Silicone-containing copolymer, method for producing same, curable resin composition, and cured product

Abstract

The present invention provides: a silicone compound that is compatible with a polymerizable monomer; and a copolymer of said silicone compound and a polymerizable monomer.　This silicone-containing copolymer is obtained through polymerization of a composition containing a polymerizable monomer and a compound represented by formula (1).　In formula (1), n represents an integer of 0-300, R1, R2, R3, R4, R5, R6, R7, and R8 each independently represent hydrogen or alkyl having 1-30 carbon atoms, R9 and R10 each independently represent hydrogen or methyl, and X1, X2, X3, and X4 each independently represent alkylene having 1-20 carbon atoms.

Description

Silicone-containing copolymer, its manufacturing method, curable resin composition, and cured product

[0001] The present invention relates to a silicone-containing copolymer, a method for producing the silicone-containing copolymer, and a curable resin composition. More specifically, the present invention relates to a curable resin composition containing a silicone compound and a polymerizable monomer, a silicone-containing copolymer obtained by polymerizing the composition, and a method for producing the same.

[0002] Silicones are linear polymers with siloxane bonds in the main skeleton. They are characterized by physical properties such as heat resistance, cold resistance, light resistance, insulating properties, transparency, mold releasability, water repellency, oil repellency, and slipperiness, and are therefore used in a wide range of fields, including resist materials, paints, coating materials, ophthalmic devices, and 3D printers (see, for example, Patent Documents 1 to 5).

[0003] The silicone-containing copolymers used as these materials can be obtained by radical polymerization of a composition containing a silicone compound having a (meth)acryloyl group and other polymerizable monomers by irradiation with light or heat. Polymerization by irradiation with light is particularly energy-efficient and allows partial irradiation of light to polymerize only that portion, making it an industrially viable method.

[0004] However, since silicone is hydrophobic and poorly compatible with other polymerizable monomers, there is a problem that a composition of a silicone compound and a polymerizable monomer becomes cloudy, and a copolymer obtained by polymerizing the composition also becomes cloudy and brittle. Therefore, development of silicone compounds that are compatible with other polymerizable monomers has been underway (see, for example, Patent Document 2).

[0005] International Publication No. 2009 / 075233 Japanese Patent Application Publication No. 2016-84446 Japanese Patent Application Publication No. 2016-779 Special Publication No. 2018-500192 Chinese Patent Application Publication No. 113122125

[0006] As mentioned above, there is a demand for silicone compounds that are compatible with polymerizable monomers as raw materials for silicone-containing copolymers. Accordingly, the present inventors have conducted extensive research with the aim of providing a silicone compound that is compatible with polymerizable monomers, and a copolymer of such a silicone compound and a polymerizable monomer.

[0007] As a result of intensive investigations to solve the above problems, the present inventors have found that the compound represented by formula (1) is compatible with other polymerizable monomers to give a transparent copolymer, and that the copolymer has excellent water repellency, oil repellency, stain resistance, and scratch resistance, and have completed the present invention.

[0008] The present invention includes the following configurations.

[0009] [1] A silicone-containing copolymer obtained by polymerizing a composition containing a compound represented by formula (1) and a polymerizable monomer. In formula (1), n ​​is an integer of 0 to 300, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and R ９ , and R １０ are each independently hydrogen or methyl; X １ , X ２ , X ３ , and X ４ are each independently an alkylene having 1 to 20 carbon atoms.

[0010] [2] The silicone-containing copolymer according to item [1], wherein the compound represented by formula (1) is a compound represented by formula (2): In formula (2), n is an integer from 0 to 300, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and R ９ , and R １０ are each independently hydrogen or methyl.

[0011] [3] The silicone-containing copolymer according to item [1] or [2], wherein the compound represented by formula (1) or formula (2) is a compound represented by formula (3). In formula (3), n is an integer from 0 to 300, and R ９ , and R １０ are each independently hydrogen or methyl.

[0012] [4] The silicone-containing copolymer according to any one of items [1] to [3], wherein the polymerizable monomer includes a polymerizable monomer having two or more (meth)acryloyl groups.

[0013] [5] The silicone-containing copolymer according to any one of items [1] to [3], wherein the polymerizable monomer includes a polymerizable monomer having three or more (meth)acryloyl groups.

[0014] [6] The silicone-containing copolymer according to item [4], wherein the composition contains the compound represented by formula (1) according to item [1] and a polymerizable monomer having two or more (meth)acryloyl groups, and the content of the compound represented by formula (1) is 0.5 to 4.0 wt % relative to the total amount of the compound represented by formula (1) and the polymerizable monomer.

[0015] [7] The silicone-containing copolymer according to any one of items [1] to [3], wherein the polymerizable monomer includes a polymerizable monomer having two or more acryloyl groups.

[0016] [8] The silicone-containing copolymer according to any one of items [1] to [3], wherein the polymerizable monomer includes a polymerizable monomer having three or more acryloyl groups.

[0017] [9] The silicone-containing copolymer according to item [4] or [7], wherein the composition contains the compound represented by formula (1) according to item [1] and a polymerizable monomer having two or more acryloyl groups, and the content of the compound represented by formula (1) is 0.5 to 4.0 wt % relative to the total amount of the compound represented by formula (1) and the polymerizable monomer.

[0018]

[10] The silicone-containing copolymer according to any one of items [1] to [3], wherein the polymerizable monomer includes a polymerizable monomer having one (meth)acryloyl group.

