Curing resin composition

Abstract

To provide a resin composition for curing, wherein, a polycarbonate resin having a specific branched alkyl structure is dissolved in an acrylic monomer, enabling cast molding of a composite material of a polycarbonate resin and an acrylic resin having excellent transparency.SOLUTION: A resin composition for curing contains an acrylic monomer having a saturated group, a polycarbonate resin containing the following constitutional unit (1), and a radical polymerization initiator (where, R1 is a C3-7 alkyl group having a branched structure. R2-R5 independently represent hydrogen, or a C1-20 alkyl group, a C6-12 aryl group, a C1-5 alkoxy group, or a C7-17 aralkyl group, each of which is optionally substituted. a is an integer of 1 or greater).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition that forms a composite material of polycarbonate and acrylic, and to a cast molded 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 drawback of being prone to cracking due to its low impact resistance.

[0003] For this reason, attempts have been made to form polymer alloys with polycarbonate resins, which have excellent impact resistance. A known method for uniformly blending polycarbonate resins and acrylic resins while maintaining transparency is high-shear melt-kneading until they are nano-dispersed (Patent Document 1). Other known methods include dissolving acrylic monomers and polycarbonate having unsaturated groups in dichloromethane solvent and forming a copolymer by solution polymerization (Patent Document 2), and dispersing solid polycarbonate having unsaturated groups in water, adsorbing the acrylic monomers to the polycarbonate, and then carrying out suspension polymerization (Patent Document 3).

[0004] However, these methods have room for improvement because they do not allow molding by the casting method commonly used with acrylic resins, and the long-term stability of the unsaturated groups is not necessarily sufficient. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5697143 [Patent Document 2] Special Publication No. 48-025076 [Patent Document 3] Japanese Patent Application Publication No. 06-041258 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a curable resin composition that can be used to cast a highly transparent composite material of polycarbonate resin and acrylic resin by dissolving a polycarbonate resin having a specific structure in an acrylic monomer. [Means for solving the problem]

[0007] Means for Solving the Problems of the Prior Art As a result of extensive research, the present inventors have found that a polycarbonate resin having a specific branched alkyl structure as its main skeleton is highly soluble in acrylic monomers and serves as a curable resin composition suitable for cast molding to form a composite material of polycarbonate resin and acrylic resin with excellent transparency, thereby completing the present invention.

[0008] That is, the present invention includes the following aspects. [1] an acrylic monomer having a saturated group; A polycarbonate resin containing the following structural unit (1): Radical polymerization initiator A curable resin composition comprising: [ka] (In formula (1), R1 represents a branched alkyl group having 3 to 7 carbon atoms, R2 to R5 each independently represent hydrogen 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; a is an integer greater than or equal to 1.) [2] In the formula (1), R1 represents a branched alkyl group having 3 to 7 carbon atoms, R2 to R5 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, each of which may have a substituent; a is an integer greater than or equal to 1, The curable resin composition according to [1] above. [3] The curable resin composition according to [1] above, wherein the structural unit (1) is at least one selected from the group consisting of the following formulae (2) and (3): [ka] [ka] [4] The curable resin composition according to any one of [1] to [3] above, wherein the acrylic monomer includes an acrylic acid ester or a methacrylic acid ester. [5] The curable resin composition according to any one of the above [1] to [4], wherein the acrylic monomer includes methyl methacrylate. [6] The curable resin composition according to any one of [1] to [5] above, 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 [1] to [6] above, wherein the polycarbonate resin does not have a terminal structure having an unsaturated group at its molecular end. [8] A curing method comprising applying heat or light to the curable resin composition according to any one of the above [1] to [7] to cure it. [9] A cast product formed by the curing method described in [8] above.

