Curable resin composition, curing method thereof, and molded product

Abstract

Provided is a curable resin composition which can be molded by casting to obtain composite materials each composed of a polycarbonate resin and an acrylic resin and having high transparency and high impact strength. More specifically, provided is a curing resin composition comprising an acrylic monomer having a saturated group, a polycarbonate resin having an unsaturated-group-containing terminal structure at a molecular end, and a free-radical polymerization initiator.

Description

[Technical field]

[0001] The present invention relates to a curable resin composition that forms a composite material of a polycarbonate resin and an acrylic resin, and to a cast article obtained by curing the same. [Background technology]

[0002] Acrylic resin, whose main raw material is methyl methacrylate, has excellent transparency and hardness and is widely used in resin windows, lenses, light guide plates, etc. However, acrylic resin has the disadvantage of having low impact resistance and being easily broken.

[0003] Therefore, attempts have been made to make a polymer alloy of polycarbonate resin and acrylic resin, which have excellent impact resistance. As a method for uniformly blending polycarbonate resin and acrylic resin while maintaining transparency, a method of high shear melt kneading until nano-dispersion is known (Patent Document 1). In addition, a method of dissolving an acrylic monomer and a polycarbonate having an unsaturated group in a dichloromethane solvent and forming a copolymer by solution polymerization (Patent Document 2), and a method of dispersing a polycarbonate solid having an unsaturated group in water, adsorbing the acrylic monomer to the polycarbonate, and carrying out suspension polymerization (Patent Document 3, Patent Document 4) are also known.

[0004] However, in these methods, the polycarbonate resin is not completely soluble in the acrylic monomer, making it difficult to mold the resin by the casting method generally used with acrylic resins, and there was room for improvement. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] WO2010 / 061872 (Patent No. 5697143) [Patent Document 2] Special Publication No. 48-025076 [Patent Document 3] Japanese Patent Application Publication No. 05-65320 [Patent Document 4] Japanese Patent Application Publication No. 06-041258 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a castable curable resin composition for obtaining a composite material of a polycarbonate resin and an acrylic resin, which has excellent transparency and high impact strength. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the problems of the related art, and have found that a polycarbonate resin having a specific main skeleton with an unsaturated group at the molecular end is a curable resin solution composition suitable for cast molding to form a composite material of a polycarbonate resin and an acrylic resin, which has good solubility in an acrylic monomer, excellent transparency, and high impact strength, and have thus completed the present invention. That is, the present invention includes the following aspects.

[0008] [1] an acrylic monomer having a saturated group; A polycarbonate resin including the following structural unit (2) in which a terminal structure represented by the following structural formula (1) having an unsaturated group is bonded to a molecular end; Radical polymerization initiator A curable resin composition comprising: [ka] (In formula (1), A represents a vinyl group, an isopropenyl group, a styryl group, or a methine group. R 1 ~R 2 each independently represents a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms, R 3 ~R 4each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a benzotriazole group, each of which may have a substituent; Z represents an ether group, a carbonyl group, an ester group, or a single bond; a is an integer from 1 to 3; Y represents an ether bond or an ester group. [ka] (In formula (2), R 5 ~R 8 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; b is an integer equal to or greater than 1; X is [ka] and where R 9 and R 10 each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; 9 and R 10 represents a group which is bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements, R 11 and R 12 each independently represents hydrogen, fluorine, chlorine, bromine or iodine, or represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R 13 represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, c represents an integer from 0 to 20; d represents an integer from 1 to 500; However, R 5 ~R 8 is hydrogen, R 9 and R 10 is a methyl group, the composition further comprises a second polycarbonate resin.

[0009] [2] The curable resin composition according to the above item [1], wherein the structural unit (2) is at least one selected from the group consisting of the following formulae (4) to (7): [ka] [ka] [ka] [ka]

[0010] [3] The curable resin composition according to the above-mentioned [1], wherein the structural unit (2) is derived from a bisphenol compound.

[0011] [4] At least one of the bisphenol compounds is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, and 2,2-bis(4-hydroxyphenyl)-4-methylpentane. The curable resin composition according to [3] above.