[0019]

[11] The silicone-containing copolymer according to item

[10] , wherein the composition contains the compound represented by formula (1) according to item [1] and a polymerizable monomer having one (meth)acryloyl group, and the content of the compound represented by formula (1) is 0.5 to 9.0 wt % relative to the total amount of the compound represented by formula (1) and the polymerizable monomer.

[0020]

[12] The silicone-containing copolymer according to item

[10] , wherein the composition contains the compound represented by formula (1) according to item [1] and a polymerizable monomer having one methacryloyl group, and the content of the compound represented by formula (1) is 0.5 to 9.0 wt % relative to the total amount of the compound represented by formula (1) and the polymerizable monomer.

[0021]

[13] The silicone-containing copolymer according to any one of items [1] to

[12] , wherein the silicone-containing copolymer is obtained by ultraviolet irradiation.

[0022]

[14] The silicone-containing copolymer according to any one of items [1] to

[12] , wherein the silicone-containing copolymer is obtained by thermal polymerization.

[0023]

[15] A cured product comprising the silicone-containing copolymer according to any one of items [1] to

[14] and reacted with a crosslinking agent.

[0024]

[16] A method for producing the silicone-containing copolymer according to any one of items [1] to

[14] .

[0025]

[17] A photocurable resin composition comprising a compound represented by formula (1) and a polymerizable monomer having two or more acryloyl groups, wherein the content of the compound represented by formula (1) is 0.5 to 4.0 wt % relative to the total amount of the compound represented by formula (1) and the polymerizable monomer. In formula (1), n ​​is an integer of 0 to 300, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and R ９ , and R １０ are each independently hydrogen or methyl; X １ , X ２ , X ３ , X ４ are each independently an alkylene having 1 to 20 carbon atoms.

[0026]

[18] A thermosetting resin composition comprising a compound represented by formula (1) and a polymerizable monomer having one methacryloyl group, wherein the content of the compound represented by formula (1) is 0.5 to 9.0 wt % relative to the total amount of the compound represented by formula (1) and the polymerizable monomer. In formula (1), n ​​is an integer of 0 to 300, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and R ９ , and R １０ are each independently hydrogen or methyl; X １ , X ２ , X ３ , and X ４ are each independently an alkylene having 1 to 20 carbon atoms.

[0027] The silicone compound used as the raw material for the silicone-containing copolymer of the present invention is compatible with other polymerizable monomers, making it possible to provide a transparent copolymer. Furthermore, the copolymer can be used to provide articles such as resist materials, paints, coating materials, ophthalmic devices, and 3D printers.

[0028] The present invention will be described in detail below. The following description of the constituent elements may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In the present invention, a "compound represented by formula (1)" may be referred to as a "compound of formula (1)." In the present invention, a composition containing a compound represented by formula (1) may be referred to as a "raw material composition," and a copolymer obtained by polymerizing the raw material composition may be referred to as a "copolymer of the present invention" or a "polymer of the present invention." "(Meth)acrylate" means "either one or both of an acrylate and a methacrylate." "(Meth)acryloyl group" means "either one or both of an acryloyl group and a methacryloyl group."

[0029] <Silicone-Containing Copolymer> The silicone-containing copolymer of the present invention can be obtained by copolymerizing a raw material composition containing the compound represented by formula (1) and a polymerizable monomer by light irradiation or heat.

[0030] <Compound Represented by Formula (1)> The compound represented by formula (1) is a silicone compound having a (meth)acryloyl group. In formula (1), n ​​is an integer of 0 to 300; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms; R ９ , and R １０ are each independently hydrogen or methyl; X １ , X ２ , X ３ , and X ４are each independently an alkylene having 1 to 20 carbon atoms.

[0031] Here, the "alkyl having 1 to 30 carbon atoms" may be any of a linear group having 1 to 30 carbon atoms, a branched group having 3 to 30 carbon atoms, and a cyclic group having 3 to 30 carbon atoms, and the "alkylene having 1 to 20 carbon atoms" may be any of a linear group having 1 to 20 carbon atoms and a branched group having 3 to 20 carbon atoms.

[0032] The number average molecular weight (Mn) of the compound represented by formula (1) is preferably small in order to prevent deterioration of compatibility with the polymerizable monomer, and is preferably large in order to express the physical properties of silicone, and is therefore preferably 500 to 20,000, more preferably 500 to 15,000, and even more preferably 500 to 10,000.

[0033] The molecular weight distribution (Mw / Mn) of the compound represented by formula (1) is preferably 1 to 2, more preferably 1 to 1.5, and even more preferably 1 to 1.3, in order to exhibit good silicone properties.

[0034] The number average molecular weight (Mn) and weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC). In this case, polystyrene is used as a standard sample, and the number average molecular weight (Mn) and weight average molecular weight (Mw) of the compound represented by formula (1) are determined by calculating the molecular weight in terms of polystyrene. The molecular weight distribution can be calculated by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

[0035] The compound represented by formula (1) is compatible with polymerizable monomers. The reason why the compound is compatible with polymerizable monomers is not entirely clear, but is thought to be as follows.

[0036] Generally, silicones are hydrophobic and therefore difficult to dissolve in polymerizable monomers. However, the compound represented by formula (1) has two urethane bonds in the molecule, and the urethane bonds exhibit strong hydrogen bonding, making it hydrophilic. Therefore, the hydrophobicity of the entire molecule is reduced, and it is thought that the compound is compatible with polymerizable monomers.

[0037] The compound represented by formula (1) has two (meth)acryloyl groups, and therefore, when the raw material composition is polymerized, the compound represented by formula (1) can be easily crosslinked.

