Curing resin composition and molded article and method for producing the same

Abstract

The present invention provides a curable resin composition having excellent transparency and impact resistance of the obtained molded product. The curable resin composition contains a polycarbonate resin and a styrene-based monomer, wherein the polycarbonate resin contains a terminal structure having an unsaturated group represented by the following formula (1) and a structural unit represented by the following formula (2).

Description

Technical Field

[0001] The present invention relates to a curing resin composition, a molded product and a method for producing the same. Background Art

[0002] Polycarbonate resins are widely used in applications such as lenses, cover parts of touch panels, and housings of devices due to their excellent impact resistance, heat resistance, electrical insulation, and dimensional stability. However, polycarbonate resins have room for improvement in optical properties such as large birefringence.

[0003] As a method for improving the above optical properties, a method for modifying a polycarbonate (PC) resin is known. For example, Patent Document 1 describes a method for producing a modified polycarbonate resin composition, characterized in that a mixture containing (A) a polycarbonate resin having a Tg of 170° C. or higher, (B) an aromatic vinyl monomer, and (C) a free radical polymerization initiator is melt-kneaded.

[0004] Patent Document 1 states that the photoelastic coefficient can be reduced by mixing a material having a negative intrinsic birefringence such as polystyrene with a polycarbonate resin having a large photoelastic coefficient. Patent Document 1 also states that the above-mentioned manufacturing method can reduce the photoelastic coefficient and solve the problems of insufficient transparency and secondary processability.

[0005] In addition, it is described that in the modified polycarbonate resin composition, the (B) aromatic vinyl monomer can be present in a state of being combined with the polycarbonate resin as a polymer of several to several dozen polymers or as a monomer by melt kneading, or can be present in a state of being mixed in the composition as a polymer of several to several dozen polymers or as a monomer. In addition, it is also described that as the above-mentioned (B) aromatic vinyl monomer, a styrene-based monomer is preferred.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2001-139791 Summary of the invention

[0009] Technical problem to be solved by the invention

[0010] However, it has been found that in the modified polycarbonate resin composition described in Patent Document 1, the compatibility of the polycarbonate resin with the styrene monomer or its polymer is not necessarily high, and the transparency and impact strength may not be sufficient.

[0011] Therefore, the present invention provides a curable resin composition which produces a molded article having excellent transparency and impact resistance.

[0012] Technical solutions for solving technical problems

[0013] The inventors of the present invention have conducted intensive research to solve the above technical problems. As a result, they have found that the above technical problems can be solved by using a predetermined polycarbonate resin and a styrene-based monomer, thereby completing the present invention. That is, the present invention includes the following solutions.

[0014] [1] A curable resin composition comprising a polycarbonate resin and a styrene-based monomer, wherein the polycarbonate resin comprises a terminal structure having an unsaturated group represented by the following formula (1) and a structural unit represented by the following formula (2),

[0015] Formula (1):

[0016]

[0017] (In the above formula (1),

[0018] A is vinyl, isopropenyl, styryl, or methine,

[0019] R1 and R2 are each independently selected from a single bond and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms,

[0020] R3 is independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 12 elements,

[0021] Z is independently selected from a single bond, an ether group, a carbonyl group and an ester group,

[0022] a is an integer from 1 to 3,

[0023] b is an integer from 2 to 4,

[0024] Y is an ether group or an ester group.)

[0025] Formula (2):

[0026]

[0027] (In the above formula (2),

[0028] R4 is independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 17 carbon atoms,

[0029] c are each independently an integer of 0 to 4,

[0030] X is selected from -C(R5)(R6)-, -S-, -(CH2) d -, -O-, -SO-, -CO-, -SO2- and groups represented by the following formulae (3) to (6),

[0031]

[0032] (In the above formulas (3) to (6),

[0033] R5 and R6 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or R5 and R6 are combined to form a carbocyclic group having 5 to 20 carbon atoms or a heterocyclic group having 5 to 12 elements,

[0034] R7 is each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms,

[0035] R8 is each independently a substituted or unsubstituted alkylene group having 1 to 9 carbon atoms,

[0036] d is an integer from 0 to 20,

[0037] e is an integer from 1 to 500.)

[0038] When both c are 0, X is not -C(CH3)2-).

[0039] [2] The curable resin composition according to [1] above, wherein the structural unit represented by the formula (2) comprises at least one selected from the following formulas (7) to (13):

[0040]

[0041] [3] The curable resin composition according to the above [1], wherein the structural unit represented by the above formula (2) is derived from a bisphenol compound.

[0042] [4] The curable resin composition according to [3], wherein the bisphenol compound comprises at least one selected from 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylmethane, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0043] [5] The curable resin composition according to any one of [1] to [4] above, wherein the polycarbonate resin further comprises a structural unit derived from bisphenol A represented by the following formula:

[0044]

[0045] [6] A curable resin composition as described in any one of [1] to [5] above, wherein in the above formula (1), A is an isopropenyl group or a methylenyl group, Z is a single bond or an ester group, R1 and R2 are each independently a single bond or an ethylene group, and R3 is each independently a hydrogen atom or a benzotriazole group.

[0046] [7] The curable resin composition according to [6] above, wherein the terminal structure having an unsaturated group represented by the above formula (1) is derived from 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole or p-isopropenylphenol.

[0047] [8] The curable resin composition according to any one of [1] to [7] above, wherein the styrene-based monomer contains styrene.

[0048] [9] The curable resin composition according to any one of [1] to [8] above, further comprising a radical polymerization initiator.

[0049]

[10] The curable resin composition according to any one of [1] to [9] above, wherein the polycarbonate resin has an intrinsic viscosity of 0.3 to 2.0 dL / g.

[0050]

[11] The curable resin composition as described in any one of [1] to

[10] above, wherein the content of the terminal structure having an unsaturated group represented by the above formula (1) is 0.2 mol% or more relative to the structural unit represented by the above formula (2).

[0051]

[12] A molded article obtained by curing the curing resin composition according to any one of [1] to

[11] above.

[0052]

[13] The molded article as described in

[12] above, which is a cast molded article.

[0053]

[14] A method for producing a molded article, comprising the step of curing the curing resin composition according to any one of [1] to

[11] above.

[0054] Effects of the Invention

[0055] According to the present invention, it is possible to provide a curable resin composition in which the resulting molded article has excellent transparency and impact resistance. DETAILED DESCRIPTION

[0056] <Curing resin composition>

[0057] The curing resin composition according to the present embodiment contains a polycarbonate resin and a styrene-based monomer, and may further contain a radical polymerization initiator, a solvent, an additive, and the like.

[0058] [Polycarbonate resin]

[0059] The polycarbonate resin has the function of improving the transparency and impact resistance of the molded article obtained from the curing resin composition, etc. In addition, the polycarbonate resin can exist in the molded article after the resin composition of the present invention is cured in the form of graft polymerization with a styrene-based monomer, the form of a polymer obtained by the reaction of unsaturated groups possessed by the polycarbonate resin, the form of a polycarbonate resin, etc.

[0060] The polycarbonate resin includes a terminal structure having an unsaturated group represented by the above formula (1) and a structural unit represented by the above formula (2). The polycarbonate resin may further include other terminal structures and other structural units.

[0061] The terminal structure having an unsaturated group represented by formula (1)

[0062] The terminal structure having an unsaturated group represented by formula (1) has a function of reacting with a styrene-based monomer to form a polymer when the curable resin composition is cured.

[0063] The terminal structure having an unsaturated group is represented by the following formula (1).