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

[11] A cast molding formed from the curable resin composition according to any one of [1] to [7] above. [Effects of the Invention]

[0009] 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 be used to form a composite material of polycarbonate resin and acrylic resin with excellent transparency by a casting method. DETAILED DESCRIPTION OF THE INVENTION

[0010] 1. Curing resin composition The curable resin composition of the present invention comprises: an acrylic monomer having a saturated group; A polycarbonate resin containing the following structural unit (1): Radical polymerization initiator Includes. [ka] (In formula (1), R1 represents a branched alkyl group having 3 to 7 carbon atoms, R2 to R5 each independently represent hydrogen 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; a is an integer greater than or equal to 1.)

[0011] In a preferred embodiment of the present invention, in formula (1), R1 represents a branched alkyl group having 3 to 7 carbon atoms, R2 to R5 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, each of which may have a substituent; a is an integer greater than or equal to 1, A curable resin composition is provided.

[0012] In a preferred embodiment of the present invention, the curable resin composition of the present invention comprises: an acrylic monomer having a saturated group; a polycarbonate resin containing the structural unit (1); Radical polymerization initiator The curable resin composition may be a solvent-free curable resin composition.

[0013] <Polycarbonate resin containing structural unit (1)> The polycarbonate resin used in the curable resin composition of the present invention can be produced by reacting a bisphenol that derives the structural unit (1) with a carbonate ester-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 polycarbonates 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).

[0014] <Bisphenols that derive structural unit (1)> The bisphenol from which the structural unit (1) serving as the raw material monomer for the polycarbonate resin of the present invention is derived is represented by the following structural formula (4): [ka] (In the formula, R6 represents an alkyl group having a branched structure and having 3 to 7 carbon atoms, and R7 to R 10 are each independently 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.

[0015] The raw material monomer for the polycarbonate resin of the present invention is preferably a monomer represented by structural formula (4): R6 represents a branched alkyl group having 3 to 7 carbon atoms; R7~R 10 may each independently be hydrogen or an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, each of which may have a substituent.

[0016] Specific examples of raw material monomers for the polycarbonate resin of the present invention include 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-2-ethylbutane, 1,1-bis(4-hydroxyphenyl)-3-methylbutane, 1,1-bis(4-hydroxyphenyl)-2-methylhexane, 1,1-bis(4-hydroxyphenyl)-2-methylbutane, and 1,1-bis(4-hydroxyphenyl)-3-methylpentane. These may be used in combination of two or more types. Among these, 1,1-bis(4-hydroxyphenyl)-2-methylpropane and 1,1-bis(4-hydroxyphenyl)-2-ethylhexane are particularly preferred.

[0017] Furthermore, as a raw material monomer for the polycarbonate resin of the present invention, the bisphenol of structural formula (4) can be used in combination with other bisphenols. Specific examples of bisphenols that can be used in combination with the bisphenol of structural formula (4) in 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, and bis(4-hydroxy-3-methylphenyl). Sulfone, bis(4-hydroxyphenyl) sulfoxide, 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-hydroxyphenyl)butane, 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)cycloundecane, 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,Examples include, but are not limited to, ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol, and 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol. These bisphenols other than those of structural formula (4) may be used singly or in combination of two or more. Among these bisphenols other than those of structural formula (4), 1,1-bis(4-hydroxyphenyl)ethane and 2,2-bis(4-hydroxyphenyl)butane are particularly preferred. When bisphenols other than those of structural formula (4) are used in combination, the amount of the bisphenols other than those of structural formula (4) is preferably 50 mol % or less, more preferably 30 mol % or less, based on the total amount of bisphenols, including those of structural formula (4).

[0018] <Polycarbonate resin and its manufacturing method> In the phosgene method, bisphenol of structural formula (4) is reacted with phosgene in the presence of an acid binder and a solvent. Examples of acid binders include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of solvents include methylene chloride and chloroform. To accelerate the condensation polymerization 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. Furthermore, to control the degree of polymerization, it is preferable to add a monofunctional compound such as phenol, pt-butylphenol, p-cumylphenol, or an alkyl-substituted phenol as a molecular weight regulator. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin or 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. It is also desirable to maintain the pH of the reaction system at 10 or higher during the reaction.

