C) having a methacryloyl group represented by the following general formula (I) is included in an amount of 10 mol% to 30 mol%, 【Chemistry 1】 [Z is one of the following selected types: direct bond, linked structure (I-1), and linked structure (I-2), R １ , R ２ , R ３ and R ４ Each of these is an alkyl group having 1 to 4 carbon atoms, a is an integer between 1 and 3, and n is 2 or 3. 【Chemistry 2】 【Transformation 3】 The homopolymer has a glass transition temperature of -30°C or lower, and contains at least one monomer (D) selected from those having two (meth)acryloyl groups in the molecular structure represented by the following general formulas (II) to (IV), in an amount of 0.6 mol% to 1.6 mol%, 【Chemistry 4】 [wherein, X is a methyl group or a hydrogen atom, and R ５ , R ６ , R ７ , R ８ , R ９ , and R １０ are each independently an alkyl group having 1 to 6 carbon atoms, n １ is 3 or 4, and n ２ is an integer of 12 or more and 40 or less. ] 【Transformation 5】 [In the formula, X １ is a methyl group or a hydrogen atom, n ３ [This is an integer between 12 and 30, inclusive.] 【Transformation 6】 [In the formula, n ４ n is an integer between 4 and 15, and ５ [This is an integer between 6 and 20, inclusive.] A hydrophilic monomer (E) having one unsaturated double bond in its molecular structure is present in an amount of 18 mol% to 25 mol%, The homopolymer has a glass transition temperature of 190°C or higher and contains a monomer (F) having two methacryloyl groups in its molecular structure. A hard contact lens material in which the molar ratio of monomer (D) to monomer (F) is 0.12 or more and 0.2 or less.

2. In the hard contact lens material according to claim 1, The fluoroalkyl methacrylate (A) is a hard contact lens material comprising 1,1,1,3,3,3-hexafluoroisopropyl methacrylate.

3. In the hard contact lens material according to claim 1, The styrene (B) having the silicon-containing group is a hard contact lens material in which the number of silicon atoms in the silicon-containing group is 4 or more and 6 or less.

4. These are hard contact lenses. A hard contact lens comprising a polymer of the hard contact lens material described in any one of claims 1 to 3, or a processed product of the polymer.

5. In the hard contact lens described in claim 4, The hard contact lens described above has a bending deformation of 70% or more at the time of breakage.

6. In the hard contact lens described in claim 4, The oxygen permeability coefficient of the hard contact lens is 120 × 10 －１１ (cm ２ / sec)・(mLO ２ Hard contact lenses with a pressure of 1 / (mL × mmHg) or higher.

7. In the hard contact lens described in claim 4, The hard contact lens having a durometer hardness (Type D) of 74 or higher and 78 or lower, measured under a test environment of 23°C and 50% humidity.

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