[0038] An example of the compound represented by formula (1) is a compound represented by the following formula (2). In formula (2), n is an integer of 0 to 300; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms; R ９ , and R １０ are each independently hydrogen or methyl.

[0039] A preferred example of the compound represented by formula (2) is a compound represented by the following formula (3). In formula (3), n is an integer of 0 to 300; R ９ , and R １０ are each independently hydrogen or methyl.

[0040] For the method of producing the compound represented by formula (3), reference can be made to JP 2017-8124 A.

[0041] In a composition containing a compound represented by formula (1) and a polymerizable monomer for producing the copolymer of the present invention, a certain amount of the compound represented by formula (1) is required to exhibit the physical properties of silicone, and even if the compound contains more than a certain amount, the physical properties of the copolymer do not change. When the copolymer of the present invention is obtained by photoirradiation, the amount of the compound represented by formula (1) is preferably 0.01 to 40 wt%, more preferably 0.1 to 10 wt%, and even more preferably 0.5 to 4.0 wt%, based on the total amount of the compound represented by formula (1) and the polymerizable monomer. When the copolymer of the present invention is obtained by thermal polymerization, the amount of the compound represented by formula (1) is preferably 0.01 to 40 wt%, more preferably 0.1 to 10 wt%, and even more preferably 0.5 to 9.0 wt%, based on the total amount of the compound represented by formula (1) and the polymerizable monomer.

[0042] <Polymerizable Monomer> The compound represented by formula (1) has good compatibility with polymerizable monomers and can be suitably used as a raw material for a silicone-containing copolymer. The other polymerizable monomer used as a raw material for the silicone-containing copolymer can be selected without limitation from monomers having a polymerizable group. Examples of the polymerizable group include a (meth)acryloyl group, an ethylenic double bond, and maleimide. Polymerizable monomers having a (meth)acryloyl group can be classified as monofunctional (meth)acrylates, where a polymerizable monomer has one (meth)acryloyl group in the molecule, and as polyfunctional (meth)acrylates, where a polymerizable monomer has two or more (meth)acryloyl groups in the molecule. The polymerizable monomer may be one type or two or more types.

[0043] Examples of monofunctional (meth)acrylates are listed below.

[0044] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, ethoxydiethylene glycol acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, methoxypolyethylene glycol acrylate, polyalkylene glycol acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone, methyl acrylate ... lactone-added tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl alcohol acrylic acid polymer ester, 2-phenoxyethyl acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, γ-butyrolactone (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3,Examples of the methacrylate include 5-dimethyl-7-hydroxyadamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, methacryloyloxynorbornane (meth)acrylate, tetramethylpiperidinyl (meth)acrylate, pentamethylpiperidinyl (meth)acrylate, (meth)acrylates having an imide ring, cyclic trimethylolpropane formal (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate.

[0045] Examples of polyfunctional (meth)acrylates are listed below.

[0046] Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A alkylene oxide adduct di(meth)acrylate, bisphenol F alkylene oxide adduct di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol Examples of the alkylene oxide-added tris(methacryloxyethyl)isocyanurate include tetra(meth)acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added tris((meth)acryloxyethyl)isocyanurate, di((meth)acryloyloxyethyl)isocyanurate, tri((meth)acryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate.

[0047] The polyfunctional acrylate may also be urethane (meth)acrylate, which can be obtained by reacting a polyfunctional isocyanate with a polyfunctional hydroxy compound, followed by further reacting the resulting mixture with a hydroxyl group-containing (meth)acrylate and, if necessary, a hydroxyl group-containing allyl ether compound.

[0048] <Polyfunctional Isocyanate> The number of isocyanate groups (-N=C=O) in the polyfunctional isocyanate is usually 2 or more, preferably 2 to 6. Examples of polyfunctional isocyanates include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate. Commercially available products include Burnock D-750 (manufactured by DIC Corporation), Crisvon NK (manufactured by DIC Corporation), Desmodur L (manufactured by Sumika Covestro Urethane Co., Ltd.), Coronate L (manufactured by Tosoh Corporation), Takenate D-102 (manufactured by Mitsui Chemicals, Inc.), and Isonate 143L (manufactured by Dow Chemical Japan Co., Ltd.).

[0049] <Polyfunctional Hydroxy Compound> The polyfunctional hydroxy compound refers to, for example, a compound having a number of hydroxy groups (—OH) of usually 2 or more, preferably 2 to 4. Examples of the polyfunctional hydroxy compound include polyether polyol, polyester polyol, and polycarbonate polyol.

[0050] Examples of polyether polyols include glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, and dipentaerythritol-ethylene oxide propylene oxide adduct.

[0051] Examples of polyester polyols include polycondensates obtained by reacting a polyhydric alcohol with a polybasic acid under known conditions. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, p-xylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2,7-decalin glycol, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A.

[0052] Examples of polybasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, and other saturated aliphatic dicarboxylic acids (having 11 to 13 carbon atoms); for example, maleic acid, fumaric acid, itaconic acid, and other unsaturated aliphatic dicarboxylic acids; for example, orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, and other aromatic dicarboxylic acids; for example, hexahydrophthalic acid, and other alicyclic dicarboxylic acids. Examples of the acid include carboxylic acids such as dimer acid, hydrogenated dimer acid, HET acid, and other carboxylic acids; acid anhydrides derived from these carboxylic acids such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (having 12 to 18 carbon atoms) succinic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride; and acid halides derived from these carboxylic acids such as oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.