[0064]

[0065] A is a vinyl group, an isopropenyl group, a styryl group, or a methine group. Among these, A is preferably a vinyl group or an isopropenyl group, and more preferably an isopropenyl group.

[0066] R1 and R2 are each independently selected from a single bond and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

[0067] The alkylene group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, and pentylene.

[0068] The substituent is not particularly limited, and examples thereof include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a cyano group, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, and an alkylcarbonyloxy group having 2 to 10 carbon atoms.

[0069] The alkoxy group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy groups.

[0070] The alkoxycarbonyl group having 2 to 10 carbon atoms is not particularly limited, and examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl.

[0071] The alkylcarbonyloxy group having 2 to 10 carbon atoms is not particularly limited, and examples thereof include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, and butylcarbonyloxy groups.

[0072] Among the above, R1 and R2 are each independently preferably a single bond or a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms, and more preferably a single bond, a methylene group or an ethylene group.

[0073] R3 is independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted or unsubstituted heteroaryl group.

[0074] The alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0075] The alkoxy group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy groups.

[0076] The aryl group having 6 to 12 carbon atoms is not particularly limited, and examples thereof include phenyl, tolyl, xylyl, trimethylphenyl, tetramethylphenyl, ethylphenyl, ethylmethylphenyl, diethylphenyl, propylphenyl, isopropylphenyl, isopropylmethylphenyl, benzyl, phenethyl, phenylpropyl, naphthyl, and biphenyl.

[0077] The heteroaryl group having 5 to 12 elements is not particularly limited, and examples thereof include furanyl, benzofuranyl, isobenzofuranyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, pyridinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolidinyl, indolyl, isoindolyl, indazolyl, quinolyl, isoquinolyl, naphthyridinyl, quinoxalinyl, quinazolinyl, pteridinyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, thiophenyl, thiopyranyl, benzothiophenyl, benzothiopyranyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, furazanyl, oxadiazolyl, dithiazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, benzimidazolyl, and benzotriazolyl.

[0078] The substituent is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, and an alkylcarbonyloxy group having 2 to 10 carbon atoms.

[0079] Among the above, R3 is preferably independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted heteroaryl group, more preferably a hydrogen atom or a substituted or unsubstituted heteroaryl group, and even more preferably a hydrogen atom or a benzotriazolyl group.

[0080] Z is independently selected from a single bond, an ether group, a carbonyl group, and an ester group. In the present specification, the "ester group" may be any of "-OC(=O)-" and "-C(=O)O-".

[0081] Among the above, Z is preferably a single bond or an ester group, and more preferably an ester group.

[0082] a is an integer of 1 to 3, and preferably 1.

[0083] b is an integer of 2 to 4, and preferably 4.

[0084] Y is an ether group or an ester group, preferably an ether group or an ester group (—C(═O)O—), and more preferably an ether group.

[0085] In one embodiment, in the above formula (1), A is preferably an isopropenyl group or a methylenyl group, Z is a single bond or an ester group, R1 and R2 are each independently a single bond or an ethylene group, and R3 is each independently a hydrogen atom or a benzotriazole group.

[0086] The terminal structure having an unsaturated group represented by formula (1) is preferably derived from the corresponding monophenol compound.

[0087] The monophenol compound is not particularly limited, and examples thereof include styrene-based monophenol compounds such as p-hydroxystyrene and p-isopropenylphenol (IPP); allylphenol-based monophenol compounds such as o-allylphenol and eugenol; (meth)acrylic acid-based monophenol compounds such as 4-hydroxyphenyl (meth)acrylate, 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT), (meth)acrylate-4-hydroxyphenylbutyl, (meth)acrylate-2-phenylphenol ethyl; and methine-based monophenol compounds such as 4-ethynylphenol and 4-propargylphenol. These monophenol compounds may be used alone or in combination of two or more.

[0088] Among the above, the terminal structure having an unsaturated group represented by formula (1) is preferably derived from a styrene-based monophenol compound, a (meth) acrylic monophenol compound, more preferably derived from isopropenylphenol (IPP), 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT), and even more preferably derived from 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT). In addition, when the terminal structure having an unsaturated group represented by formula (1) is derived from MBZT, the molded article after curing of the resin composition of the present invention has high impact resistance, and the molded article can have an excellent appearance even if it is a thick film. Moreover, long-term stability can be expected. In addition, in this specification, "the molded article is a thick film" means that the film thickness of the molded article is 5 mm or more.

[0089] The terminal structure having an unsaturated group represented by formula (1) preferably contains 0.2 mol% or more, more preferably 0.2 to 20 mol%, even more preferably 0.5 to 10 mol%, and particularly preferably 1 to 7 mol% of the structural unit represented by formula (2). If the content of the terminal structure having an unsaturated group represented by formula (1) is 0.2 mol% or more, it is preferable because it reacts with the styrene monomer to form a polymer when the curable resin composition is cured, and a molded product having excellent impact resistance can be obtained.

[0090] In addition, the terminal structure having an unsaturated group represented by formula (1) is preferably 0.2 to 20 mol%, and more preferably 0.5 to 10 mol%, relative to the total molar number of the structural unit and the terminal structure of the polycarbonate resin. If the content of the terminal structure having an unsaturated group represented by formula (1) is 0.2 mol% or more, it is preferable because a molded product having excellent impact resistance can be obtained by reacting with a styrene monomer to form a polymer when the curable resin composition is cured. On the other hand, if the content of the terminal structure having an unsaturated group represented by formula (1) is 20 mol% or less, it is preferable from the perspective of improving impact resistance.

[0091] Other terminal structures

[0092] The polycarbonate resin may have other terminal structures. Such other terminal structures are terminal structures other than the terminal structure having an unsaturated group represented by formula (1), and are preferably terminal structures not having an unsaturated group.

[0093] Examples of other terminal structures include structures derived from other monohydric phenol compounds.

[0094] Examples of the other monophenol compounds include phenol, p-tert-butylphenol, p-hexylphenol, p-heptylphenol, p-octylphenol, p-cumylphenol, etc. These other monophenol compounds may be used alone or in combination of two or more.

[0095] The content of other terminal structures is preferably less than 50 mol %, more preferably 20 mol % or less, even more preferably 10 mol % or less, and particularly preferably 0.1 to 5 mol % based on the terminal structure having an unsaturated group represented by formula (1).

[0096] In addition, the other terminal structures are preferably 10 mol% or less, more preferably 0.1 to 5 mol% relative to the total molar number of the structural units and terminal structures of the polycarbonate resin. If the content of the other terminal structures is 10 mol% or less, the content of the terminal structures having unsaturated groups shown in (1) above becomes relatively high, and a molded article having excellent impact resistance can be obtained, which is preferred.

[0097] The structural unit shown in formula (2)

[0098] The structural unit represented by formula (2) has a function of improving impact resistance, a function of improving styrene solubility, and the like.

[0099] The above structural unit is represented by the following formula (2).

[0100]

[0101] R4 is independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 17 carbon atoms.

[0102] The alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0103] The aryl group having 6 to 12 carbon atoms is not particularly limited, and examples thereof include phenyl, tolyl, xylyl, mesityl, tetratolyl, ethylphenyl, ethylmethylphenyl, diethylphenyl, propylphenyl, isopropylphenyl, isopropylmethylphenyl, benzyl, phenethyl, phenylpropyl, naphthyl, and biphenylyl.

[0104] The alkoxy group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy groups.

