JP6657641B2 - Resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a resin composition and a molded article thereof.

  Polycarbonate is widely used in electric and electronic and OA equipment, optical media, automobile parts, building components, and the like because of its excellent mechanical strength, heat resistance, electrical properties, dimensional stability, flame retardancy, transparency, and the like.

  Such a polycarbonate is usually prepared by an interfacial method of directly reacting bisphenol A (aromatic dihydroxy compound) with phosgene or a transesterification reaction (polycondensation reaction) of bisphenol A and diphenyl carbonate (carbonic acid diester) in a molten state. Manufactured by a method.

  However, a molded product obtained from a polycarbonate-based resin produced using bisphenol A as an aromatic dihydroxy compound has insufficient surface hardness in outdoor uses such as, for example, automobile headlamps, eyeglass lenses, and sheets. .

  Therefore, a hard coat layer or the like may be provided on the surface layer of the polycarbonate-based resin to improve the surface hardness in some cases.

  However, providing a hard coat layer or the like on the surface layer decreases the production efficiency because the number of manufacturing steps increases by one. Furthermore, in the case of a molded article having a complicated shape, it is difficult to provide a hard coat layer.

  Therefore, many studies have been made to improve surface hardness while maintaining transparency by blending a specific resin with a polycarbonate resin. Many examples of using an acrylic resin, which is a transparent resin similarly to the polycarbonate resin, as a resin to be mixed with the polycarbonate resin have been proposed. For example, Patent Literatures 1 and 2 describe resin compositions containing a polycarbonate resin and an acrylic resin having a specific range of molecular weight.

  Further, an example in which an acrylic copolymer is blended has been proposed. For example, Patent Documents 3 to 7 describe resin compositions containing a polycarbonate resin and a (meth) acrylic copolymer.

JP-A-62-131056 JP-A-63-139935 JP-A-64-1749 JP 2010-116501 A JP-A-4-359954 JP 2011-500914 A International Publication No. WO 2013/094898

  The resin compositions proposed in Patent Literatures 1 to 7 are either difficult to provide a molded product with sufficient surface hardness and impart transparency, or have properties of surface hardness and transparency. However, there is a problem that the weather resistance is deteriorated even if both can be satisfied. Furthermore, if the weather resistance is to be improved by various additives, a large amount of addition is required, and there is a problem that the appearance of the molded product is deteriorated due to contamination of the mold during injection molding.

  Therefore, an object of the present invention is to provide a molded article having excellent surface hardness and transparency and to improve the hue and weather resistance after molding by adding an additive that does not cause a problem in appearance of the molded article due to mold contamination. It is to provide an excellent resin composition.

  The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a resin composition containing a (meth) acrylate unit having a specific skeleton can efficiently form a molded article excellent in surface hardness and transparency. The present inventors have found that they can be produced at low cost, and that the hue and weather resistance after molding can be remarkably improved by using a specific ultraviolet absorber and an antioxidant in combination. That is, the present invention is, for example, as follows.