[0053] Examples of polycarbonate polyols include ring-opening polymers of one or more of ε-caprolactone, γ-butyrolactone, γ-valerolactone, etc., and copolymers of ring-opening polymers with dihydric alcohols such as 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.

[0054] Examples of the polyfunctional hydroxy compound include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, an adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, and 2,7-decalin glycol.

[0055] <Hydroxyl Group-Containing (Meth)acrylate> The hydroxyl group-containing (meth)acrylate is preferably, for example, a hydroxyl group-containing (meth)acrylic acid ester, and specific examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, di(meth)acrylate of tris(hydroxyethyl)isocyanuric acid, and pentaerythritol tri(meth)acrylate.

[0056] When the copolymer of the present invention is obtained by photoirradiation, the polymerizable monomer preferably contains a polymerizable monomer having two or more (meth)acryloyl groups, more preferably a polymerizable monomer having three or more (meth)acryloyl groups, from the viewpoint of curability. Also, from the viewpoint of curability, the polymerizable monomer preferably contains a polymerizable monomer having two or more acryloyl groups, more preferably a polymerizable monomer having three or more acryloyl groups.

[0057] When the polymerizable monomer includes a polymerizable monomer having two or more (meth)acryloyl groups, in a composition containing the compound represented by formula (1) and the polymerizable monomer for producing the copolymer of the present invention, the content of the polymerizable monomer having two or more (meth)acryloyl groups is preferably 60 to 99.9 wt %, more preferably 90 to 99.9 wt %, and even more preferably 96 to 99.9 wt %, based on the total amount of the compound represented by formula (1) and the polymerizable monomer, from the viewpoint of curability.

[0058] When the copolymer of the present invention is obtained by thermal polymerization, the polymerizable monomer preferably contains a polymerizable monomer having one (meth)acryloyl group, for ease of handling.

[0059] When the polymerizable monomer includes a polymerizable monomer having one (meth)acryloyl group, in a composition containing the compound represented by formula (1) and the polymerizable monomer for producing the copolymer of the present invention, the content of the polymerizable monomer having one (meth)acryloyl group is preferably 50 to 99.9 wt %, more preferably 80 to 99.9 wt %, and even more preferably 91 to 99.9 wt %, based on the total amount of the compound represented by formula (1) and the polymerizable monomer.

[0060] <Polymerization initiator> The silicone-containing copolymer of the present invention may contain a polymerization initiator in the raw material composition. The polymerization initiator is preferably a thermal polymerization initiator that generates radicals when heated, or a photopolymerization initiator that generates radicals when irradiated with ultraviolet or visible light. One type of polymerization initiator may be used, or two or more types may be used.

[0061] <Thermal Polymerization Initiator> The thermal polymerization initiator is not particularly limited as long as it is a compound that can generate radicals by heat, but azo-based or peroxide-based thermal polymerization initiators are preferred.

[0062] Examples of the azo-based thermal polymerization initiator include 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, ... midazolin-2-yl)propane], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n hydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(isobutyric acid) dimethyl, 4,4'-azobis(4-cyanovaleric acid), 1-[(1-cyano-1-methylethyl)azo]formamide.

[0063] Examples of peroxide-based thermal polymerization initiators include benzoyl peroxide, t-butyl hydroperoxide, 1-methyl-1-phenylethyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, di-t-hexyl peroxide, didodecanoyl peroxide, 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxybenzoate, and t-butylperoxybenzoate.

[0064] Among these, 2,2'-azobisisobutyronitrile and 2,2'-azobis(2-methylpropionate)dimethyl are preferred because of their excellent curability.

[0065] <Photopolymerization Initiator> The photopolymerization initiator is not particularly limited as long as it is a compound that can generate radicals when irradiated with ultraviolet or visible light, but an α-hydroxyl alkylphenone-based photopolymerization initiator is preferred.

[0066] Examples of the photopolymerization initiator include benzophenone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, camphorquinone, benzanthrone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, oxy-phenyl-acetic acid 2-(2-oxo-2-phenyl-acetoxy-ethoxy)-ethyl ester, oxy-phenyl-acetic acid 2-(2-hydroxy-ethoxy)-ethyl ester, oxy-phenyl-acetic acid 2-(2-oxo-2-phenyl-acetoxy-ethoxy)-ethyl ester and oxy-phenyl-acetic acid Mixtures with 2-(2-hydroxy-ethoxy)-ethyl ester of phenylglyoxylic acid methyl ester, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl) )-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxide Sazol, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2, 4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0067] Among these, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one, and 1-hydroxycyclohexyl phenyl ketone are preferred because of their excellent sensitivity to ultraviolet light.

[0068] <Solvent> The raw material composition of the silicone-containing copolymer of the present invention may contain a solvent. By containing a solvent, the compatibility of the compound represented by formula (1) with the raw material composition can be improved. Preferred examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, benzonitrile, ethyl acetate, isobutyl acetate, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxyisobutyrate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, methyl 3-methoxyisobutyrate, dioxane, ethylene glycol, diethyl ether, diethylene glycol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, glycerin, benzyl alcohol, cyclohexanol, 1,4-butanediol, triethylene glycol, tripropylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate Examples of the solvent include dipropylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, toluene, xylene, anisole, γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, and dimethylimidazolidinone. The solvent may be one type or two or more types.

[0069] Among these, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, butyl acetate, methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, N,N-dimethylacetamide, N,N-dimethylformamide, and N,N-diethylformamide are preferred because they have high solubility in the raw material composition and can shorten the drying time.