[0012] [5] In the formula (1), Z is a single bond or an ester group, and R 1 ~R 2 are each independently a single bond or an ethylene group, A is an isopropenyl group or a methine group, and R 3 ~R 4Each of the following is independently a hydrogen atom or a benzotriazole group:

[0013] [6] The curable resin composition according to the above [5], wherein the terminal structure represented by the formula (1) is a monohydric phenol derived from 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole or p-isopropenylphenol.

[0014] [7] The curable resin composition according to any one of the above [1] to [6], wherein the acrylic monomer includes an acrylic acid ester or a methacrylic acid ester.

[0015] [8] The curable resin composition according to any one of the above [1] to [7], wherein the acrylic monomer includes methyl methacrylate.

[0016] [9] The curable resin composition according to any one of the above [1] to [8], wherein the polycarbonate resin has an intrinsic viscosity of 0.3 to 2.0 dl / g.

[0017]

[10] The curable resin composition according to any one of the above [1] to [9], wherein the terminal structure represented by the structural formula (1) is contained in an amount of 0.2 mol % or more relative to the structural unit (2).

[0018]

[11] A curing method comprising applying heat or light to the curable resin composition according to any one of the above [1] to

[10] to cure it.

[0019]

[12] A cast product that has been hardened in a mold using the hardening method described in

[11] above.

[0020]

[13] A method for producing a cast molding, comprising placing the curable resin composition according to any one of the above [1] to

[10] in a mold and curing the composition.

[0021]

[14] A cast molding formed from the curable resin composition according to any one of the above items [1] to

[10] . Effect of the Invention

[0022] The curable resin composition of the present invention can be cured by reacting a polycarbonate resin with an acrylic monomer without using a solvent, and can form a composite material of polycarbonate resin and acrylic resin having excellent transparency and impact strength by a casting method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] 1. Curing resin composition The curable resin composition of the present invention comprises: an acrylic monomer having a saturated group; A polycarbonate resin including the following structural unit (2) in which a terminal structure represented by the following structural formula (1) having an unsaturated group is bonded to a molecular end; Radical polymerization initiator Includes. [ka] (In formula (1), A represents a vinyl group, an isopropenyl group, a styryl group, or a methine group. R 1 ~R 2 each independently represents a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms, R 3 ~R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a benzotriazole group, each of which may have a substituent; Z represents an ether group, a carbonyl group, an ester group, or a single bond; a is an integer from 1 to 3; Y represents an ether bond or an ester group. [ka] (In formula (2), R 5 ~R 8 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; b is an integer equal to or greater than 1; X is [ka] and where R 9 and R 10 each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; 9 and R 10 represents a group which is bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements, R 11 and R 12 each independently represents hydrogen, fluorine, chlorine, bromine or iodine, or represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R 13 represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, c represents an integer from 0 to 20; d represents an integer from 1 to 500; However, R 5 ~R 8 is hydrogen, R 9 and R 10 is a methyl group, the composition further comprises a second polycarbonate resin.

[0024] In a preferred embodiment of the present invention, the curable resin composition of the present invention is an acrylic monomer having a saturated group; A polycarbonate resin including the following structural unit (2) in which a terminal structure represented by the following structural formula (1) having an unsaturated group is bonded to a molecular end; Radical polymerization initiator The curable resin composition may be a curable resin composition that does not contain a solvent.

[0025] <Polycarbonate resin containing structural unit (2) having a terminal structure represented by the following structural formula (1) having an unsaturated group bonded to the molecular end> The polycarbonate resin used in the curable resin composition of the present invention can be produced by reacting a monohydric phenol that derives structural formula (1) at the molecular end, a bisphenol that derives structural unit (2), and a carbonate-forming compound. The polycarbonate resin used in the curable resin composition of the present invention can be produced by a known method used in producing a polycarbonate derived from bisphenol A, such as a direct reaction of a bisphenol with phosgene (phosgene method) or a transesterification reaction of a bisphenol with a bisarylcarbonate (transesterification method).