[1] A polymer (A) containing 45% by mass or more of a (meth) acrylate unit (a) represented by the following formula (1) and a polymer containing 60% by mass or more of a methyl (meth) acrylate unit (b), A resin composition comprising a polymer (B) having an average molecular weight of 5,000 to 20,000, a polycarbonate resin (C), an ultraviolet absorber (D) and an antioxidant (E), wherein (A) Resin composition containing 0.1 to 1.5 parts by mass of (D) and 0.05 to 1.0 part by mass of (E) based on 100 parts by mass of resin component containing, (B) and (C) .
(In equation (1),
R ₁ is a hydrogen atom or a methyl group;
R ₂ is each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a linear alkyl group having 1 to 10 carbon atoms. Alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group which may have a substituent or a phenyl which may have a substituent A phenyl group;
n is an integer of 0-5. )
[2] In the resin component, the total content of the polymer (A) and the polymer (B) is 5 to 60% by mass, and the content of the polycarbonate resin (C) is 40 to 95%. Item 2. The resin composition according to item 1, which is% by mass.
[3] The first or second item, wherein a mass ratio ((A) / (B)) of the polymer (A) and the polymer (B) is 0.5 / 99.5 to 30/70. Item 3. The resin composition according to Item 2.
[4] The resin composition according to any one of items 1 to 3, wherein the ultraviolet absorber (D) has a benzotriazole structure.
[5] The resin according to any one of Items 1 to 4, wherein the compounding amount of the ultraviolet absorbent (D) is 0.3 to 0.6 parts by mass with respect to 100 parts by mass of the resin component. Composition.
[6] The resin composition according to any one of items 1 to 5, wherein the antioxidant (E) contains a phenolic antioxidant.
[7] The resin composition according to item 6, further comprising a phosphite-based antioxidant.
[8] The resin according to any one of Items 1 to 7, wherein the compounding amount of the antioxidant (E) is 0.2 to 0.4 parts by mass with respect to 100 parts by mass of the resin component. Composition.
[9] A molded article obtained by molding the resin composition according to any one of Items 1 to 8.
[10] A polymer (A) containing 45% by mass or more of (meth) acrylate units (a) represented by the following formula (1) and 60% by mass or more of methyl (meth) acrylate units (b) And a polymer (B) having a weight average molecular weight of 5,000 to 20,000.
(In equation (1),
R ₁ is a hydrogen atom or a methyl group;
R ₂ is each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a linear alkyl group having 1 to 10 carbon atoms. Alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group which may have a substituent or a phenyl which may have a substituent A phenyl group;
n is an integer of 0-5. )

  According to the present invention, it is possible to efficiently and inexpensively mold a molded article having excellent surface hardness and transparency, and without causing appearance defects due to mold contamination, a resin composition having excellent hue and weather resistance after molding. Can be provided.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention comprises a polymer (A) containing 45% by mass or more of a (meth) acrylate unit (a) represented by the following formula (1) and a methyl (meth) acrylate unit (b) of 60%. A polymer having a weight-average molecular weight of 5,000 to 20,000 (B), a polycarbonate resin (C), an ultraviolet absorber (D), and an antioxidant (E); ), (B) and (C), 100 to 100 parts by mass of the resin component, 0.1 to 1.5 parts by mass of (D) and 0.05 to 1.0 part by mass of (E).

Hereinafter, each component contained in the resin composition of the present invention will be described in order.
[1] Polymer (A)
The polymer (A) which is a component in the resin composition of the present embodiment contains 45% by mass or more of a (meth) acrylate unit (a) represented by the following formula (1).

  The polymer (A) which is a component in the resin composition of the present embodiment is represented by the following formula (1). In this specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. Further, in the present specification, the expression “polymer” includes a case where it is a copolymer.

In the above formula (1), R ₁ is a hydrogen atom or a methyl group, preferably a methyl group.

R ₂ is each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a linear alkyl group having 1 to 10 carbon atoms. An alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group. These may have a substituent. Examples of the substituent include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, and a cyclic alkyl group having 3 to 10 carbon atoms. Groups, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom and the like.
R ₂ is preferably a methyl group, a methoxy group, a chloro group, a bromo group or a phenyl group, more preferably a phenyl group.

  n is an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0.