[0070] <Other Components> The copolymer of the present invention may contain other components. The other components can be selected and used according to the respective purposes in order to improve various properties of the article containing the silicone-containing copolymer. Examples of other components include silicone compounds other than the compound represented by formula (1), surfactants, fine particles, polymerization inhibitors, flame retardants, UV absorbers, light stabilizers, antioxidants, and pigments.

[0071] <Method for Producing Silicone-Containing Copolymer> Next, the silicone-containing copolymer of the present invention and its method for producing it will be described. The silicone-containing copolymer of the present invention can be obtained by polymerizing (curing) a raw material composition containing a compound represented by formula (1) and a polymerizable monomer.

[0072] The silicone-containing copolymer of the present invention can be obtained by a conventional method for producing a silicone-containing copolymer from a raw material composition. The silicone-containing copolymer can be obtained by applying the raw material composition to a substrate or pouring it into a mold and polymerizing (curing) it by ultraviolet irradiation or by baking it. Alternatively, the silicone-containing copolymer can be obtained by preheating the raw material composition, polymerizing the resulting solution, applying it to a substrate or pouring it into a mold and baking it. The method for producing the silicone-containing copolymer of the present invention is described below.

[0073] The substrate or mold may be made of aluminum foil, glass, silicon nitride, acrylic, polycarbonate, polyimide, etc. Commonly known methods for applying the coating to the substrate include spinning, printing, dipping, dropping, and inkjet methods. These methods are also applicable to the present invention.

[0074] In the case of a raw material composition containing a solvent, a drying treatment may be carried out to remove the solvent before ultraviolet irradiation or heating and baking. Commonly known drying methods include drying in an oven or infrared furnace, and drying on a hot plate. The drying treatment is preferably carried out at a temperature within a range that allows evaporation of the solvent, and more preferably at a temperature relatively lower than the temperature used for heating and baking. Although it depends on the composition of the raw material composition, the drying temperature is usually 70 to 120°C, and the drying time is, for example, 5 to 15 minutes if using an oven or 1 to 10 minutes if using a hot plate.

[0075] The substrate or mold onto which the raw material composition has been applied can be polymerized by irradiating it with ultraviolet light or by baking it with heat to obtain a silicone-containing copolymer. Baking may be performed after ultraviolet light irradiation, after baking with heat, or while baking with UV light.

[0076] As the light source for ultraviolet irradiation, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a deep UV lamp, a halogen lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a mercury xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave excited electrodeless lamp, and the like can be used without limitation.

[0077] The heating and baking can be carried out under conditions necessary to remove traces of residual solvent after drying or under conditions necessary for polymerizing the raw material composition. Commonly known methods of heating and baking include heating in an oven or infrared furnace, and heating on a hot plate. The heating temperature is preferably in the range of 70°C to 300°C, and more preferably in the range of 100°C to 250°C. The heating time is preferably 1 minute to 5 hours, and more preferably 10 minutes to 2 hours. The temperature during heating and baking can be increased gradually; for example, heating and baking can be carried out multiple times at different temperatures while gradually increasing the temperature, or heating can be carried out by changing the temperature from low to high. Alternatively, both heating methods can be combined.

[0078] When the raw material composition is preheated and polymerized, a copolymer solution can be obtained by heating the raw material composition containing a solvent while stirring. The heating temperature is preferably in the range of 30°C to 300°C, and more preferably in the range of 50°C to 200°C. The heating time is preferably 1 minute to 100 hours, and more preferably 30 minutes to 50 hours. The copolymer solution can be applied to a substrate or poured into a mold, dried, and then heated and baked to obtain a silicone-containing copolymer.

[0079] It is also possible to add another polymer to the copolymer solution to use a copolymer solution containing two or more types of polymers.

[0080] The method for producing the silicone-containing copolymer of the present invention may further include other steps in addition to the steps described above, such as surface modification.

[0081] The silicone-containing copolymer of the present invention can be used in articles such as resist materials, paints, coating materials, ophthalmic devices, and 3D printers.

[0082] The present invention will be described below with reference to examples, in which the compounds used are as follows:

[0083] <Compounds Represented by Formula (1)> Of the compounds represented by formula (1), silicone compounds X to Z were used in the examples. The structural formula of silicone compound X is represented by formula (3-1), and the structural formulas of silicone compounds Y and Z are represented by formula (3-2).

[0084] The molecular weight of the compound represented by formula (1) was measured by the following method, and the results are shown in Table 1.

[0085] The molecular weight was measured by gel permeation chromatography (GPC), and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was defined as the molecular weight distribution (Mw / Mn). Polystyrene was used as a standard sample to measure the molecular weight in terms of polystyrene. The polystyrene-equivalent molecular weight measurement by GPC was carried out under the following measurement conditions: a) Measuring instrument: JASCO Corporation HPLC LC-2000Plus series b) Column: Shodex KF-804L x 2 (in series) c) Oven temperature: 40°C d) Eluent: toluene 0.7 mL / min e) Standard sample: polystyrene f) Injection amount: 20 μL g) Concentration: 0.05 g / 10 mL h) Sample preparation for molecular weight measurement: Toluene was used as a solvent and dissolved by stirring at room temperature.