[0026] <Bisphenols that derive structural unit (2)> The bisphenol from which the structural unit (2) that is the raw material monomer for the polycarbonate resin of the present invention is derived is represented by the following structural formula (8): [ka] (In the formula, R 14 ~R 17 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; W is [ka] where R 18 and R 19 each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; 18 and R 19 represents a group which is bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements, R 20 and R 21 each independently represents hydrogen, fluorine, chlorine, bromine or iodine, or represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R 22 represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, e represents an integer from 0 to 20; f represents an integer from 1 to 500; However, R 14 ~R 17 is hydrogen, R 18 and R 19 is a methyl group, the composition further comprises a second polycarbonate resin.

[0027] The raw material monomer for the polycarbonate resin of the present invention is preferably a monomer represented by structural formula (8): R 14 ~R 17 each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms; R 18 and R 19 each independently represents hydrogen or fluorine, or each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; 18and R 19 may represent a group which combines to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements, R 20 and R 21 each independently represents hydrogen or fluorine, or each may have a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 22 may be an alkylene group having 1 to 6 carbon atoms which may have a substituent.

[0028] Specific examples of raw material monomers for the polycarbonate resin of the present invention include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(2-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfonate, and bis(4-hydroxyphenyl)sulfonate. bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, 4,Examples of bisphenols include, but are not limited to, 4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol and 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol. These bisphenols can be used alone or in combination of two or more. Among these bisphenols, it is particularly preferable to use 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, and 2,2-bis(4-hydroxyphenyl)-4-methylpentane as the main component. It is further preferable to use 2,2-bis(4-hydroxyphenyl)-4-methylpentane as the main component. In addition, when 2,2-bis(4-hydroxyphenyl)propane is used alone, it has low solubility in acrylic monomers, so 2,2-bis(4-hydroxyphenyl)propane is not used alone in the present invention.

[0029] <Monohydric phenols that lead to structural formula (1)> The monohydric phenol which induces the structural formula (1) at the molecular end is represented by the following structural formula (10). [ka] In formula (10), E represents a vinyl group, an isopropenyl group, a styryl group, or a methine group; R 23 ~R 24 each independently represents a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms, R 25 ~R 26 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a benzotriazole group, each of which may have a substituent; J represents an ether group, a carbonyl group, an ester group, or a single bond; g is an integer from 1 to 3.

[0030] In a preferred embodiment of the present invention, in structural formula (10), J is a single bond, an ether group, or an ester group, and R 23 ~R 24 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, E is a vinyl group, an isopropenyl group or a methine group, R 25 ~R 26 are each independently hydrogen, a methoxy group, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a benzotriazole group. More preferably, J is a single bond or an ester group, and R 23 ~R 24 are each independently a single bond or an ethylene group, E is an isopropenyl group or a methine group, and R 25 ~R 26 may each independently be hydrogen or a benzotriazole group.

[0031] Specific examples of the monohydric phenol of structural formula (10) include, but are not limited to, styrene derivatives such as p-hydroxystyrene and p-isopropenylphenol, allylphenol derivatives such as O-allylphenol and eugenol, methacryl derivatives such as 4-hydroxyphenyl methacrylate, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, 4-hydroxyphenyl butyl acrylate and 2-phenylphenol ethyl acrylate, and methine derivatives such as 4-ethynylphenol and 4-propargylphenol. These monohydric phenols are used alone or in combination of two or more. As the monohydric phenol of structural formula (10), p-isopropenylphenol and 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole are preferred, and 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole is more preferred.

[0032] The amount of the monohydric phenol of structural formula (10) used may be 0.2 mol or more, preferably in the range of 0.2 to 20 mol, more preferably in the range of 0.5 to 10 mol, and even more preferably in the range of 1 to 7 mol, based on 100 mol of the total bisphenols.

[0033] <Polycarbonate resin and its manufacturing method> In the phosgene method, the bisphenol of the structural formula (8), the monohydric phenol of the structural formula (10), and phosgene are reacted in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine, and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. Examples of the solvent include methylene chloride and chloroform. In addition, in order to promote the polycondensation reaction, it is preferable to use a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride. The monohydric phenol of the structural formula (10) functions as a polymerization degree regulator, but it is also possible to use other monohydric phenols such as phenol, pt-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenol in an amount of less than 50% by mass relative to the monohydric phenol of the structural formula (10). If desired, small amounts of antioxidants such as sodium sulfite and hydrosulfite, and branching agents such as phloroglucin and isatin bisphenol may be added. The reaction temperature is usually 0 to 150° C., preferably 5 to 40° C. The reaction time varies depending on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. During the reaction, it is desirable to maintain the pH of the reaction system at 10 or higher.