[0019] On the other hand, in the transesterification method, the bisphenol of structural formula (4) is mixed with a bisaryl carbonate and reacted at high temperature under reduced pressure. Examples of bisaryl carbonates 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 typically carried out at a temperature ranging from 150 to 350°C, preferably from 200 to 300°C, and the final pressure reduction is preferably 1 mmHg or less, allowing the phenols derived from the bisaryl carbonate produced by the transesterification reaction to be distilled out of the system. The reaction time varies depending on the reaction temperature and the degree of vacuum, but is typically 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 in the presence of a monofunctional compound such as phenol, pt-butylphenol, p-cumylphenol, or an alkyl-substituted phenol, a molecular weight regulator, or by adding an antioxidant or a branching agent.

[0020] 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 required for the curable resin composition and its cured product. If the resin's intrinsic viscosity is too low, the mechanical strength will be insufficient, while if the intrinsic viscosity is too high, the solubility in acrylic monomers will decrease and the viscosity of the resin composition will increase, making 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.

[0021] 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, a good balance is achieved between solubility in the acrylic monomer, castability, and mechanical strength, improving workability and the appearance of the cast molded article.

[0022] The polycarbonate resin contained in the curable resin composition of the present invention does not have a reactive unsaturated group such as an alkenyl group or an alkynyl group in any of its main chain, side chain, or molecular terminal.

[0023] The curable resin composition of the present invention is a resin solution composition in which the polycarbonate resin can be dissolved in an acrylic monomer and which contains a radical polymerization initiator, and is a substantially transparent liquid composition. The curable resin composition of the present invention can be further colored by dissolving or dispersing a desired dye or pigment in the curable resin composition.

[0024] <Acrylic monomer> The acrylic monomer used in the curable resin composition of the present invention may be an acrylic monomer having a saturated group, 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.

[0025] 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.

[0026] <Radical polymerization initiator> As the radical polymerization initiator, other monomers copolymerizable with the monomer and the modified unsaturated monomer can also be used.

[0027] Examples of radical polymerization initiators 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. One radical polymerization initiator may be used alone, or two or more radical polymerization initiators may be used in combination. The amount of radical polymerization initiator 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.

[0028] <Cast molding and its manufacturing method> The curable resin composition of the present invention can be cured as it is by applying heat or light to give a transparent and strong cast molding.

[0029] The curable resin composition of the present invention can be prepared by dissolving the polycarbonate resin of the present invention in an acrylic monomer, adding a radical polymerization initiator, and bulk polymerization without solvent, and cast moldings can be easily obtained by cell casting or continuous casting. The polymerization temperature for heat curing can be set as desired, but is preferably below the boiling point of the acrylic monomer, and is preferably 40 to 100°C, more preferably 50 to 90°C, and even more preferably 60 to 80°C.

[0030] The polymerization time can be set arbitrarily, but is preferably 5 minutes to 48 hours, more preferably 10 minutes to 30 hours, and even more preferably 30 minutes to 24 hours.

[0031] 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 mJ / cm2 to 100 J / cm2.2 , preferably 100m to 50J / cm 2 , and more preferably 300 m to 20 J / cm 2 is preferred.

[0032] It is also possible to put the curable resin composition into water and polymerize and cure it by suspension polymerization, in which case the above-mentioned solvent can also be used in combination.

[0033] 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.

[0034] In one embodiment of the present invention, a cast article is provided that is cured in a mold using the above-described curing method.

[0035] In one embodiment of the present invention, there is provided a method for producing a cast article, which comprises placing the curable resin composition of the present invention in a mold and curing it.

[0036] In one embodiment of the present invention, a cast article is provided that is formed from the curable resin composition of the present invention.

[0037] 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 can be ensured.

[0038] The cast molding of the present invention preferably has an impact strength (impact resistance) that is 1.1 times or more 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 / m2 , and even more preferably 8.2 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, Ltd.). If the impact strength of the cast molded article is within the above range, it is possible to obtain a molded article that is less likely to break than PMMA and is thin and strong.

[0039] <Other ingredients> Various solvents may be added to the curable resin solution of the present invention for the purpose of adjusting viscosity, etc. Specific examples of the various solvents that can be added include: Halogenated 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; Furthermore, 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.