[0086] [Table 1]

[0087] <Compounds used in Comparative Examples> FM-0711: One-terminal methacrylic-modified organosilicon compound (trade name: Silaplane FM-0711, manufactured by JNC Corporation, number average molecular weight: 1000) FM-0721: One-terminal methacrylic-modified organosilicon compound (trade name: Silaplane FM-0721, manufactured by JNC Corporation, number average molecular weight: 5000)

[0088] <Polymerizable Monomers> BMA: butyl methacrylate GMA: glycidyl methacrylate A-HD-N: 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) TMAPTA: trimethylolpropane triacrylate M-305: pentaerythritol tri- and tetraacrylate (trade name: Aronix M-305, manufactured by Toagosei Co., Ltd.) A-DPH: dipentaerythritol polyacrylate (trade name: NK Ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0089] <Polymerization initiator> Polymerization initiator A: 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone Polymerization initiator B: 2,2'-azobis(2-methylpropionate)dimethyl <Solvent> PGMEA: propylene glycol monomethyl ether acetate

[0090] <Preparation of Photocurable Resin Composition> The photocurable resin composition used in this example was prepared according to the following procedure.

[0091] Preparation Example 1 Preparation of Photocurable Resin Composition A1 Silicone compound X (0.0364 g, 1 part by weight), TMPTA (3.6 g, 99 parts by weight), polymerization initiator A (0.3636 g, 10 parts by weight), and PGMEA (1.0 g) were mixed to prepare a photocurable resin composition with a concentration of 80% by weight.

[0092] [Preparation Examples 2 to 9] Preparation of photocurable resin compositions A2 to A6 and C1 to C6 Photocurable resin compositions A2 to A6 and C1 to C6 were prepared in the same manner as in Preparation Example 1, except that the compound represented by formula (1), polymerizable monomer, polymerization initiator, solvent, and concentration were changed as shown in Table 2.

[0093] <Evaluation of Appearance of Photocurable Resin Composition> The appearance of the prepared photocurable resin composition was visually confirmed. If the silicone compound and the polymerizable monomer have good compatibility, a transparent, uniform solution can be obtained. On the other hand, if the compatibility is poor, the photocurable resin composition becomes cloudy or undergoes phase separation. The results are shown in Table 2. In Table 2, the numbers in square brackets represent weight ratios.

[0094] [Table 2]

[0095] The photocurable resin compositions A1 to A6 of the present invention using the compound represented by formula (1) are transparent and homogeneous solutions, and can be said to have excellent compatibility with polymerizable monomers.

[0096] <Evaluation of Coatability> The prepared photocurable resin composition was spin-coated on a glass substrate at 1000 rpm for 10 seconds, and then pre-baked on a hot plate at 100° C. for 2 minutes. Further, the coating was heated with a high-pressure mercury lamp (H08-L41, rated power 160 W / cm, manufactured by Iwasaki Electric Co., Ltd.). ２ ) was used, and the illuminance was 200 mW / cm ２ , exposure dose 1000 mJ / cm ２The substrate was irradiated with ultraviolet light at 1000 kJ / min at 1000 kJ / min, thereby obtaining a glass substrate with a cured film having a film thickness of 5 μm. The exposure dose was measured using an illuminance meter (UVPF-A1 / PD-365) manufactured by Iwasaki Electric Co., Ltd. The appearance of the glass substrate with the cured film was visually confirmed. If a uniform and transparent cured film was formed, the coatability was good and the coating was evaluated as "Good." On the other hand, if liquid or gel-like components remained on the surface of the cured film, i.e., if there was uncured material or if the cured film was cloudy or uneven, the coating was unsuitable and evaluated as "Poor."

[0097] <Measurement of Contact Angle> The prepared photocurable resin composition was spin-coated on a glass substrate at 1000 rpm for 10 seconds, and then pre-baked on a hot plate at 100° C. for 2 minutes. Further, a high-pressure mercury lamp (H08-L41, rated 160 W / cm, manufactured by Iwasaki Electric Co., Ltd.) was used to measure the contact angle. ２ ) was used, and the illuminance was 200 mW / cm ２ , exposure dose 1000 mJ / cm ２ The substrate was irradiated with ultraviolet light at 1000 K, and then heated in an oven at 230°C for 30 minutes to obtain a glass substrate with a cured film having a thickness of 5 μm. The exposure dose was measured using an illuminance meter (UVPF-A1 / PD-365) manufactured by Iwasaki Electric Co., Ltd. 2 μL of water and diiodomethane were dropped onto the glass substrate with the cured film, and the contact angle was measured using a contact angle measuring device (trade name: Drop Master DM500, manufactured by Kyowa Interface Science Co., Ltd.). A contact angle of water greater than 95° is considered to be good. In addition, the contact angle of diiodomethane (CH ２ I ２ ) is considered to be good if the contact angle is greater than 50°. <Evaluation of antifouling properties> The prepared photocurable resin composition was spin-coated on a glass substrate at 1000 rpm for 10 seconds, and then pre-baked on a hot plate at 100°C for 2 minutes. Further, a high-pressure mercury lamp (H08-L41, rated 160 W / cm, manufactured by Iwasaki Electric Co., Ltd.) was used for the coating. ２ ) was used, and the illuminance was 200 mW / cm ２ , exposure dose 1000 mJ / cm ２The substrate was then irradiated with ultraviolet light at 1000 rpm, followed by heating in an oven at 230°C for 30 minutes to obtain a glass substrate with a cured film having a thickness of 5 μm. The exposure dose was measured using an illuminance meter (UVPF-A1 / PD-365) manufactured by Iwasaki Electric Co., Ltd. A line was drawn on the glass substrate with the cured film using Hi-Mackey (registered trademark) (black) manufactured by Zebra Corporation, and then wiped off with Kimwipe (registered trademark) manufactured by Nippon Paper Crecia Co., Ltd. If no trace of the line remained, the stain resistance was good and was evaluated as "Good." If the trace of the line could be confirmed, it was evaluated as "Poor." <Measurement of pencil hardness> The prepared photocurable resin composition was spin-coated on a glass substrate at 1000 rpm for 10 seconds, and then pre-baked on a hot plate at 100°C for 2 minutes. Further, a high-pressure mercury lamp (H08-L41, rated 160 W / cm) manufactured by Iwasaki Electric Co., Ltd. was used to draw a line. ２ ) was used, and the illuminance was 200 mW / cm ２ , exposure dose 1000 mJ / cm ２ The glass substrate was irradiated with ultraviolet light at 1000 K, and then heated in an oven at 230°C for 30 minutes to obtain a glass substrate with a cured film having a film thickness of 5 μm. The exposure dose was measured using an illuminance meter (UVPF-A1 / PD-365) manufactured by Iwasaki Electric Co., Ltd. The pencil hardness of the cured film was measured by subjecting the glass substrate with the cured film to the scratch hardness test (pencil method) according to JIS K-5600-5-4. A pencil hardness of 3H or more was evaluated as ◯, which means that the scratch resistance was good. A pencil hardness of 2H or less was evaluated as ×.