[0034] On the other hand, in the transesterification method, the bisphenol of the structural formula (8), the monohydric phenol of the structural formula (10), and the bisaryl carbonate are mixed and reacted at high temperature under reduced pressure. Examples of the bisaryl carbonate include bisaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. These compounds can be used alone or in combination of two or more. The reaction is usually carried out at a temperature in the range of 150 to 350°C, preferably 200 to 300°C, and the final degree of vacuum is preferably 1 mmHg or less, and the phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. The reaction time depends on the reaction temperature and the degree of vacuum, but is usually about 1 to 24 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. If desired, the reaction may be carried out by using a small amount of a molecular weight regulator other than the monohydric phenol of structural formula (10) in combination, or by adding an antioxidant or a branching agent.

[0035] The polycarbonate resin contained in the curable resin composition of the present invention preferably maintains a good balance of solubility and compatibility with acrylic monomers, transparency, and mechanical strength, which are necessary for the curable resin composition and its cured product. If the intrinsic viscosity of the resin is too low, the mechanical strength is insufficient, and if the intrinsic viscosity is too high, the solubility in acrylic monomers decreases and the viscosity of the resin composition increases, which may make it difficult to handle during cast molding. The intrinsic viscosity is preferably in the range of 0.3 to 2.0 dl / g, and more preferably in the range of 0.35 to 1.5 dl / g.

[0036] The concentration of the polycarbonate resin contained in the curable resin composition of the present invention may be in the range of 0.5 to 50 mass%, preferably 1 to 50 mass%, more preferably 1 to 30 mass%, and even more preferably 5 to 30 mass%, based on the total curable resin composition. When the blending amount of the polycarbonate resin in the curable resin composition is within the above range, the balance between solubility in the acrylic monomer, castability, and mechanical strength is good, and the workability and the appearance of the cast molded product are improved.

[0037] The curable resin composition of the present invention is a resin solution composition capable of dissolving the polycarbonate resin in an acrylic monomer and further containing a radical polymerization initiator, and is a nearly transparent liquid composition. The curable resin composition of the present invention can further be made into a colored resin solution composition by dissolving or dispersing a desired dye or pigment therein.

[0038] <Acrylic monomer> As the acrylic monomer used in the curable resin composition of the present invention, an acrylic monomer having a saturated group can be used, for example, Acrylic acid esters: for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, etc.; Methacrylic acid esters: for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, etc.; Ethylenically unsaturated carboxylic acids: for example, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc.; Among these acrylic monomers, methyl methacrylate (methyl methacrylate), ethyl methacrylate, methyl acrylate, and ethyl acrylate are preferred, and methyl methacrylate (methyl methacrylate) is more preferred.

[0039] The concentration of the acrylic monomer contained in the curable resin composition of the present invention may be in the range of 99.5 to 50 mass%, preferably 99.1 to 50 mass%, more preferably 95 to 70 mass%, and even more preferably 85 to 70 mass%, based on the total curable resin composition.

[0040] <Radical polymerization initiator> As the radical polymerization initiator, other monomers copolymerizable with the monomer and the modified unsaturated monomer can also be used.

[0041] Examples of the radical polymerization initiator include, but are not limited to, azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate. The radical polymerization initiator may be used alone or in combination of two or more. The amount of the radical polymerization initiator to be added is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass, and even more preferably 0.01 to 1% by mass, based on the total curable resin composition.

[0042] <Cast molding and its manufacturing method> The curable resin composition of the present invention can be cured as is by applying heat or light to give a transparent and strong cast molding.

[0043] The curable resin composition of the present invention can be bulk polymerized without solvent by dissolving the polycarbonate resin of the present invention in an acrylic monomer and adding a radical polymerization initiator, and cast molded products can be easily obtained by cell casting or continuous casting. The polymerization temperature for heat curing can be set arbitrarily, but it is preferably below the boiling point of the acrylic monomer, and is 40 to 100°C, more preferably 50 to 90°C, and even more preferably 60 to 80°C.