  Examples of the compound constituting the (meth) acrylate unit (a) represented by the above formula (1) include, for example, phenyl (meth) acrylate, 4-phenylphenyl (meth) acrylate, 3-phenylphenyl (meth) acrylate, -Phenylphenyl (meth) acrylate, 4-biphenylphenyl (meth) acrylate, 3-biphenylphenyl (meth) acrylate, 2-biphenylphenyl (meth) acrylate, 4-methylphenyl (meth) acrylate, 3-methylphenyl (meth) ) Acrylate, 2-methylphenyl (meth) acrylate, 4-ethylphenyl (meth) acrylate, 3-ethylphenyl (meth) acrylate, 2-ethylphenyl (meth) acrylate, 4-normalpropylphenyl (meth) acrylate, -Normal propyl phenyl (meth) acrylate, 2-normal propyl phenyl (meth) acrylate, 4-isopropyl phenyl (meth) acrylate, 3-isopropyl phenyl (meth) acrylate, 2-isopropyl phenyl (meth) acrylate, 4-cyclohexyl phenyl (Meth) acrylate, 3-cyclohexylphenyl (meth) acrylate, 2-cyclohexylphenyl (meth) acrylate 4-methoxyphenyl (meth) acrylate, 3-methoxyphenyl (meth) acrylate, 2-methoxyphenyl (meth) acrylate, 4 -Ethoxyphenyl (meth) acrylate, 3-ethoxyphenyl (meth) acrylate, 2-ethoxyphenyl (meth) acrylate, 4-fluorophenyl (meth) acryl , 3-fluorophenyl (meth) acrylate, 2-fluorophenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, 3-chlorophenyl (meth) acrylate, 2-chlorophenyl (meth) acrylate, 4-bromophenyl ( Examples include (meth) acrylate, 3-bromophenyl (meth) acrylate, 2-bromophenyl (meth) acrylate, 4-iodophenyl (meth) acrylate, 3-iodophenyl (meth) acrylate, and 2-iodophenyl (meth) acrylate. be able to. These can be used alone or in combination of two or more. Of these, phenyl (meth) acrylate, 4-phenylphenyl (meth) acrylate, 4-methylphenyl (meth) acrylate, and 4-methoxyphenyl (meth) acrylate are preferred, and phenyl (meth) acrylate is more preferred. 4-phenylphenyl (meth) acrylate.

The polymer (A) in the present embodiment contains the (meth) acrylate unit (a) represented by the formula (1) in a proportion of 45% by mass or more based on the polymer (A). The polymer (A) needs to be added in order to improve the compatibility between the polymer (B) described later and the polycarbonate resin (C). (Meth) acrylate unit (a). Therefore, the proportion of the (meth) acrylate unit (a) in the polymer (A) is preferably from 50 to 99% by mass, and more preferably from 60 to 97% by mass.
When the proportion of the (meth) acrylate unit (a) is 45% by mass or more, the compatibility between the polymer (B) and the polycarbonate resin (C) is sufficiently improved, and the transparency of the polycarbonate resin (C) is improved. Is maintained. On the other hand, in order to suppress thermal decomposition, other monomers described below may be copolymerized, so that the ratio of the (meth) acrylate unit (a) is preferably 99% by mass or less.

  The polymer (A) used in the present embodiment is produced by copolymerizing another monomer (hereinafter, sometimes referred to as a component (s)) at a ratio of less than 50% by mass, if necessary. Is also good. The component (s) is not particularly limited as long as it does not adversely affect the properties of the resin composition. For example, methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate; methyl acrylate, ethyl acrylate, Acrylates such as butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate and glycidyl acrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; diene monomers such as butadiene, isoprene and dimethylbutadiene; vinyl methyl ether and vinyl Vinyl ether monomers such as ethyl ether; carboxylic acid vinyl monomers such as vinyl acetate and vinyl butyrate; olefins such as ethylene, propylene and isobutylene Ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid and itaconic acid; vinyl halide monomers such as vinyl chloride and vinylidene chloride; maleimide, N-phenylmaleimide; Maleimide monomers such as N-cyclohexylmaleimide and N-methylmaleimide; and crosslinking agents such as allyl (meth) acrylate, divinylbenzene, and 1,3-butylene methacrylate. Of these, methacrylate, acrylate, or vinyl cyanide monomer is preferable, and methacrylate or acrylate is more preferable. These monomers can be used alone or in combination of two or more.

  When the polymer (A) is obtained by copolymerizing the component (s), the constituent unit derived from the component (s) is contained at a ratio of 0.1 to 5% by mass based on the polymer (A). Is preferably 0.5 to 4% by mass, and particularly preferably 1 to 3% by mass.

  The mass average molecular weight of the polymer (A) is preferably from 50,000 to 5,000,000, more preferably from 80,000 to 3,000,000, and particularly preferably from 100,000 to 2,000,000. When the mass average molecular weight is from 50,000 to 5,000,000, the compatibility with the polycarbonate resin (C) is good, and it is preferable from the viewpoint of mechanical properties and surface hardness.