[0105] The aralkyl group having 7 to 17 carbon atoms is not particularly limited, and examples thereof include benzyl, 1-methylbenzyl, 1,1-dimethylbenzyl, 1-ethylbenzyl, 1-ethyl-1-methylbenzyl, phenethyl, 1-methylphenethyl, 2-methylphenethyl, and 1-ethylphenethyl.

[0106] The substituent is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, and an alkylcarbonyloxy group having 2 to 10 carbon atoms.

[0107] Among the above, R4 is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, still more preferably methyl and ethyl, particularly preferably methyl.

[0108] c is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1, respectively.

[0109] X is selected from -C(R5)(R6)-, -S-, -(CH2) d -, -O-, -SO-, -CO-, -SO2- and groups represented by the following formulae (3) to (6).

[0110]

[0111] R5 and R6 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or R5 and R6 are combined to form a carbocyclic group having 5 to 20 carbon atoms or a heterocyclic group having 5 to 12 elements.

[0112] The alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0113] The alkoxy group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy groups.

[0114] The aryl group having 6 to 12 carbon atoms is not particularly limited, and examples thereof include phenyl, tolyl, xylyl, mesityl, tetratolyl, ethylphenyl, ethylmethylphenyl, diethylphenyl, propylphenyl, isopropylphenyl, isopropylmethylphenyl, benzyl, phenethyl, phenylpropyl, naphthyl, and biphenylyl.

[0115] The substituent is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, and an alkylcarbonyloxy group having 2 to 10 carbon atoms.

[0116] The carbocyclic group having 5 to 20 carbon atoms is not particularly limited, and examples thereof include cycloalkylene groups such as cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, methylcyclopentylene, ethylcyclopentylene, methylcyclohexylene, ethylcyclohexylene, and 3,3,5-trimethylcyclohexylene; and arylalkylidenes such as benzylene, phenethylidene, and phenylpropylidene.

[0117] The heterocyclic group having 5 to 12 elements is not particularly limited, and examples thereof include heterocyclic groups in which a methylene chain portion contained in pyrrolidine, 2-pyrroline, pyrazoline, pyrazolidine, imidazoline, pyran, 2-imidazoline, 1,3-dioxolane, dioxolane, tetrahydrofuran, tetrahydrothiophene, piperazine, 1,4-dioxane, morpholine, 1,2-oxathiolane, 1,4-dithiane, succinimide, 2-oxazolidinone, indoline, isoindoline, chroman, isochroman, quinuclidine, etc., is bonded to two phenylene groups of the formula (2).

[0118] Among them, R5 and R6 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a carbocyclic group having 5 to 20 carbon atoms formed by combining R5 and R6; more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a carbocyclic group having 5 to 10 carbon atoms formed by combining R5 and R6; and even more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a cyclohexyl group (cyclohexane-1,1-diyl group) or a 3,3,5-trimethylcyclohexyl group (3,3,5-trimethylcyclohexane-1,1-diyl group) formed by combining R5 and R6.

[0119] R7 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

[0120] The alkyl group having 1 to 9 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl.

[0121] The alkoxy group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy groups.

[0122] The aryl group having 6 to 12 carbon atoms is not particularly limited, and examples thereof include phenyl, tolyl, xylyl, trimethylphenyl, tetramethylphenyl, ethylphenyl, ethylmethylphenyl, diethylphenyl, propylphenyl, isopropylphenyl, isopropylmethylphenyl, benzyl, phenethyl, phenylpropyl, naphthyl, and biphenylyl.

[0123] The substituent is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, and an alkylcarbonyloxy group having 2 to 10 carbon atoms.

[0124] Among these, R7 is preferably independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and even more preferably a hydrogen atom or a methyl group.

[0125] R8 is each independently a substituted or unsubstituted alkylene group having 1 to 9 carbon atoms.

[0126] Examples of the alkylene group having 1 to 9 carbon atoms include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, and pentylene.

[0127] The substituent is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, and an alkylcarbonyloxy group having 2 to 10 carbon atoms.

[0128] Among the above, R8 is preferably independently a methylene group, an ethylene group, or a propylene group, and more preferably a methylene group or an ethylene group.

[0129] d is an integer of 0-20, preferably an integer of 0-10, and more preferably an integer of 0-3.

[0130] e is an integer of 1-500, preferably an integer of 1-100.

[0131] In the structural unit represented by formula (2), when both c are 0, X is not -C(CH3)2-. That is, the structural unit represented by formula (2) does not contain a structural unit derived from bisphenol A (BPA, 2,2-bis(4-hydroxyphenyl)propane). The above-mentioned bisphenol A (BPA) has a symmetrical structure and high crystallinity, so it tends to have low solubility in styrene.

[0132] The structural unit represented by formula (2) is preferably derived from a bisphenol compound (a divalent phenol compound). Examples of the bisphenol compound include, but are not particularly limited to, bis(4-hydroxyphenyl)methane (bisphenol F: BPF), bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E: BPE), 1,1-bis(4-hydroxy-3-methylphenyl)ethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (bisphenol G: BPG), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B: BPB), 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (bisphenol G: BPG), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B: BPB), 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (bisphenol G: BPG), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B: BPB), 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxy-3-tert-butyl ... C: BPC), 2,2 Propane, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane (bisphenol PH: BPPH), 1,1-bis(4-hydroxyphenyl)-2-methylpropane (bisphenol IBTD), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (bisphenol MIBK), 1,1-bis(4-hydroxyphenyl)-2-ethylhexane (bisphenol IOTD), 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z: BPZ), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1 Bisphenol compounds in which X in the formula (2) is -C(R5)(R6)-, such as -bis(4-hydroxyphenyl)cycloundecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP: BPAP), bis(4-hydroxyphenyl)diphenylmethane (bisphenol BP; BPBP); bisphenol compounds in which X in the formula (2) is -S-, such as bis(4-hydroxyphenyl)sulfide; bisphenol compounds in which X in the formula (2) is -O-, such as bis(4-hydroxyphenyl)ether; bisphenol compounds in which X in the formula (2) is -SO-, such as bis(4-hydroxyphenyl)sulfoxide; bisphenol compounds in which X in the formula (2) is -CO-, such as bis(4-hydroxyphenyl)ketone; Bisphenol compounds; bisphenol compounds in which X in formula (2) is -SO2-, such as bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(2-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, etc.; bisphenol compounds in which X in formula (2) is a group represented by formula (3), such as 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene, etc.; bisphenol compounds in which X in formula (2) is a group represented by formula (4), such as 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, etc.;Bisphenol compounds such as 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, in which X in formula (2) is a group represented by formula (5); bisphenol compounds such as α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane and α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane, in which X in formula (2) is a group represented by formula (6);

[0133] Among the above, the structural unit represented by formula (2) preferably includes at least one structural unit derived from a bisphenol compound in which X in formula (2) is -C(R5)(R6)-, and more preferably includes structural units derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B: BPB), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (bisphenol MIBK), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E: BPE), 1,1-bis(4-hydroxyphenyl) ...-3-methylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxyphenyl)-3-methylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxyphenyl)-3-methylphenyl)butane (bisphenol B: BPB), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (bisphenol MIBK), 1,1-bis(4-hydroxyphenyl)-3-methylphenyl)propane (bisphenol E: BPE), 1,1-bis(4-hydroxyphenyl)-3-methylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxyphenyl)-3-methylphenyl)propane (bisphenol C: B The present invention further preferably contains at least one of the structural units derived from bisphenol C, bisphenol E, bisphenol Z, bisphenol MIBK, bisphenol AP, and bisphenol TMC, and particularly preferably contains at least one of the structural units derived from bisphenol C, bisphenol Z, bisphenol MIBK, and bisphenol TMC. That is, in one embodiment, the bisphenol compound preferably includes at least one selected from 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B: BPB), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (bisphenol MIBK), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol AP: BPAP), 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z: BPZ), 1,1-bis(4-hydroxyphenyl)-1-phenylmethane (bisphenol AP: BPAP), and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC: TMC).