[0040] To enhance color effects, pigments, dyes, colored particles, and particles with optical coherence can be added to the curable resin composition of the present invention. Examples of pigments and dyes include organic pigments such as azo pigments and phthalocyanine pigments. Specific examples 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. To achieve white, pearlescent, metallic, or glitter colors, titanium dioxide, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silica, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, and nickel can also be used. Optical coherence particles are particles that enhance color effects by reflecting or scattering light, and examples include glass beads, tiny shells, and mica. These are preferably added in the range of 0.0001 to 10.0 mass % in the coating as desired.

[0041] Furthermore, if necessary, rust inhibitors, antioxidants, dispersants, ultraviolet absorbers, antifoaming agents, leveling agents, etc. may be added.

[0042] <Physical properties of curable resin composition> In the curable resin composition of the present invention, the polycarbonate resin is completely dissolved in the acrylic monomer, so there is no need to add a solvent to dissolve the polycarbonate resin. Therefore, the curable resin composition of the present invention does not lose volume due to the solvent, and can be molded by a casting method that is commonly used for acrylic resins.

[0043] The solution viscosity of the curable resin composition of the present invention can be set arbitrarily depending on the desired casting method, but may be in the range of 1 to 20,000 mPa·s, preferably 2 to 10,000 mPa·s, 1 to 10,000 mPa·s, preferably 2 to 6,000 mPa·s, more preferably 3 to 5,000 mPa·s, and even more preferably 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. [Example]

[0044] Examples of the present invention will be shown below together with comparative examples to explain the details of the invention, but the present invention is not limited to these examples.

[0045] <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. ◯ indicates no residual dissolution, and × indicates residual dissolution.

[0046] <Method for measuring intrinsic viscosity> The viscosity of a 0.5% by mass / volume solution of polycarbonate resin in dichloromethane was measured using an Ubbelohde viscosity tube at 20°C with a Huggins constant of 0.45.

[0047] <Method for 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.).

[0048] <Measurement of total light transmittance of cast moldings> 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.).

[0049] <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 measurements were carried out under conditions of an Izod 2J weight and a 150-degree downward swing.

[0050] Example 1 80 g (0.33 mol) of 1,1-bis(4-hydroxyphenyl)-2-methylpropane (hereinafter abbreviated as "IBTD": 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.

[0051] 400 ml of methylene chloride was added to the mixture, and while stirring, 46 g of phosgene was blown in over about 60 minutes while maintaining the temperature at 15 to 20°C.

[0052] After the phosgene injection was completed, 1.65 g (0.011 mol) of p-tert-butylphenol (hereinafter abbreviated as "PTBP": manufactured by DIC Corporation) and 100 ml of a 10% by mass / mass aqueous sodium hydroxide solution were added, and the mixture was stirred vigorously 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 allow polymerization.

[0053] After the polymerization was completed, the reaction mixture 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 conductivity of the washings (aqueous phase) reached 10 μS / cm or less. The resulting polymer solution was added dropwise to warm water maintained at 60°C, and the solvent was evaporated to obtain a white powdery precipitate. The resulting precipitate was filtered and dried at 110°C for 24 hours to obtain a polymer powder.

[0054] The intrinsic viscosity of a 0.5 g / dl solution of this polymer in methylene chloride at 20°C was 0.53 dl / g. The obtained polymer was analyzed by infrared absorption spectroscopy, and the intrinsic viscosity was 1770 cm -1 Absorption due to carbonyl groups at a position near 1240 cm -1Absorption due to ether bonds was observed in the vicinity, and it was confirmed that the resin was a polycarbonate resin having carbonate bonds (hereinafter abbreviated as "PC-1").