[0098] [Example 1] When the coatability of the photocurable resin composition A1 was visually confirmed, a uniform and transparent cured film was formed, and therefore it was rated as "good." When the contact angle of water was measured, it was 96°. Similarly, when the contact angle of diiodomethane was measured, it was 56°. When the antifouling property was evaluated, no line marks remained, and therefore it was rated as "good." When the pencil hardness was measured, it was 3H, and therefore it was rated as "good."

[0099] Examples 2 to 6, Comparative Examples 1 to 6 Evaluation of coating properties and measurement of contact angles were carried out in the same manner as in Example 1, except that the photocurable resin composition was changed as shown in Table 3. The results are shown in Table 3 together with the results of Example 1. Evaluation of antifouling properties and measurement of pencil hardness were carried out in the same manner as in Example 1, except that the photocurable resin composition was changed as shown in Table 4. The results are shown in Table 4 together with the results of Example 1. In Examples 3 and 4 and Comparative Example 1, pre-baking was not carried out in the production of the cured film-coated glass substrates.

[0100] [Table 3]

[0101] [Table 4]

[0102] The copolymers of the present invention, photocurable resin compositions A1 to A6, which used a compound represented by formula (1), exhibited good coatability. Furthermore, the contact angles with water and diiodomethane were good, indicating excellent water and oil repellency. Furthermore, the stain resistance and pencil hardness were good. On the other hand, the copolymers of photocurable resin compositions C1 to C3 and C5, which did not use a compound represented by formula (1), exhibited poor coating properties, low contact angles with water and diiodomethane, and the stain resistance and pencil hardness of the copolymer of photocurable resin composition C5 were poor. The copolymers of photocurable resin compositions C4 and C6 exhibited good coatability, but low contact angles with water and diiodomethane, and poor stain resistance and pencil hardness.

[0103] [Example 7] Preparation of composition Silicone compound X (0.96 g, 3 parts by weight), BMA (24.64 g, 77 parts by weight), GMA (6.4 g, 20 parts by weight), polymerization initiator B (1.60 g, 5 parts by weight), and PGMEA (19.2 g) were mixed to prepare composition B1 with a concentration of 63 wt%.

[0104] [Examples 8-9, Comparative Example 7] Preparation of Compositions B2-B3, and D1 Compositions B2-B3, and D1 were prepared in the same manner as in Example 7, except that the compound represented by formula (1), polymerizable monomer, polymerization initiator, solvent, and concentration were changed as shown in Table 5. In Table 5, the values ​​in square brackets represent weight ratios.

[0105] [Table 5]

[0106] <Evaluation of the Appearance of the Copolymer Solution> PGMEA (28.8 g) was placed in a 100 mL three-neck flask equipped with a stirring blade and a nitrogen inlet tube, and heated to 100°C under a nitrogen atmosphere. The prepared composition was added dropwise to the solvent, and the mixture was stirred at 100°C for 1 hour to polymerize, preparing a 40 wt% copolymer solution. The appearance of the copolymer solution was visually confirmed. If a uniform copolymerization reaction was achieved and the resulting copolymer had good compatibility with the solvent, a transparent, uniform solution could be obtained. On the other hand, if the copolymerization reaction proceeded unevenly and the resulting copolymer contained copolymers with poor compatibility with the solvent, the copolymer solution would become cloudy or phase-separated.

[0107] <Measurement of Contact Angle> The prepared copolymer solution was spin-coated onto a glass substrate at 600 rpm for 10 seconds, and then pre-baked on a hot plate at 100°C for 2 minutes. Further, by heating in an oven at 200°C for 30 minutes, a glass substrate with a cured film having a film thickness of 5 μm was obtained. The exposure dose was measured using an illuminance meter (UVPF-A1 / PD-365) manufactured by Iwasaki Electric Co., Ltd. 2 μL of water and diiodomethane were dropped onto the glass substrate with the cured film, and the contact angle was measured using a contact angle measuring device (trade name: Drop Master DM500, manufactured by Kyowa Interface Science Co., Ltd.). A contact angle of water greater than 95° is considered to be good. Furthermore, the contact angle of diiodomethane (CH ２ I ２ ) is considered to be good if the contact angle is greater than 50°.