[0044] The polymerization time can be set arbitrarily, but is preferably 5 minutes to 48 hours, more preferably 10 minutes to 30 hours, and further preferably 30 minutes to 24 hours.

[0045] When photocuring is performed, visible to ultraviolet light can be irradiated for a certain period of time to cause curing. The wavelength of the irradiated light is 450 to 190 nm, preferably 400 to 200 nm, and more preferably 380 to 250 nm. The irradiation time is 1 second to 2 hours, preferably 3 seconds to 1 hour, and preferably 5 seconds to 30 minutes, depending on the accumulated light amount. The accumulated light amount can be set arbitrarily depending on the conditions, but is preferably 50 m to 100 J / cm. 2 , preferably 100m to 50J / cm 2 , and more preferably 300 m to 20 J / cm 2 is preferred.

[0046] It is also possible to put the curable resin composition into water and polymerize and cure it by a suspension polymerization method. In this case, the above-mentioned solvent can also be used in combination.

[0047] In one embodiment of the present invention, there is provided a curing method which comprises applying heat or light to the curable resin composition to cure it.

[0048] In one embodiment of the present invention, a cast article is provided which is cured in a mold using the above curing method.

[0049] In one embodiment of the present invention, there is provided a method for producing a cast article, comprising placing the curable resin composition of the present invention in a mold and curing it.

[0050] In one embodiment of the present invention, there is provided a method for producing a cast article made of a grafted polycarbonate resin, which comprises dissolving the polycarbonate resin of the present invention in an acrylic monomer, adding a radical polymerization initiator, and carrying out grafting.

[0051] In one embodiment of the present invention, a cast article is provided that is formed from the curable resin composition of the present invention.

[0052] The cast molding of the present invention may have a total light transmittance in the range of 80 to 100%, preferably 85 to 95%, more preferably 87 to 94%, and even more preferably 88 to 93%. The total light transmittance can be measured by a conventional method, for example, using a commercially available haze meter (NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.). If the total light transmittance of the cast molding falls within the above range, sufficient transparency as a general transparent member is ensured.

[0053] The cast molding of the present invention preferably has an impact strength (impact resistance) of at least 1.1 times that of a PMMA molding of the same mold. The impact strength can be set arbitrarily, but is preferably 6.5 to 100 kJ / m 2 and preferably in the range of 7.0 to 80 kJ / m 2 , more preferably 8.0 to 50 kJ / m 2 , and even more preferably 8.5 to 20 kJ / m 2 The impact strength can be measured by a conventional method, for example, using a commercially available impact tester (Impact Tester IT manufactured by Toyo Seiki Seisakusho Co., Ltd.). If the impact strength of the cast molding is within the above range, it is possible to obtain a molded product that is less likely to break than PMMA and is thin and strong.

[0054] <Other ingredients> Various solvents may be added to the curable resin solution of the present invention for the purpose of adjusting the viscosity, etc. Specific examples of the various solvents that can be added include: Halogen-based 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, pseudocumene, and mesitylene; In addition, it is also possible to use a small amount of an alcohol-based poor solvent such as ethanol or isopropyl alcohol, or a hydrocarbon-based poor solvent such as n-heptane, cyclohexane, or mineral spirits in combination.

[0055] In order to enhance the color effect, pigments, dyes, colored particles, and particles having optical coherence can be added to the curable resin composition of the present invention. As the pigments and dyes, organic pigments include azo pigments and phthalocyanine pigments, and specific examples thereof include 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. In addition, in order to produce white, pearl color, metallic color, and glitter, it is also possible to use titanium mica, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silica, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, nickel, and the like. Particles having optical coherence are particles that enhance the color effect by reflecting or scattering light, and examples thereof include glass beads, minute shells, and mica. These are preferably added in the range of 0.0001 to 10.0% by mass in the coating as desired.

[0056] Furthermore, if necessary, rust inhibitors, antioxidants, dispersants, ultraviolet absorbers, antifoaming agents, leveling agents, etc. may be added.