  The polymerization method for obtaining the polymer (A) in the present embodiment is not particularly limited. For example, a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method may be used. it can. The suspension polymerization method and the bulk polymerization method are preferred, and the suspension polymerization method is more preferred. In addition, additives necessary for the polymerization can be appropriately added as needed, and examples of the additives include a polymerization initiator, an emulsifier, a dispersant, and a chain transfer agent.

  The polymerization temperature depends on additives such as a (meth) acrylate monomer composition and a polymerization initiator, but is preferably from 50C to 150C, more preferably from 70C to 130C. The polymerization may be carried out by raising the temperature in multiple stages.

  The polymerization time varies depending on the polymerization method, the (meth) acrylate monomer composition, and additives such as a polymerization initiator, but is preferably 1 hour to 8 hours at the target temperature, more preferably 2 hours to 6 hours. In addition, the time until the temperature is raised to the target temperature is further added to the polymerization time.

  The reaction pressure varies depending on the polymerization method, the composition of the (meth) acrylate monomer, and the like, but it is preferably polymerization at normal pressure to 3 MPa, and more preferably at normal pressure to 1 MPa.

[2] Polymer (B)
The polymer (B) in this embodiment contains the methyl (meth) acrylate unit (b) in an amount of 60% by mass or more, and has a weight average molecular weight of 5,000 to 20,000.

  The content of the methyl (meth) acrylate unit (b) in the polymer (B) is 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. .

  The upper limit of the content of the methyl (meth) acrylate unit (b) in the polymer (B) is preferably 99.5% by mass or less, more preferably 99% by mass or less.

  When the content of the methyl (meth) acrylate unit (b) in the polymer (B) is within the above range, a molded article having excellent surface hardness can be obtained.

  The polymer (B) may contain structural units derived from other monomers in a range of less than 40% by mass. The structural unit derived from the other monomer may be a structural unit derived from a monomer copolymerizable with methyl (meth) acrylate, and may be a structural unit derived from an α, β-unsaturated monomer. Is preferred.

  Examples of such a monomer include alkyl methacrylates such as ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; alkyl acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; phenyl methacrylate, benzyl methacrylate, phenyl acrylate and benzyl acrylate Aromatic (meth) acrylates such as styrene; aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.

  Of these, alkyl acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and styrene are preferred.

  The weight average molecular weight (Mw) of the polymer (B) is 5,000 or more, preferably 7,000 or more, and more preferably 9,000 or more.

  When the Mw of the polymer (B) is 5,000 or more, the obtained molded article has excellent surface hardness. When the Mw of the polymer (B) is less than 5,000, the glass transition temperature of the polymer (B) is lowered, and the effect of improving the surface hardness in the obtained molded product may be reduced.

  The Mw of the polymer (B) is 20,000 or less, preferably 15,000 or less, more preferably 13,000 or less.

  When the Mw of the polymer (B) is 20,000 or less, the compatibility with the polycarbonate (C) is good, and the effect of improving the surface hardness is excellent.

  The polymerization method for obtaining the polymer (B) is not particularly limited, and for example, a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method can be used. The suspension polymerization method and the bulk polymerization method are preferred, and the suspension polymerization method is more preferred. In addition, additives necessary for the polymerization can be appropriately added as needed, and examples of the additives include a polymerization initiator, an emulsifier, a dispersant, and a chain transfer agent.

  The polymerization temperature depends on additives such as a (meth) acrylate monomer composition and a polymerization initiator, but is preferably from 50C to 150C, more preferably from 70C to 130C. The polymerization may be carried out by raising the temperature in multiple stages.

  The polymerization time varies depending on the polymerization method, the (meth) acrylate monomer composition, and additives such as a polymerization initiator, but is preferably 1 hour to 8 hours at the target temperature, more preferably 2 hours to 6 hours. In addition, the time until the temperature is raised to the target temperature is further added to the polymerization time.