[0134] In a preferred embodiment, the structural unit represented by the above formula (2) includes at least one selected from the following formulas (7) to (13). Among them, from the viewpoint of excellent impact resistance, the structural unit represented by formula (2) more preferably includes at least one selected from the following formulas (7) to (8) and the following formulas (10) to (13), and more preferably includes at least one selected from the following formulas (7), (10), (11) and (13). In addition, in another preferred embodiment, from the viewpoint of excellent appearance when the molded article is a thick film, the structural unit represented by the above formula (2) more preferably includes at least one selected from the following formulas (7) to (11) and (13), and more preferably includes at least one selected from the following formulas (7) and (9). In addition, formula (7) is derived from bisphenol C, formula (8) is derived from bisphenol E, formula (9) is derived from bisphenol B, formula (10) is derived from bisphenol Z, formula (11) is derived from bisphenol MIBK, formula (12) is derived from bisphenol AP, and formula (13) is derived from bisphenol TMC.

[0135]

[0136] The above-mentioned bisphenol compounds may be used alone or in combination of two or more.

[0137] The content of the structural unit represented by formula (2) is preferably 1 mol% or more, more preferably 2 to 100 mol%, even more preferably 5 to 100 mol%, and particularly preferably 10 to 100 mol% relative to all structural units of the polycarbonate resin. If the content of the structural unit represented by formula (2) is 1 mol% or more, the impact strength and styrene solubility of the polycarbonate resin can be improved, so it is preferred.

[0138] In addition, the total molar number of the structural unit represented by formula (2) relative to the structural unit and the terminal structure of the polycarbonate resin is preferably 2 to 99.8 mol%, and more preferably 5 to 99 mol%. If the content of the structural unit represented by formula (2) is 2 mol% or more, the impact strength and styrene solubility of the polycarbonate resin can be improved, so it is preferred. On the other hand, if the content of the structural unit represented by formula (2) is 99.8 mol% or less, it is easy to control the molecular weight, so it is preferred.

[0139] Other structural units

[0140] The polycarbonate resin may have other structural units. The other structural units are structural units other than the structural unit represented by formula (2).

[0141] Examples of the other structural units include structural units derived from other bisphenol compounds and structural units derived from organosiloxane.

[0142] The above-mentioned other bisphenol compounds are compounds other than the above-mentioned bisphenol compounds, and compounds not derived from the structural unit of formula (2) can be cited. Specific examples include alicyclic bisphenol compounds such as cyclohexanedimethanol, tricyclodecane dimethanol, adamantane diol, and pentacyclopentadecanedimethanol; and aromatic ring bisphenol compounds such as 4,4'-phenylene bisphenol and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A: BPA).

[0143] Examples of the organosiloxane include polydimethylsiloxane and polydiethylsiloxane.

[0144] Among these, the polycarbonate resin preferably contains a structural unit derived from other bisphenol compounds, more preferably contains a structural unit derived from an aromatic ring bisphenol compound, and even more preferably contains a structural unit derived from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A: BPA).

[0145]

[0146] In addition, when the polycarbonate resin also contains a structural unit derived from bisphenol A, it is preferred because the raw material has high market liquidity, thereby reducing manufacturing costs, the viscosity of the resulting resin composition is improved, thereby making it easy to handle, and the impact strength and thick film transparency of the resulting cured product are improved. In addition, even if the polycarbonate resin has a structural unit derived from bisphenol A, by having a structural unit shown in formula (2), the styrene solubility of the polycarbonate resin can be improved.

[0147] The content of other structural units is preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 0 to 60 mol % based on the structural unit represented by formula (2).

[0148] In addition, the other structural units are preferably 80 mol% or less, more preferably 0 to 60 mol% relative to the total molar number of the structural units and terminal structures of the polycarbonate resin. If the content of the other structural units is 80 mol% or less, the content of the structural unit represented by formula (2) is relatively increased, and the styrene solubility can be increased, which is preferred.

[0149] Physical properties of polycarbonate resin, etc.

[0150] When the polycarbonate resin has two or more structural units, that is, when it is a copolymer, the copolymer may be a random polymer, a block copolymer, or an alternating copolymer.

[0151] Since polycarbonate resin has high styrene solubility, it is dissolved in styrene monomers in the curable resin composition. Therefore, when the curable resin composition is cured, polycarbonate resin and styrene monomers can be appropriately graft-polymerized, and the impact resistance of the obtained molded body can be improved. In addition, the transparency of the obtained molded body can also be improved. Moreover, through the high styrene solubility of polycarbonate resin, the formation of graft polymers, etc., a molded body with excellent chemical resistance can be obtained. In addition, since the styrene solubility of polycarbonate resin is high, even if the curable resin composition does not contain a solvent, it can be easily molded, and a curable resin composition with a composition suitable for casting molding can be obtained. In addition, whether the styrene solubility is high can be confirmed by the method described in the examples.

[0152] The intrinsic viscosity of the polycarbonate resin is preferably 0.3 to 2.0 dL / g, more preferably 0.35 to 1.5 dL / g, and even more preferably 0.40 to 0.6 dL / g. If the intrinsic viscosity of the polycarbonate resin is 0.3 dL / g or more, the mechanical strength is improved, so it is preferred. On the other hand, if the intrinsic viscosity of the polycarbonate resin is 2.0 dL / g or less, the moldability is improved, so it is preferred.

[0153] The content of the polycarbonate resin is preferably 0.5 to 50% by mass, more preferably 1 to 50% by mass, more preferably 1 to 30% by mass, particularly preferably 5 to 30% by mass, and most preferably 10 to 20% by mass relative to the total mass of the curing resin composition. If the content of the polycarbonate resin is within the above range, the solubility, moldability, and mechanical strength in the styrene monomer are well balanced, and the workability and appearance of the cast molded product are improved, so it is preferred.

[0154] Method for producing polycarbonate resin

[0155] The above-mentioned polycarbonate resin can be produced by a known method. Specific examples of the production method of the polycarbonate resin include a phosgene method and an ester exchange method.

[0156] The phosgene method is a method of reacting monohydric phenol, bisphenol (dihydric phenol) and phosgene in a solvent in the presence of an acid binder.

[0157] The monophenol includes a monophenol compound from which a terminal structure having an unsaturated group represented by formula (1) is derived. In addition, other monophenol compounds from which other terminal structures are derived may also be included. In addition, the monophenol functions as a polymerization degree regulator.

[0158] The bisphenol (divalent phenol) includes a bisphenol compound from which the structural unit represented by formula (2) is derived, and may also include other bisphenol compounds from which other structural units are derived.

[0159] Moreover, when the polycarbonate resin contains a structural unit derived from an organosiloxane as another structural unit, the organosiloxane may be used in combination.

[0160] The acid binder is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine, etc. These acid binders may be used alone or in combination of two or more.

[0161] The solvent is not particularly limited, and examples thereof include dichloromethane, chloroform, etc. These solvents may be used alone or in combination of two or more.