[0057] <Physical Properties of Curable Resin Composition> In the curable resin composition of the present invention, since the polycarbonate resin is completely dissolved in the acrylic monomer, it is not necessary to add a solvent to dissolve the polycarbonate resin. Therefore, the curable resin composition of the present invention can be molded by a casting method generally used for acrylic resins because the volume of the solvent does not decrease.

[0058] The solution viscosity of the curable resin composition of the present invention can be arbitrarily set depending on the desired casting method, but may be in the range of 1 to 20,000 mPa·s, preferably in the range of 2 to 10,000 mPa·s, 1 to 10,000 mPa·s, preferably in the range of 2 to 6,000 mPa·s, more preferably in the range of 3 to 5,000 mPa·s, and even more preferably in the range of 4 to 4,000 mPa·s. If the solution viscosity of the curable resin composition is in the above range, it is easy to handle. EXAMPLES

[0059] EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0060] <Solvent solubility> When the polycarbonate resin of each of the Examples and Comparative Examples was dissolved in 5 to 30% by mass of methyl methacrylate, the solution was placed in a sealed container and shaken for 24 hours with a shaker, after which the presence or absence of residual dissolution was visually confirmed. ◯: no residual dissolution, ×: some residual dissolution.

[0061] <Method of measuring intrinsic viscosity> The viscosity of a 0.5% by mass / volume solution of polycarbonate resin in dichloromethane was measured at 20° C. with a Huggins constant of 0.45 using an Ubbelohde viscosity tube.

[0062] <Method of measuring viscosity of curable resin composition> The viscosity of the curable resin composition was measured at 25° C. using a vibration viscometer (CJV5000 manufactured by A&A Co., Ltd.).

[0063] <Measurement of total light transmittance of cast molding> A molded article having a diameter of 53 mm and a thickness of 0.5 mm obtained from the curable resin composition was measured using a commercially available haze meter (NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.).

[0064] <Impact resistance (impact strength) test for molded products> A cylindrical molded product with an inner diameter of approximately 4.4 mm and a height of approximately 30 mm obtained from the curable resin composition was fixed to a homemade jig using a commercially available impact tester (Impact Tester IT manufactured by Toyo Seiki Seisakusho Co., Ltd.) and measured under conditions of an Izod 2J weight and a 150 degree downward swing.

[0065] Example 1 108 g (0.4 mol) of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter abbreviated as "MIBK": manufactured by Honshu Chemical Industry Co., Ltd.) and 0.2 g of hydrosulfite were dissolved in 1100 ml of a 5% by mass / mass aqueous solution of sodium hydroxide.

[0066] To this was added 400 ml of methylene chloride, and while stirring, 60 g of phosgene was blown in over about 60 minutes while maintaining the temperature at 15 to 20°C.

[0067] After the injection of phosgene was completed, 4.3 g (0.0133 mol) of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (hereinafter abbreviated as "MBZT": manufactured by Otsuka Chemical Co., Ltd.) and 100 ml of a 10 mass / mass% aqueous sodium hydroxide solution were added and vigorously stirred to emulsify the reaction liquid. After emulsification, 0.4 ml of triethylamine was added and the mixture was stirred at 20 to 30°C for approximately 40 minutes to polymerize.

[0068] After the polymerization was completed, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and repeatedly washed with water until the electrical conductivity of the washing liquid (aqueous phase) was 10 μS / cm or less. The obtained polymer solution was dropped into warm water kept at 60°C, and the solvent was evaporated and removed to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 110°C for 24 hours to obtain a polymer powder.

[0069] The intrinsic viscosity of this polymer in a 0.5 g / dl solution in methylene chloride at 20° C. was 0.51 dl / g. The polymer was analyzed by infrared absorption spectroscopy to find a peak at 1770 cm -1 Absorption due to carbonyl groups at the position near 1240 cm -1 Absorption due to ether bonds was observed in the vicinity, and it was confirmed that the material was a polycarbonate resin having carbonate bonds (hereinafter abbreviated as "PC-1").