  The reaction pressure varies depending on the polymerization method, the composition of the (meth) acrylate monomer, and the like, but it is preferably polymerization at normal pressure to 3 MPa, and more preferably at normal pressure to 1 MPa.

[3] Polycarbonate resin (C)
The polycarbonate-based resin (C) is not particularly limited as long as it contains a carbonate bond in the molecular main chain, that is, has a-[OR-OCO]-unit. R in the formula may be an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group. Among them, an aromatic polycarbonate obtained by using an aromatic dihydroxy compound such as bisphenol A is preferable in terms of cost. These polycarbonate resins can be used alone or in combination of two or more.

  The viscosity average molecular weight (Mv) of the polycarbonate resin (C) can be calculated by a viscosity method, and is preferably from 15,000 to 30,000, more preferably from 17,000 to 25,000. . When the viscosity average molecular weight is in the above range, the compatibility with the polymer (A) and the polymer (B) in the present embodiment is good, and a molded article having more excellent transparency and surface hardness can be obtained.

  The method for producing the polycarbonate resin (C) can be appropriately selected depending on the monomer used as a raw material, and examples thereof include a phosgene method and a transesterification method. In addition, those on the market can also be applied. For example, Iupilon (registered trademark) S-3000 (manufactured by Mitsubishi Engineering-Plastics Corporation, Mv = 22,000), Tufflon (registered trademark) FN1700 (Idemitsu Kosan) Mv = 18,000).

[4] UV absorber (D)
The ultraviolet absorber (D) used in the present embodiment includes inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, Organic ultraviolet absorbers such as ogizanilide compounds, malonic ester compounds, hindered amine compounds, and oxalic anilide compounds can be mentioned. Among these, organic ultraviolet absorbers are preferable, and benzotriazole compounds (compounds having a benzotriazole structure) are more preferable.

  Specific examples of the benzotriazole-based compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethyl) Benzyl) phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5) '-Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy- 3 ′, 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among which 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] Is preferable, and 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole is particularly preferable. Such benzotriazole-based compounds include, for example, "Seesorb 701", "Seesorb 705", "Seesorb 703", "Seesorb 702", "Seesorb 704", "Seesorb 709", manufactured by Kypro Kasei Co., Ltd. "Biosorb 520", "Biosorb 582", "Biosorb 580", "Biosorb 583", "Cemisorb 71" and "Cemisorb 72" manufactured by Chemipro Kasei, "Siasorb UV5411" manufactured by Cytec Industries, "LA-32" manufactured by Adeka "," LA-38 "," LA-36 "," LA-34 "," LA-31 "," Tinuvin P "," Tinuvin 234 "," Tinuvin 326 "," Tinuvin 327 "manufactured by Ciba Specialty Chemicals. , "Tinuvin 328" and the like.

  Specific examples of the benzophenone-based compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n-octo. Xybenzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy- 4,4′-dimethoxybenzophenone and the like. Examples of such a benzophenone-based compound include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cipro Kasei Corporation. 103 ", Kyodo Yakuhin "Biosorb 100", "Biosorb 110", "Biosorb 130", "Cemisorb 10", "Cemisorb 11", "Cemisorb 11S", "Cemisorb 12", "Cemisorb 13", "Cemisorb 111", BASF manufactured by Chemipro Kasei Corporation, BASF “Ubinul 400” manufactured by BASF, “Uvinul M-40” manufactured by BASF, “Ubinul MS-40” manufactured by BASF, “Siasorb UV9”, “Siasorb UV284”, “Siasorb UV531”, “Siasorb UV24” manufactured by Cytec Industries And "ADEKA STAB 1413" and "ADEKA STAB LA-51" manufactured by Adeka Corporation.

  Specific examples of the salicylate-based compound include, for example, phenyl salicylate, 4-tert-butylphenyl salicylate, and the like. Examples of such salicylate-based compounds include, for example, "Seesorb 201" and "Seesorb 202" manufactured by Cipro Kasei. And "Cemisorb 21" and "Chemisorb 22" manufactured by Chemipro Kasei.