[0162] In order to promote the above reaction, a catalyst may also be used. The catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine and quaternary ammonium salts such as benzyltriethylammonium chloride. These catalysts may be used alone or in combination of two or more.

[0163] Furthermore, in the above reaction, an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucinol or isatin bisphenol may be added.

[0164] The reaction temperature of the phosgene method is preferably 0 to 150°C, more preferably 5 to 40°C.

[0165] The reaction time of the phosgene method is preferably 0.5 minutes to 10 hours, more preferably 1 minute to 2 hours.

[0166] In addition, the pH of the reaction solution is preferably 10 or higher.

[0167] The transesterification method is a method of reacting monohydric phenol, bisphenol (dihydric phenol) and diaryl carbonate. In this case, the above-mentioned organosiloxane, antioxidant and branching agent may be added to the above-mentioned reaction.

[0168] The monohydric phenol, the bisphenol (dihydric phenol), the organosiloxane, the antioxidant and the branching agent may be the same as those used in the phosgene method.

[0169] Examples of the diaryl carbonate include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate, etc. These diaryl carbonates may be used alone or in combination of two or more.

[0170] From the viewpoint of suitably performing transesterification, it is preferred to distill off the phenols derived from the diaryl carbonate to the outside of the system.

[0171] The reaction temperature of the transesterification method is preferably 150 to 350°C, more preferably 200 to 300°C.

[0172] The degree of reduced pressure in the transesterification method is preferably 1 mmHg or less.

[0173] The reaction time of the transesterification method varies depending on the reaction temperature, the degree of reduced pressure, etc., but is preferably 1 to 24 hours.

[0174] The reaction atmosphere of the transesterification method is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

[0175] [Styrene monomer]

[0176] The styrene monomer has the function of improving the impact strength, optical properties, etc. of the molded product obtained from the curing resin composition. In addition, the styrene monomer can exist in the molded product after the resin composition of the present invention is cured in the form of graft polymerization with a polycarbonate resin, in the form of a polymer of a styrene monomer (polystyrene), in the form of a styrene monomer, etc.

[0177] The styrene monomers are not particularly limited, and examples thereof include styrene, α-methylstyrene, m-chlorostyrene, p-chlorostyrene, p-fluorostyrene, pentafluorostyrene, p-methoxystyrene, m-tert-butoxystyrene, p-tert-butoxystyrene, 4-(1-ethoxyethoxy)styrene, p-vinylbenzoic acid, p-vinylbenzaldehyde, p-chloro-α-methylstyrene, p-fluoro-α-methylstyrene, p-methyl-α-methylstyrene, p-tert-butoxy-α-methylstyrene, p-vinyltoluene, 1,1-diphenylethylene, diphenylphosphinostyrene, isopropenylphenol, p-hydroxystyrene, chloromethylstyrene, p-styrenesulfonic acid, sodium p-styrenesulfonate, 3,4-dimethoxystyrene, p-trifluoromethylstyrene, 3-acetoxy-5-hydroxystyrene, 4-cyanostyrene, m-bromostyrene, p-bromostyrene, 2,4,6-trimethylstyrene, tert-butoxycarbonyloxystyrene, etc. These styrene monomers may be used alone or in combination of two or more.

[0178] Among the above, the styrene-based monomer preferably contains at least one of styrene, α-methylstyrene, and p-hydroxystyrene, and more preferably contains styrene.

[0179] The content of the styrene monomer is preferably 50 to 99.5% by mass, more preferably 50 to 99.1% by mass, more preferably 70 to 95% by mass, particularly preferably 70 to 90% by mass, and most preferably 80 to 90% by mass relative to the total mass of the curing resin composition. If the content of the styrene monomer is within the above range, the impact strength and optical properties of the resulting molded article can be improved, so it is preferred.

[0180] [Free Radical Polymerization Initiator]

[0181] The curing resin composition preferably further contains a radical polymerization initiator. The radical polymerization initiator has the function of generating radicals from the unsaturated groups of the terminal structure represented by formula (1) in the polycarbonate resin and / or the styrene monomers to initiate polymerization reaction when producing a molded article.

[0182] The free radical polymerization initiator is not particularly limited, and examples thereof include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis(2,4-dimethylvaleronitrile); peroxides such as benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate. These free radical polymerization initiators may be used alone or in combination of two or more.

[0183] Among the above, the radical polymerization initiator preferably includes 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide, hydrogen peroxide, or cumene hydroperoxide, preferably includes 2,2'-azobisisobutyronitrile (AIBN) and benzoyl peroxide, and more preferably includes 2,2'-azobisisobutyronitrile (AIBN).

[0184] The content of the radical polymerization initiator is preferably 0.001 to 5 mass %, more preferably 0.005 to 3 mass %, and even more preferably 0.01 to 1 mass % relative to the total mass of the curing resin composition. The content of the styrene monomer within the above range is preferred because the polymerization reaction can proceed appropriately.

[0185] [Solvent]

[0186] The curable resin composition may further contain a solvent. The solvent has a function of adjusting viscosity, etc.

[0187] The above-mentioned solvent is not particularly limited, and examples thereof include halogen organic solvents such as dichloromethane, 1,2-dichloroethane, chloroform, and monochlorobenzene; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-ethoxyethyl acetate, 2-methoxy-1-methylethyl acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; carbonate solvents such as dimethyl carbonate and ethyl methyl carbonate; ether solvents such as tetrahydrofuran, 1,4-dioxane, diethyl ether, dimethoxymethane, ethyl cellosolve, and anisole; aromatic hydrocarbon solvents such as toluene, ethylbenzene, xylene, unitylene, and mesitylene; alcohol poor solvents such as ethanol and isopropanol; hydrocarbon poor solvents such as n-heptane, cyclohexane, and mineral spirits. These solvents may be used alone or in combination of two or more.

[0188] Among the above, the solvent preferably includes a carbonate-based organic solvent, a ketone-based organic solvent, and a toluene-based organic solvent, and more preferably includes ethyl acetate, methyl ethyl ketone, and toluene.

[0189] In addition, since the polycarbonate resin has high styrene solubility, it can be properly molded even without a solvent. Therefore, in one embodiment, the curable resin composition is preferably solvent-free. Wherein, "solvent-free" means that the content of the solvent in the curable resin composition is less than 0.5% by mass, preferably less than 0.1% by mass, relative to the total mass of the curable resin composition.

[0190] [additive]

[0191] The curing resin composition may further contain additives.

[0192] The additives are not particularly limited, and examples thereof include other polycarbonate resins, other polymerizable components, colorants, rust preventives, antioxidants, dispersants, ultraviolet absorbers, defoamers, leveling agents, and the like.

[0193] For example, examples of the other polycarbonate resin include polycarbonate resins other than the polycarbonate resins described above.

[0194] Moreover, as another polymerizable component, ethylene, propylene, butadiene, acrylonitrile etc. are mentioned, for example.

[0195] Furthermore, as colorants, azo pigments and phthalocyanine pigments such as Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 215, Red No. 220, Orange No. 203, Orange No. 204, Blue No. 1, Blue No. 404, Yellow No. 205, Yellow No. 401, and Yellow No. 405; inorganic colorants such as mica titanium oxide, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silicon dioxide, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, and nickel; and optical interference particles such as glass beads, shells, and mica.

[0196] The above-mentioned additives may be used alone or in combination of two or more.