[0070] 3 parts by mass of the obtained PC-1 was dissolved in 17 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA": Fujifilm Wako Pure Chemical Industries, Ltd.) which was dehydrated with anhydrous sodium sulfate after removing the polymerization inhibitor with a 5 mass / mass% aqueous sodium hydroxide solution as an acrylic monomer having a saturated group, and after complete dissolution, 0.01 parts by mass of azobisisobutyronitrile was added as a radical polymerization initiator and dissolved to obtain a curable resin solution composition. 1.3 g of this curable resin solution composition was placed in a cylindrical glass mold with an inner diameter of 53 mm, sealed, immersed in a water bath at 70°C for 24 hours, cured, and a cast molded product with a thickness of 0.5 mm was obtained. The total light transmittance of the obtained molded product was measured and was 89.0%. In addition, a cylindrical glass tube with an inner diameter of 4.4 mm and a height of 30 mm was filled with the curable resin solution composition in the same manner and cured under the same conditions to obtain a cast molded product. The impact strength of the obtained molded product was measured using a tensile tester.

[0071] Example 2 A polycarbonate resin (intrinsic viscosity 0.54 dl / g, hereinafter abbreviated as "PC-2") was obtained by polymerization in the same manner as in Example 1, except that 96.8 g of 1,1-bis(4-hydroxyphenyl)-2-methylpropane (hereinafter abbreviated as "IBTD": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of MIBK. Using the obtained PC-2, a cured resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded product was obtained, and the total light transmittance and impact strength were measured in the same manner.

[0072] Example 3 Polymerization was carried out in the same manner as in Example 1, except that 119.2 g of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane (hereinafter abbreviated as "IOTD": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of MIBK, to obtain a polycarbonate resin (intrinsic viscosity 0.51 dl / g, hereinafter abbreviated as "PC-3"). Using the obtained PC-3, a cured resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded product was obtained, and the total light transmittance and impact strength were measured in the same manner.

[0073] Example 4 Except for changing MBZT to 1.78 g of p-isopropenylphenol (hereinafter abbreviated as "IPP": manufactured by Mitsui Chemicals, Inc.), polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity 0.59 dl / g, hereinafter abbreviated as "PC-4"). Using the obtained PC-4, a cured resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded article was obtained, and the total light transmittance and impact strength were measured in the same manner.

[0074] Example 5 Instead of MIBK, 72.6 g of IBTD and 22.8 g of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as "BPA": manufactured by Mitsubishi Chemical Corporation) were used, and 1.62 g of MBZT was used. Except for this, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity 0.96 dl / g, hereinafter abbreviated as "PC-5"). Using the obtained PC-5, a cured resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded product was obtained. The total light transmittance and impact strength were measured in the same manner.

[0075] Example 6 Except for changing the amount of MIBK to 81 g, using 24.2 g of 2,2-bis(4-hydroxyphenyl)butane (hereinafter abbreviated as "BPB": manufactured by Honshu Chemical Industry Co., Ltd.), and changing the amount of MBZT to 7.17 g, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity 0.36 dl / g, hereinafter abbreviated as "PC-6"). Using the obtained PC-6, a cured resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded product was obtained, and the total light transmittance and impact strength were measured in the same manner.

[0076] Example 7 A curable resin solution composition was prepared in the same manner as in Example 1, except that the amount of PC-1 was changed to 1 part by mass and the amount of MMA was changed to 19 parts by mass, and the composition was cured to obtain a cast molding. The total light transmittance and impact strength were measured in the same manner.

[0077] Example 8 A curable resin solution composition was prepared in the same manner as in Example 1, except that the amount of PC-1 was changed to 6 parts by mass and the amount of MMA was changed to 14 parts by mass, and the composition was cured to obtain a cast molding. The total light transmittance and impact strength were measured in the same manner.

[0078] Comparative Example 1 Except for using 2.0 g of p-tert-butylphenol (hereinafter abbreviated as "PTBP": manufactured by DIC Corporation) instead of MBZT, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity 0.49 dl / g, hereinafter abbreviated as "PC-7"). Using the obtained PC-7, a cured resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded article was obtained, and the total light transmittance and impact strength were measured in the same manner.