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and the like. Examples thereof include "Seesorb 501" manufactured by Cipro Kasei, "Biosorb 910" manufactured by Kyodo Yakuhin, "Ubisolator 300" manufactured by Daiichi Kasei, "Ubinur N-35", and "Ubinur N-539" manufactured by BASF. Is mentioned.

  Specific examples of the oxanilide-based compound include, for example, 2-ethoxy-2′-ethyloxalinic acid bisarinide, and such an oxalinide-based compound is, for example, “Sandubore VSU” manufactured by Clariant. And the like.

  As the malonic ester compound, 2- (alkylidene) malonic esters are preferable, and 2- (1-arylalkylidene) malonic esters are more preferable. Examples of such a malonic ester compound include “PR-25” manufactured by Clariant Japan, and “B-CAP” manufactured by Ciba Specialty Chemicals.

The compounding amount of the ultraviolet absorber (D) used in the present embodiment is 0.1 to 100 parts by mass of the resin component containing the polymer (A), the polymer (B) and the polycarbonate resin (C). 1 to 1.5 parts by mass. Preferably it is 0.2 to 1.0 part by mass, more preferably 0.25 to 0.9 part by mass, still more preferably 0.3 to 0.8 part by mass.
If the compounding amount is 0.1 parts by mass or more, sufficient weather resistance tends to be exhibited, and if the compounding amount is 1.5 parts by mass or less, the amount of outgas during molding can be suppressed, and mold contamination can occur. Problems tend to hardly occur.
In addition, one kind may be contained in an ultraviolet absorber, and two or more kinds may be contained in arbitrary combinations and ratios.

[5] Antioxidant (E)
Examples of the antioxidant (E) used in the present embodiment include a phenolic antioxidant, an amine antioxidant, a phosphite antioxidant, and a thioether antioxidant. One kind of the antioxidant may be contained, or two or more kinds thereof may be contained in an optional combination and ratio. Among these, the use of a phenolic antioxidant or the combined use of a phenolic antioxidant and a phosphite antioxidant is preferred.

Specific examples of the phenolic antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphoate, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyi -A, a ', a''-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [ 3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert- Butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.
Above all, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferred. preferable. Such phenolic antioxidants include, for example, "Irganox 1010" and "Irganox 1076" manufactured by Ciba, "Adeka Stub AO-50" and "Adeka Stub AO-60" manufactured by Adeka.

  Specific examples of the phosphite-based antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, Tris (tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol Tetraphosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6 -Tert-butylphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, di Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol Diphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Specific examples of the amine antioxidant include poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, phenyl- α-naphthylamine, 4,4-bis (α, α-dimethyldensyl) diphenylamine, (p-toluenesulfonylamide) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β- Naphthyl-p-phenylenediamine, N, N'-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-1, Aromatic amines such as 3-dimethylbutyl-p-phenylenediamine, N- (1-methylheptyl) -N′-phenyl-p-phenylenediamine And the like.

  Specific examples of thioether-based antioxidants include pentaerythrityltetrakis (3-laurylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, Stearyl-3,3'-thiodipropionate and the like.

The compounding amount of the antioxidant (E) is 0.05 to 1.0 part by mass based on 100 parts by mass of the resin component containing the polymer (A), the polymer (B), and the polycarbonate resin (C). It is. Preferably, it is 0.05 to 0.8 part by mass, more preferably 0.1 to 0.7 part by mass, and still more preferably 0.15 to 0.6 part by mass.
When the content of the antioxidant is 0.05 parts by mass or more, a sufficient effect as an antioxidant tends to be exhibited, and when the content of the antioxidant is 1.0 parts by mass or less, the effect is reduced. It tends to be economical because excessive addition due to peaking can be suppressed.