[0197] [Physical properties of curing resin composition]

[0198] The viscosity of the curing resin composition is preferably 1 to 20,000 mPa·s, more preferably 2 to 6,000 mPa·s, even more preferably 5 to 4,000 mPa·s, particularly preferably 50 to 200 mPa·s, and most preferably 90 to 180 mPa·s. If the solution viscosity of the curing resin composition is within the above range, it is easy to handle, so it is preferred. In addition, the solution viscosity of the curing resin composition can be measured by the method described in the examples.

[0199] <Method for producing curable resin composition>

[0200] The method for producing the curing resin composition is not particularly limited and can be produced by a known method. In one embodiment, the method for producing the curing resin composition includes a step of mixing a polycarbonate resin and a styrene monomer. It may also include a step of mixing at least one of a free radical polymerization initiator, a solvent, and an additive. For example, for a styrene monomer, a polycarbonate resin and a free radical polymerization initiator are added in sequence, thereby being able to produce a curing resin composition.

[0201] <Molding products>

[0202] According to one aspect of the present invention, there is provided a molded article formed by curing the above-mentioned curing resin composition.

[0203] The molded article includes a graft polymer of a polycarbonate resin and a styrene-based monomer, and may also include a polymer obtained by reacting unsaturated groups of a polycarbonate resin with each other, a polymer of a styrene-based monomer (polystyrene), a polycarbonate resin, a styrene-based monomer, and the like.

[0204] Polycarbonate resin has unsaturated groups and high styrene solubility. Therefore, polycarbonate resin can be appropriately graft-polymerized with styrene monomers to obtain a molded body with excellent impact resistance. In addition, due to the high styrene solubility of polycarbonate resin, a molded body with excellent transparency can be obtained. In addition, due to the high styrene solubility of polycarbonate resin, the formation of graft polymers, etc., a molded body with excellent chemical resistance can be obtained.

[0205] As molded products, there are no particular restrictions, and injection molded products, extrusion molded products, stretch molded products, thermoformed products, cast molded products, etc. can be cited. Among them, cast molded products are preferred. Polycarbonate resin has high solubility in styrene, so the moldability of the curable resin composition is excellent. Therefore, the molded products obtained by casting can have higher physical properties compared with existing products. In particular, in a preferred embodiment, the curable resin composition does not contain solvent. In this case, deformation caused by solvent volatilization does not occur or does not occur substantially, so the molded products (cast molded products) obtained by casting can have higher physical properties.

[0206] [Physical properties of molded products, etc.]

[0207] The total light transmittance of the molded article is preferably 80 to 100%, more preferably 85 to 95%, even more preferably 87 to 94%, and particularly preferably 88 to 93%. If the total light transmittance of the molded article is within the above range, it will be a molded article with excellent transparency, so it is preferred. In addition, in this specification, the value of "the total light transmittance of the molded article" adopts the value measured by the method described in the examples.

[0208] The impact strength of the molded product is preferably 5.0 to 100 kJ / m 2 , more preferably 8.0 to 80 kJ / m 2 , more preferably 8.0 to 50 kJ / m 2 , particularly preferably 9 to 30 kJ / m 2 , the most preferred is 10 to 20 kJ / m 2 If the impact strength of the molded article is within the above range, it is preferred because the molded article has excellent impact resistance. In addition, in this specification, the value of "impact strength of the molded article" is the value measured by the method described in the examples.

[0209] The molded product can have chemical resistance. Therefore, it can be suitably applied to applications requiring chemical resistance of the molded product. In addition, whether or not the molded product has chemical resistance can be confirmed by the method described in the examples, for example.

[0210] The molded article can be suitably used in various applications, specifically, lenses, cover parts of touch panels, housings of devices, resin glasses, automotive glass substitutes, water tanks, light guide plates, hard coatings, coatings, photoresists, 3D printers, and the like.

[0211] <Production method of molded products>

[0212] According to one aspect of the present invention, there is provided a method for producing a molded article, comprising the step of curing the curing resin composition.

[0213] The curing generally includes a step of graft-polymerizing the polycarbonate resin and the styrene-based monomers contained in the curing resin composition. Alternatively, the curing may include polymerization of the polycarbonate resin and polymerization of the styrene-based monomers.

[0214] The curing (polymerization) is preferably bulk polymerization. Since polycarbonate resin has high solubility in styrene, bulk polymerization can be preferably performed using a curable resin composition that does not contain a solvent.

[0215] In another embodiment, the curing (polymerization) may be performed by suspension polymerization. For example, the suspension polymerization method includes a method of putting the curing resin composition into water for polymerization. In this case, a solvent may be used together with the water.

[0216] The curing method is not particularly limited, and examples thereof include thermal curing and photocuring.

[0217] The curing temperature (polymerization temperature) during heat curing is preferably not more than the boiling point of the styrene-based monomer, more preferably 40 to 100°C, further preferably 50 to 90°C, particularly preferably 60 to 80°C.

[0218] The curing time (polymerization time) during thermal curing is not particularly limited, but is preferably 5 minutes to 48 hours, more preferably 10 minutes to 30 hours, and even more preferably 30 minutes to 24 hours.

[0219] The irradiation light used for photocuring is preferably visible light to ultraviolet light, more preferably irradiation light with a wavelength of 190 to 450 nm, more preferably irradiation light with a wavelength of 200 to 400 nm, and even more preferably irradiation light with a wavelength of 250 to 380 nm.

[0220] The irradiation time during photocuring is preferably 1 second to 2 hours, more preferably 3 seconds to 1 hour, and even more preferably 5 seconds to 30 minutes.

[0221] The accumulated light intensity during photocuring is preferably 50m to 100J / cm 2 , more preferably 100m~50J / cm 2 , more preferably 300m~20J / cm 2 .

[0222] The molding method of the above-mentioned molded product can include injection molding, extrusion molding, stretch molding, thermoforming, casting molding, etc. Among these, the molding method is preferably casting molding. As mentioned above, the styrene solubility of polycarbonate resin is high, and by using a solvent-free curable resin composition, a cast molded product can be appropriately manufactured. At this time, the above-mentioned cast molded product will not or substantially not produce deterioration over time caused by the volatilization of the solvent.

[0223] In a preferred embodiment, the method for producing a molded article includes the steps of injecting the curable resin composition into a mold, curing the curable resin composition injected into the mold, and removing the obtained cured product from the mold.

[0224] In addition, examples of the mold include a metal mold and a mold made of silicone.

[0225] Examples of the method for injecting the material into the mold (casting method) include gravity casting methods such as top pouring method and bottom pouring method, vacuum casting method, centrifugal method, etc. These casting methods may be used alone or in combination of two or more.

[0226] Example

[0227] Examples of the present invention are shown below, but the present invention is not limited to the examples. <Styrene Solubility of Polycarbonate Resin>

[0228] The polycarbonate resin and styrene were mixed so that the concentration of the polycarbonate resin was 5 to 30% by mass. The obtained solution was shaken on a shaker for 24 hours and evaluated by visual observation according to the following criteria.

[0229] ○: No dissolved polycarbonate resin remains.

[0230] ×: Dissolved polycarbonate resin remains.

[0231] <Method for measuring intrinsic viscosity of polycarbonate resin>

[0232] A polycarbonate resin was dissolved in dichloromethane to prepare a solution (0.5 mass / volume %). The intrinsic viscosity of the obtained solution was measured using an Ubbelohde viscometer at 20° C. and a Huggins constant of 0.45.

[0233] <Method for measuring viscosity of curing resin composition>

[0234] The viscosity of the curable resin composition was measured at 25° C. using a vibration viscometer CJV5000 (manufactured by A&D Corporation).