[0055] Three parts by mass of the resulting PC-1 were dissolved in 17 parts by mass of methyl methacrylate (hereafter abbreviated as "MMA"; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), an acrylic monomer having a saturated group. The polymerization inhibitor had been removed with a 5% by mass aqueous solution of sodium hydroxide, followed by dehydration with anhydrous sodium sulfate. 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, and immersed in a water bath at 70°C for 24 hours to cure, yielding a 0.5 mm thick cast molded product. The total light transmittance of the resulting molded product was measured and found to be 89.0%. A cylindrical glass tube with an inner diameter of 4.4 mm and a height of 30 mm was similarly filled with the curable resin solution composition and cured under the same conditions to obtain a cast molded product. The impact strength of the resulting molded product was measured.

[0056] Example 2 Polymerization was carried out in the same manner as in Example 1, except that 90.0 g of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane (hereinafter abbreviated as "IOTD": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of IBTD, and the amounts of phosgene and PTBP were changed to 42 g and 1.50 g, respectively, to obtain a polycarbonate resin (intrinsic viscosity 0.52 dL / g, hereinafter abbreviated as "PC-2"). Using the obtained PC-2, a curable resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded article was obtained. The total light transmittance and impact strength were measured in the same manner.

[0057] Example 3 Polymerization was carried out in the same manner as in Example 1, except that the amount of IBTD was changed to 60 g and 20 g of 2,2-bis(4-hydroxyphenyl)butane (hereinafter abbreviated as "BPB": manufactured by Honshu Chemical Industry Co., Ltd.) was also used, to obtain a polycarbonate resin (intrinsic viscosity 0.54 dL / g, hereinafter abbreviated as "PC-3"). Using the obtained PC-3, a curable 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.

[0058] Example 4 Polymerization was carried out in the same manner as in Example 1, except that the amount of IBTD was changed to 60 g, 20 g of 1,1-bis(4-hydroxyphenyl)ethane (hereinafter abbreviated as "BPE": manufactured by Honshu Chemical Industry Co., Ltd.) was also used, and the amount of phosgene and the amount of PTBP were changed to 48 g and 1.76 g, respectively, to obtain a polycarbonate resin (intrinsic viscosity 0.50 dL / g, hereinafter abbreviated as "PC-4"). Using the obtained PC-4, a curable resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded article was obtained. The total light transmittance and impact strength were measured in the same manner.

[0059] Example 5 A polycarbonate resin (intrinsic viscosity 0.95 dL / g, hereinafter abbreviated as "PC-5") was obtained by polymerization in the same manner as in Example 1, except that the amount of PTBP was changed to 0.71 g. Using the obtained PC-5, a curable resin solution composition was prepared in the same manner as in Example 1, and the composition was cured to obtain a cast molded article, and the total light transmittance and impact strength were measured in the same manner.

[0060] Example 6 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 molded article, and the total light transmittance and impact strength were measured in the same manner.

[0061] Example 7 A curable resin solution composition was prepared and cured 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 a cast molded article was obtained. The total light transmittance and impact strength were measured in the same manner.

[0062] Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that 90 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter abbreviated as "MIBK": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of IBTD and the amount of PTBP was changed to 1.67 g, to obtain a polycarbonate resin (intrinsic viscosity 0.49 dL / g, hereinafter abbreviated as "PC-6"). Using the obtained PC-6, a curable 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.

[0063] Comparative Example 2 IBTD Instead of Bisphenol A (hereinafter referred to as BPA ") Use 75.4g there was Except for the above, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity 0.50 dl / g, hereinafter abbreviated as "PC-7"). An attempt was made to prepare a curable resin solution composition using the obtained PC-7 in the same manner as in Example 1, but it did not dissolve in MMA, and the obtained cast molded article became cloudy. The total light transmittance and impact strength of the cast molded article were measured in the same manner as in Example 1.

[0064] Comparative Example 3 Polymerization was carried out in the same manner as in Example 1, except that 90 g of 2,2-bis(4-hydroxyphenyl)butane (hereinafter abbreviated as "BPB": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of IBTD, and the amounts of phosgene and PTBP were changed to 49 g and 1.85 g, respectively, to obtain a polycarbonate resin (intrinsic viscosity 0.50 dL / g, hereinafter abbreviated as "PC-8"). Using the obtained PC-8, a curable resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded article was obtained. The total light transmittance and impact strength were measured in the same manner.