[Resin composition]
The resin composition of the present embodiment contains the polymer (A), the polymer (B), the polycarbonate resin (C), the ultraviolet absorber (D), and the antioxidant (E).
The resin composition of the present embodiment contains 5 to 60% by mass of a (meth) acrylic polymer obtained by combining the polymer (A) and the polymer (B), based on the mass of the resin component. It is preferable to contain 40 to 95% by mass of the polycarbonate resin (C). The resin composition of the present embodiment contains 10 to 50% by mass of a (meth) acrylic polymer obtained by combining the polymer (A) and the polymer (B), based on the mass of the resin component. And it is more preferable to contain 50-90 mass% of polycarbonate resin (C). If the content of the (meth) acrylic polymer obtained by combining the polymer (A) and the polymer (B) in the resin component is 5% by mass or more, the compatibility with the polycarbonate resin (C) is obtained. The improvement and the improvement of the fluidity can be achieved. On the other hand, if the content of the (meth) acrylic polymer in which the polymer (A) and the polymer (B) are combined is too large, the haze tends to increase, but the polymer (A) and the polymer ( When the content of the (meth) acrylic polymer combined with B) is 60% by mass or less, it is possible to suppress a decrease in the transparency of the obtained molded article.

The resin component in the present embodiment contains another resin (R) in addition to the polymer (A), the polymer (B), and the polycarbonate resin (C) as long as the effects of the present invention are not impaired. May be.
Examples of such a resin (R) include polystyrene resins such as ABS, HIPS, PS, and PAS; polyester resins such as polyethylene terephthalate and polybutylene terephthalate for improving chemical resistance; polyolefin resins; A polymer alloy such as an elastomer containing another thermoplastic resin may be used. The content of these resins is preferably within a range that does not impair the inherent properties of the polycarbonate resin (C) such as heat resistance, impact resistance, and flame retardancy. In the present embodiment, the resin (R) is preferably contained in the resin component at a ratio of 0 to 50% by mass, more preferably 0 to 30% by mass, and still more preferably 0 to 10% by mass.

  Further, from the viewpoint of improving surface hardness and compatibility with the polycarbonate resin (C), the mass ratio ((A) / (B)) of the polymer (A) and the polymer (B) is 0.5 / It is preferably in the range of 99.5-30 / 70, more preferably in the range of 2 / 98-25 / 75, and even more preferably in the range of 5 / 95-20 / 80. If the mass ratio of the polymer (A) to the polymer (B) ((A) / (B)) is 0.5% by mass or more, the compatibility with the polycarbonate should be improved. Can be. On the other hand, if the polymer (B) is 70% by mass or more in the mass ratio ((A) / (B)) of the polymer (A) and the polymer (B), the surface hardness is sufficiently improved. Can be.

  The resin composition of the present embodiment may contain additives and the like as needed, as long as the effects of the present invention are not impaired.

  Examples of the additives that may be contained in the resin composition of the present embodiment include, for example, stabilizers, reinforcing agents, weathering agents, inorganic fillers, impact modifiers, flame retardants, antistatic agents, release agents , Dyes and pigments, and fluoroolefins. Specifically, talc, mica, calcium carbonate, glass fiber, carbon fiber, potassium titanate fiber, or the like can be used to improve the strength, rigidity, flame retardancy, and the like of the molded body. Further, a rubber-like elastic body having a core-shell two-layer structure for improving impact resistance may be contained.

The resin composition of the present embodiment comprises the polymer (A), the polymer (B), the polycarbonate resin (C), the ultraviolet absorber (D) and the antioxidant (E) in a powder state. It can be manufactured by a method of blending or a method of blending these by heating and melting.
In addition, the resin composition of the present embodiment is obtained by blending the polymer (A) and the polymer (B) in a powder state, or by blending them by heating and melting, and then further mixing the polycarbonate resin. (C) It can be manufactured by adding and blending the ultraviolet absorber (D) and the antioxidant (E) in a powder state, or blending by heating and melting.
For the blending method, for example, a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two-roller, a kneader, a Brabender and the like can be used.

[Molded body]
The molded article of the present embodiment is obtained by molding the resin composition.