[0079] Comparative Example 2 Except for using 91.2 g of BPA instead of MIBK and 2.0 g of PTBP instead of MBZT, polymerization was performed in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity 0.50 dl / g, hereinafter abbreviated as "PC-8"). Using the obtained PC-8, an attempt was made to prepare a cured resin solution composition in the same manner as in Example 1, but it did not dissolve in MMA, and the obtained cast molding became cloudy. The total light transmittance and impact strength of the cast molding were measured in the same manner as in Example 1.

[0080] Comparative Example 3 Except for not using any PC-1 at all and curing only MMA, a curable resin solution composition was prepared and cured in the same manner as in Example 1 to obtain a cast molding. The total light transmittance and impact strength of the cast molding were measured in the same manner as in Example 1.

[0081] For Examples 1 to 8 and Comparative Examples 1 to 3, the evaluation results of acrylic solubility, intrinsic viscosity of polycarbonate resin, solution viscosity of curable resin composition, total light transmittance of cast molded product, and impact strength of cast molded product are shown in Table 1 below.

[0082] [Table 1]

[0083] An example of the application of the present invention is that it is used as a modifier for acrylic resin, and specifically, it can be used in applications such as resin glass that requires transparency and strength, a replacement for automotive glass, aquariums, light guide panels, various lenses, hard coats, and paints.

Claims

1. an acrylic monomer having a saturated group; A polycarbonate resin including the following structural unit (2) in which a terminal structure represented by the following structural formula (1) having an unsaturated group is bonded to a molecular end; Radical polymerization initiator A curable resin composition comprising: 【Chemistry 1】 (In formula (1), A represents a vinyl group, an isopropenyl group, a styryl group, or a methine group; R １ ~R ２ each independently represents a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms, R ３ ~R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a benzotriazole group, each of which may have a substituent; Z represents an ether group, a carbonyl group, an ester group, or a single bond; a is an integer from 1 to 3, Y represents an ether bond or an ester group. 【Chemistry 2】 (In formula (2), R ５ ~R ８ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; b is an integer of 1 or more, X is 【Chemistry 3】 where R 9 and R 10 each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R 9 and R 10 represents a group which combines to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms, R 11 and R 12 each independently represents hydrogen, fluorine, chlorine, bromine or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R 13 represents an alkylene group having a carbon number of 1 to 9 which may have a substituent, c represents an integer from 0 to 20; d represents an integer from 1 to 500; However, R 5 ~R 8 is hydrogen, R 9 and R 10 is a methyl group, the composition further comprises a second polycarbonate resin. And, the acrylic monomer having a saturated group comprises a monomer selected from the group consisting of an acrylic acid ester, a methacrylic acid ester, and an ethylenically unsaturated carboxylic acid; The curable resin composition, wherein the structural unit (2) is at least one selected from the group consisting of the following formulas (4) to (7): 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】

2. In the formula (1), Z is a single bond or an ester group, and R １ ~R ２ are each independently a single bond or an ethylene group, A is an isopropenyl group or a methine group, R ３ ~R ４ The curable resin composition according to claim 1 , wherein each independently represents hydrogen or a benzotriazole group.

3. The curable resin composition according to claim 2, wherein the terminal structure represented by the formula (1) is a monohydric phenol derived from 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole or p-isopropenylphenol.

4. The curable resin composition according to any one of claims 1 to 3, wherein the acrylic monomer having a saturated group includes an acrylic acid ester or a methacrylic acid ester.

5. The curable resin composition according to any one of claims 1 to 4, wherein the acrylic monomer having a saturated group includes methyl methacrylate.

6. The curable resin composition according to any one of claims 1 to 5, wherein the polycarbonate resin has an intrinsic viscosity of 0.3 to 2.0 dl / g.

7. The curable resin composition according to any one of claims 1 to 6, wherein the terminal structure represented by the structural formula (1) is contained in an amount of 0.2 mol% or more relative to the structural unit (2).

8. A curing method comprising applying heat or light to the curable resin composition according to any one of claims 1 to 7 to cure the composition.

9. A cast product cured in a mold by the curing method according to claim 8.

10. A method for producing a cast molding, comprising placing the curable resin composition according to any one of claims 1 to 7 in a mold and curing the composition.

11. A cast molding formed from the curable resin composition according to any one of claims 1 to 7.

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