[0108] [Example 10] The appearance of the copolymer solution of Composition B1 was transparent and uniform. In addition, the contact angle of water on a glass substrate with a cured film prepared from the copolymer solution of Composition B1 was measured and found to be 97°. Similarly, the contact angle of diiodomethane was measured and found to be 56°.

[0109] [Examples 11 and 12, Comparative Example 8] Preparation of copolymer solutions and measurement of contact angles were carried out in the same manner as in Example 10, except that the compositions were changed as shown in Table 6. The results are shown in Table 6 together with the results of Example 10.

[0110] [Table 6]

[0111] The copolymer solutions of compositions B1 to B3, which used the compound represented by formula (1), were transparent and homogeneous. Furthermore, the contact angles of water and diiodomethane of the cured films were good, indicating excellent water and oil repellency. On the other hand, the contact angle of copolymer solution D1, which did not use a silicone compound, did not exhibit a good value.

[0112] The silicone compound used as the raw material for the silicone-containing copolymer of the present invention is highly compatible with polymerizable monomers. The silicone-containing copolymer of the present invention has excellent water repellency, oil repellency, stain resistance, and scratch resistance, and is suitable for use in resist materials, paints, coating materials, ophthalmic devices, 3D printers, and other products.

Claims

1. A silicone-containing copolymer obtained by polymerizing a composition containing a compound represented by formula (1) and a polymerizable monomer. In formula (1), n ​​is an integer from 0 to 300; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms; R ９ , and R １０ are each independently hydrogen or methyl; X １ , X ２ , X ３ , and X ４ are each independently an alkylene having 1 to 20 carbon atoms.

2. The silicone-containing copolymer according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (2). In formula (2), n is an integer from 0 to 300; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms; R ９ , and R １０ are each independently hydrogen or methyl.

3. The silicone-containing copolymer according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (3). In formula (3), n is an integer from 0 to 300; R ９ , and R １０ are each independently hydrogen or methyl.

4. The silicone-containing copolymer according to claim 1, wherein the polymerizable monomer comprises a polymerizable monomer having two or more (meth)acryloyl groups.

5. The silicone-containing copolymer according to claim 1, wherein the polymerizable monomer comprises a polymerizable monomer having three or more (meth)acryloyl groups.

6. The silicone-containing copolymer according to claim 4, wherein in a composition comprising the compound represented by formula (1) according to claim 1 and a polymerizable monomer having two or more (meth)acryloyl groups, the content of the compound represented by formula (1) is 0.5 to 4.0% by weight based on the total amount of the compound represented by formula (1) and the polymerizable monomer.

7. The silicone-containing copolymer according to claim 1, wherein the polymerizable monomer comprises a polymerizable monomer having two or more acryloyl groups.

8. The silicone-containing copolymer according to claim 1, wherein the polymerizable monomer comprises a polymerizable monomer having three or more acryloyl groups.

9. The silicone-containing copolymer according to claim 7, wherein in a composition comprising the compound represented by formula (1) according to claim 1 and a polymerizable monomer having two or more acryloyl groups, the content of the compound represented by formula (1) is 0.5 to 4.0% by weight based on the total amount of the compound represented by formula (1) and the polymerizable monomer.

10. The silicone-containing copolymer according to claim 1, wherein the polymerizable monomer comprises a polymerizable monomer having one (meth)acryloyl group.

11. The silicone-containing copolymer according to claim 10, wherein in a composition comprising the compound represented by formula (1) according to claim 1 and a polymerizable monomer having one (meth)acryloyl group, the content of the compound represented by formula (1) is 0.5 to 9.0% by weight based on the total amount of the compound represented by formula (1) and the polymerizable monomer.

12. The silicone-containing copolymer according to claim 10, wherein in a composition comprising the compound represented by formula (1) according to claim 1 and a polymerizable monomer having one methacryloyl group, the content of the compound represented by formula (1) is 0.5 to 9.0% by weight based on the total amount of the compound represented by formula (1) and the polymerizable monomer.

13. The silicone-containing copolymer of claim 1, wherein the silicone-containing copolymer is obtained by ultraviolet irradiation.

14. The silicone-containing copolymer of claim 1, wherein said silicone-containing copolymer is obtained by thermal polymerization.

15. A cured product comprising the silicone-containing copolymer according to any one of claims 1 to 14 and produced by reacting with a crosslinking agent.

16. A method for producing the silicone-containing copolymer according to any one of claims 1 to 14.

17. A photocurable resin composition comprising a compound represented by formula (1) and a polymerizable monomer having two or more acryloyl groups, wherein the content of the compound represented by formula (1) is 0.5 to 4.0% by weight based on the total amount of the compound represented by formula (1) and the polymerizable monomer. In formula (1), n ​​is an integer from 0 to 300; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms; R ９ , and R １０ are each independently hydrogen or methyl; X １ , X ２ , X ３ , and X ４ are each independently an alkylene having 1 to 20 carbon atoms.

18. A thermosetting resin composition comprising a compound represented by formula (1) and a polymerizable monomer having one methacryloyl group, wherein the content of the compound represented by formula (1) is 0.5 to 9.0% by weight based on the total amount of the compound represented by formula (1) and the polymerizable monomer. In formula (1), n ​​is an integer from 0 to 300; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently hydrogen or alkyl having 1 to 30 carbon atoms; R ９ , and R １０ are each independently hydrogen or methyl; X １ , X ２ , X ３ , and X ４ are each independently an alkylene having 1 to 20 carbon atoms.

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