[0065] Comparative Example 4 Polymerization was carried out in the same manner as in Example 1, except that 80 g of 1,1-bis(4-hydroxyphenyl)ethane (hereinafter abbreviated as "BPE": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of IBTD, and the amounts of phosgene and PTBP were changed to 50 g and 2.44 g, respectively, to obtain a polycarbonate resin (intrinsic viscosity 0.49 dL / g, hereinafter abbreviated as "PC-9"). Using the obtained PC-9, a curable resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded article was obtained. The total light transmittance and impact strength were measured in the same manner.

[0066] Comparative Example 5 Polymerization was carried out in the same manner as in Example 1, except that 90 g of 1,1-bis(4-hydroxyphenyl)decane (hereinafter abbreviated as "DED": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of IBTD, and the amounts of phosgene and PTBP were changed to 39 g and 1.38 g, respectively, to obtain a polycarbonate resin (intrinsic viscosity 0.52 dL / g, hereinafter abbreviated as "PC-10"). Using the obtained PC-10, a curable resin solution composition was prepared in the same manner as in Example 1, cured, and a cast molded article was obtained. The total light transmittance and impact strength were measured in the same manner.

[0067] Comparative Example 6 A curable resin solution composition was prepared and cured in the same manner as in Example 1, except that only MMA was cured without using any PC-1, to obtain a cast molded article. The total light transmittance and impact strength of the cast molded article were measured in the same manner as in Example 1.

[0068] For Examples 1 to 7 and Comparative Examples 1 to 6, 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.

[0069] [Table 1]

[0070] As shown in Table 1 below, the composition of the present invention has the acrylic solubility required for cast molding, and cast molded articles made from the composition of the present invention can achieve transparency equivalent to that of articles made from acrylic resins without compromising impact strength compared to articles made from commonly used PC monomers.

[0071] The present invention can be utilized as a modifier for acrylic resins, and specifically can be applied to applications such as resin glass that requires transparency and strength, automotive glass replacement, aquariums, light guide plates, various lenses, hard coats, and paints.

Claims

1. an acrylic monomer having a saturated group; A polycarbonate resin containing the following structural unit (1): Radical polymerization initiator A curable resin composition comprising: 【Chemical 1】 (In formula (1), R １ represents a branched alkyl group having 3 to 7 carbon atoms, R ２ ~R ５ are each independently selected from hydrogen 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, and an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; a is an integer of 1 or greater.) And, The structural unit (1) is at least one selected from the group consisting of the following formulae (2) and (3): 【Chemistry 2】 【Chemistry 3】 the acrylic monomer having a saturated group includes a monomer selected from the group consisting of an acrylic acid ester and a methacrylic acid ester; The monomer from which the polycarbonate resin is derived optionally further contains a bisphenol compound other than the bisphenol compound from which the structural unit (1) is derived, The bisphenol compound from which the structural unit (1) is derived is contained in an amount of more than 50 mol% based on the total amount of bisphenol compounds. Curing resin composition.

2. The curable resin composition according to claim 1 , wherein the acrylic monomer having a saturated group includes methyl methacrylate.

3. 3. The curable resin composition according to claim 1, wherein the polycarbonate resin has an intrinsic viscosity of 0.3 to 2.0 dl / g.

4. The curable resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin does not have a terminal structure having an unsaturated group at its molecular end.

5. The curable resin composition according to any one of claims 1 to 4, wherein the bisphenol compound from which the structural unit (1) is derived is contained in an amount of more than 70 mol% relative to the total amount of bisphenol compounds.

6. A curing method for curing the curable resin composition according to any one of claims 1 to 5 by applying heat or light.

7. A cast product obtained by the curing method of claim 6 and molding the composition in a mold.

8. A method for producing a cast molding, comprising placing the curable resin composition according to any one of claims 1 to 5 in a mold and curing it.

9. A cast molding formed from the curable resin composition according to any one of claims 1 to 5.

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