[0235] <Method for measuring total light transmittance of molded products>

[0236] The test sample was prepared by casting. Specifically, 1.3 g of the curing resin composition was placed in a cylindrical glass mold with an inner diameter of 53 mm and the lid was tightly closed. The cylindrical glass mold enclosed with the curing resin composition was immersed in a hot water bath at 70°C for 24 hours for heating. Thus, the curing resin composition was cured to obtain a test sample (casting molded product) with a diameter of 53 mm and a thickness of 0.5 mm.

[0237] The total light transmittance of the measurement sample was measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries, Ltd.).

[0238] <Measurement of impact strength of molded products>

[0239] The test sample was prepared by casting. Specifically, 1.3 g of the curing resin composition was placed in a cylindrical glass tube with an inner diameter of 4.4 mm and a height of 30 mm, and the lid was tightly closed. The cylindrical glass tube enclosed with the curing resin composition was immersed in a hot water bath at 70°C for 24 hours and heated. Thus, the curing resin composition was cured to obtain a test sample (cylindrical cast product) with an inner diameter of about 4.4 mm and a height of about 30 mm.

[0240] Using an impact tester IT (manufactured by Toyo Seiki Seisaku-sho, Ltd.), a measurement sample was fixed to a self-made jig, and the impact strength was measured under the conditions of an Izod 2J weight and a 150-degree drop.

[0241] <Chemical resistance test of molded products>

[0242] The chemical resistance test was performed using the measurement sample (cylindrical cast molded product) prepared in the measurement of impact strength.

[0243] The measurement sample and 50 mL of dichloromethane were placed in a cylindrical glass container having a diameter of 40 mm, the container was tightly covered, and the container was left to stand. After 24 hours, the measurement sample was visually observed and evaluated according to the following criteria.

[0244] ○: Undissolved molded products were confirmed.

[0245] ×: Undissolved molded products could not be confirmed.

[0246] <Appearance test of thick film molded products>

[0247] 10 g of the curing resin composition was placed in a cylindrical glass container with a diameter of 40 mm (inner diameter of 38 mm), the lid was tightly closed, and the container was immersed in a hot water bath at 70° C. for 24 hours for heating. The lid was opened and hot air drying was performed at 100° C. for 24 hours. Since the wall thickness was 9 to 10 mm, bubbles remained or the surface was rough, and the transmittance could not be measured. Therefore, the transparency was evaluated in 5 levels by visual inspection of the appearance.

[0248] 5: No fogging or turbidity, visually transparent.

[0249] 4: Slight turbidity or slight white turbidity was observed, but the transparency was high.

[0250] 3: Turbidity or white turbidity was observed, but transparency was present.

[0251] 2: Obvious turbidity or whitishness, low transparency.

[0252] 1: Very turbid or whitish, not transparent.

[0253] [Example 1]

[0254] (Preparation of polycarbonate resin)

[0255] 61.3 g (0.24 mol) of bisphenol C (BPC: 2,2-bis(4-hydroxy-3-methylphenyl)propane, manufactured by Honshu Chemical Industry Co., Ltd.), 41.2 g (0.18 mol) of bisphenol A (BPA: 2,2-bis(4-hydroxyphenyl)propane, manufactured by Mitsubishi Chemical Corporation), 0.2 g of sodium dithionite, and 0.08 g of benzyltriethylammonium chloride (TEBAC: manufactured by Tokyo Chemical Industry Co., Ltd.) as a quaternary ammonium salt were dissolved in 1100 mL (5 mass / mass %) of an aqueous sodium hydroxide solution.

[0256]

[0257] 400 mL of dichloromethane was added to the obtained solution, and the mixture was stirred and cooled to 15 to 20° C. Then, 60 g of phosgene was bubbled into the solution over about 60 minutes.

[0258] After the bubbling of phosgene was completed, 4.05 g (0.0133 mol) of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (MBZT, manufactured by Otsuka Chemical Co., Ltd.) and 100 mL (10 mass / mass%) of an aqueous sodium hydroxide solution were added to the reaction solution, and the reaction solution was vigorously stirred to emulsify the reaction solution. After emulsification, 0.5 mL of triethylamine was added, and the mixture was stirred at 20 to 30° C. for about 40 minutes to perform a polymerization reaction.

[0259]

[0260] After the polymerization reaction is completed, the reaction solution is separated into an aqueous phase and an organic phase. After the organic phase is neutralized with phosphoric acid, it is repeatedly washed with water until the conductivity of the washing liquid (aqueous phase) reaches 10μS / cm or less. The obtained solution is added dropwise to warm water at 60°C, and the solvent is evaporated to obtain a white powdery precipitate. The obtained precipitate is filtered and dried at 110°C for 24 hours to obtain a powdery polycarbonate resin.

[0261] The styrene solubility and intrinsic viscosity of the obtained polycarbonate resin were measured. The obtained results are shown in Table 1 below.

[0262] In addition, the results of infrared absorption spectroscopy analysis showed that －1 Absorption due to carbonyl was confirmed at 1240 cm －1 Absorption due to an ether bond was observed at a nearby position, confirming that it was a polycarbonate resin having a carbonate bond.

[0263] (Manufacture of curable composition)

[0264] A polymerization inhibitor was removed from a styrene monomer (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) using an aqueous sodium hydroxide solution (5% by mass) to obtain a styrene monomer (ST) dehydrated with anhydrous sodium sulfate. 3 parts by mass of the polycarbonate resin prepared above was dissolved in 17 parts by mass of the styrene monomer. Then, 0.01 parts by mass of azobisisobutyronitrile (AIBN) was added as a free radical polymerization initiator to prepare a curing resin composition.

[0265] The viscosity of the obtained curable resin composition was measured. In addition, a molded article was manufactured from the obtained curable resin composition, and the total light transmittance, impact strength, chemical resistance, and appearance of the thick film molded article were evaluated. The obtained results are shown in Table 1 below.

[0266] [Example 2]

[0267] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that 90 g of bisphenol Z (BPZ: 1,1-bis(4-hydroxyphenyl)cyclohexane) was used instead of BPC and BPA, MBZT was changed to 3.60 g, phosgene was changed to 47 g, and TEBAC was not used.

[0268]

[0269] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0270] [Example 3]

[0271] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1, except that 80 g of bisphenol B (BPB: 2,2-bis(4-hydroxyphenyl)butane, manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC and BPA, MBZT was changed to 3.55 g, phosgene was changed to 47 g, and TEBAC was not used.

[0272]

[0273] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0274] [Example 4]

[0275] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1, except that 80 g of bisphenol E (BPE: 1,1-bis(4-hydroxyphenyl)ethane, manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC and BPA, MBZT was changed to 4.05 g, phosgene was changed to 52 g, and TEBAC was not used.

[0276]

[0277] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0278] [Example 5]

[0279] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1, except that 80 g of MIBK (2,2-bis(4-hydroxyphenyl)-4-methylpentane, manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC and BPA, MBZT was changed to 3.58 g, phosgene was changed to 49 g, and TEBAC was not used.

[0280]

[0281] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0282] [Example 6]

[0283] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that the amount of the polycarbonate resin used was changed to 1 part by mass and the amount of the styrene monomer used was changed to 19 parts by mass.

[0284] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0285] [Example 7]

[0286] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that the amount of the polycarbonate resin used was changed to 6 parts by mass and the amount of the styrene monomer used was changed to 14 parts by mass.

[0287] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0288] [Example 8]

[0289] A polycarbonate resin and a curing resin composition were produced by the same method as in Example 1 except that 1.68 g of p-isopropenylphenol (IPP, manufactured by Mitsui Fine Chemicals Co., Ltd.) was used instead of MBZT.

[0290]

[0291] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0292] [Example 9]

[0293] A polycarbonate resin and a curing resin composition were produced by the same method as in Example 1, except that 116 g of bisphenol AP (BPAP: 1,1-bis(4-hydroxyphenyl)-1-phenylmethane, manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC and BPA, MBZT was changed to 3.58 g, phosgene was changed to 49 g, and TEBAC was not used.

[0294]

[0295] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0296] [Example 10]

[0297] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that 102.4 g of BPC alone was used instead of BPC and BPA, MBZT was changed to 4.10 g, and phosgene was changed to 58 g.

[0298] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0299] [Example 11]

[0300] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1, except that 108.5 g of bisphenol TMC (TMC: 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, manufactured by SONGWON) was used instead of BPC and BPA, MBZT was changed to 3.10 g, phosgene was changed to 50 g, and TEBAC was not used.

[0301]

[0302] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0303] [Comparative Example 1]

[0304] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that 2.63 g of p-tert-butylphenol (PTBP, manufactured by DIC Corporation) was used instead of MBZT.

[0305]

[0306] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0307] [Comparative Example 2]

[0308] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 2 except that 1.44 g of PTBP was used instead of MBZT.

[0309] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0310] [Comparative Example 3]

[0311] A polycarbonate resin and a curing resin composition were produced by the same method as in Example 3 except that 1.65 g of PTBP was used instead of MBZT.

[0312] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0313] [Comparative Example 4]

[0314] A polycarbonate resin and a curing resin composition were produced by the same method as in Example 4 except that 2.34 g of PTBP was used instead of MBZT.

[0315] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0316] [Comparative Example 5]

[0317] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 5 except that 1.67 g of PTBP was used instead of MBZT.

[0318] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0319] [Comparative Example 6]

[0320] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that 91.2 g of BPA alone was used instead of BPC and BPA, 2.00 g of PTBP was used instead of MBZT, phosgene was changed to 55 g, and TEBAC was not used.

[0321] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0322] [Comparative Example 7]

[0323] A polycarbonate resin and a curing resin composition were produced by the same method as in Example 1 except that 91.2 g of BPA alone was used instead of BPC and BPA, MBZT was changed to 4.97 g, and TEBAC was not used.

[0324] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0325] [Comparative Example 8]

[0326] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that the polycarbonate resin was not used.

[0327] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0328] [Comparative Example 9]

[0329] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that 102.4 g of BPC alone was used instead of BPC and BPA, 1.42 g of PTBP was used instead of MBZT, phosgene was changed to 58 g, and TEBAC was not used.

[0330] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0331] [Comparative Example 10]

[0332] A polycarbonate resin and a curing resin composition were produced in the same manner as in Example 1 except that 108.5 g of TMC was used instead of BPC and BPA, 1.42 g of PTBP was used instead of MBZT, phosgene was changed to 50 g, and TEBAC was not used.

[0333] In addition, the styrene solubility and intrinsic viscosity of the polycarbonate resin, the viscosity of the curable resin composition, and the total light transmittance, impact strength, chemical resistance, and thick film molded product appearance of the molded product obtained by casting the curable resin composition were evaluated by the same method as in Example 1. The obtained results are shown in the following Table 1.

[0334] [Table 1]

[0335]

[0336] The results in Table 1 show that the molded articles produced from the curable resin compositions of Examples 1 to 11 have high total light transmittance, excellent transparency, and high impact strength. Furthermore, it is also known that the molded articles have excellent chemical resistance.

[0337] On the other hand, it was found that the impact strength of the molded articles produced from the curable resin compositions of Comparative Examples 1 to 6 and 9 to 10 was low. The reason for this is that since the polycarbonate resin does not have an unsaturated group in the terminal structure, the styrene monomer cannot form a covalent bond with the polycarbonate resin during curing.

[0338] In addition, it can be seen that the total light transmittance and impact strength of the molded products produced from the curable resin compositions of Comparative Examples 6 and 7 are low. As a reason for this, it can be considered that when the structural unit of the polycarbonate resin is only BPA, the styrene solubility is low. In particular, although the polycarbonate resin of Comparative Example 7 has an unsaturated group in the terminal structure, it is considered that due to the low styrene solubility, the reaction between the terminal unsaturated group of the polycarbonate resin and the styrene monomer cannot be properly carried out during curing.

Claims

1. A curing resin composition, characterized in that: Contains polycarbonate resin and styrene monomers, The polycarbonate resin comprises a terminal structure represented by the following formula (1) derived from a (meth)acrylic monophenol compound and a structural unit represented by the following formula (2). Formula (1): In the formula (1), A is vinyl or isopropenyl, R1 is a single bond, and R2 is independently selected from a single bond and a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R3 is independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 12 elements, Z is an ester group, a is an integer from 1 to 3, b is an integer from 2 to 4, Y is an ether group or an ester group, Formula (2): In the formula (2), R4 is independently selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 17 carbon atoms, c are each independently an integer of 0 to 4, X is selected from -C(R5)(R6)-, -S-, -(CH2) d -, -O-, -SO-, -CO-, -SO2- and the groups represented by the following formulae (3) to (6), wherein when both c are 0, X is not -C(CH3)2-, Formula (3) to (6): In the formulas (3) to (6), R5 and R6 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or R5 and R6 are combined to form a carbocyclic group having 5 to 20 carbon atoms or a heterocyclic group having 5 to 12 elements, R7 is each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R8 is each independently a substituted or unsubstituted alkylene group having 1 to 9 carbon atoms, d is an integer from 0 to 20, e is an integer from 1 to 500.

2. The curable resin composition according to claim 1, wherein: The structural unit represented by the formula (2) comprises at least one selected from the following formulae (7) to (13), Formula (7) to (13):

3. The curable resin composition according to claim 1, wherein: The structural unit represented by the formula (2) is derived from a bisphenol compound.

4. The curable resin composition according to claim 3, wherein: The bisphenol compound includes at least one selected from 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylmethane, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

5. The curing resin composition according to any one of claims 1 to 4, characterized in that: The polycarbonate resin further comprises a structural unit derived from bisphenol A represented by the following formula:

6. The curable resin composition according to any one of claims 1 to 4, characterized in that: In the formula (1), A is isopropenyl, Z is an ester group -OC(=O)-, R2 is independently a single bond or ethylene, R3 are each independently a hydrogen atom or a benzotriazolyl group.

7. The curable resin composition according to claim 6, wherein: The terminal structure represented by the formula (1) is derived from 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole.

8. The curable resin composition according to any one of claims 1 to 4, characterized in that: The styrenic monomer includes styrene.

9. The curable resin composition according to any one of claims 1 to 4, characterized in that: A free radical polymerization initiator is also included.

10. The curable resin composition according to any one of claims 1 to 4, characterized in that: The intrinsic viscosity of the polycarbonate resin is 0.3 to 2.0 dL / g.

11. The curable resin composition according to any one of claims 1 to 4, characterized in that: The content of the terminal structure represented by the formula (1) is 0.2 mol% or more based on the structural unit represented by the formula (2).

12. A molded product, characterized in that: This is a molded article obtained by curing the curing resin composition according to any one of claims 1 to 11.

13. The molded article according to claim 12, wherein: It is a cast product.

14. A method for manufacturing a molded product, characterized in that: include: A step of curing the curing resin composition according to any one of claims 1 to 11.

Images