By using the resin composition of the present embodiment, it is possible to obtain a molded article having both excellent transparency and surface hardness even when molded under high-temperature conditions. For example, a blend of the polymer (A) and the polymer (B) and a polycarbonate resin (C) (viscosity average molecular weight: 22,000) are melt-kneaded at a ratio of 30/70 (mass%) and injected. The haze of a 1.5 mm-thick plate specimen obtained by injection molding at a temperature of 300 ° C., an injection speed of 300 m / sec, and a mold temperature of 80 ° C. is preferably 12% or less, and more preferably 10% or less. More preferably, it is particularly preferably at most 5%. The flat plate specimen preferably has a pencil hardness of HB or more, more preferably F or more.
Furthermore, the yellowness of the test piece is preferably 4 or less, more preferably 3.8 or less, and particularly preferably 3.5% or less. The yellowness of the test piece after performing a weather resistance test for 500 hours with a sunshine weather meter (85 ° C., no rain) is preferably 30 or less, more preferably 25 or less, and 20%. It is particularly preferred that:

  As described above, the molded article of the present embodiment maintains excellent mechanical strength, heat resistance, electrical properties, dimensional stability, flame retardancy, transparency, and the like of the polycarbonate resin (C), and Excellent in surface hardness. Therefore, the molded article of the present embodiment can be used for electric and electronic devices, OA equipment, optical media, automobile parts, building members, and the like.

  Examples of the molding method of the molded article of the present embodiment include compression molding, transfer molding, injection molding, blow molding, extrusion molding, lamination molding, and calendar molding. When injection molding is used, the injection molding conditions are as follows: an injection temperature of 230 to 330 ° C., an injection speed of 10 to 500 mm / sec, and a mold temperature of 60 ° C. or higher from the viewpoint of improving the surface hardness. preferable. In addition, in the case of the resin composition of the present embodiment, the injection speed can be increased, so that it is preferable from the viewpoint of productivity.

[blend]
The blend of the present embodiment comprises a polymer (A) containing 45% by mass or more of the (meth) acrylate unit (a) represented by the formula (1) and 60% by mass of the methyl (meth) acrylate unit (b). % Or more and a polymer (B) having a mass average molecular weight of 5,000 to 20,000.

  Further, from the viewpoint of improving surface hardness and compatibility with the polycarbonate resin (C), the mass ratio ((A) / (B)) of the polymer (A) and the polymer (B) in the blend is 0.1%. It is preferably in the range of 5 / 99.5 to 30/70, more preferably in the range of 2/98 to 25/75, and still more preferably in the range of 5/95 to 20/80. If the mass ratio of the polymer (A) to the polymer (B) ((A) / (B)) is 0.5% by mass or more, the compatibility with the polycarbonate should be improved. Can be. On the other hand, if the polymer (B) is 70% by mass or more in the mass ratio ((A) / (B)) of the polymer (A) and the polymer (B), the surface hardness is sufficiently improved. Can be.

  The blend of the present embodiment may contain the above-mentioned other resins and additives as needed, as long as the effects of the present invention are not impaired.

  The blend of the present embodiment can be manufactured by a method of blending the polymer (A) and the polymer (B) in a powder state, or a method of blending them by heating and melting. As a blending method, for example, a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two-roll, kneader, a Brabender, or the like can be used.

  Hereinafter, the present invention will be described in detail with reference to examples, but the technical scope of the present invention is not limited thereto. “Parts” and “%” in the examples represent “parts by mass” and “% by mass”, respectively.

  The measurement of each physical property in the examples and comparative examples was performed by the following methods.

[Molecular weight of polymer]
Each polymer was dissolved in tetrahydrofuran (THF), and the measurement was performed using gel permeation chromatography. In addition, Mw, Mn, and Mw / Mn of each copolymer were calculated based on a calibration curve using standard polystyrene.

Apparatus: Tosoh Corporation HLC-8320GPCEcoSEC
Column: Tosoh Corporation TSK gel Super H MH x 3 Mobile phase solvent: THF
Flow rate: 0.6 mL / min Temperature: 40 ° C
Sample concentration: 0.1%
Sample injection volume: 10 μL
Detector: RI (UV)

[Pencil hardness]
A flat plate test piece having a thickness of 1.5 mm was prepared, and the pencil hardness at which no scratch was observed on the test piece surface was measured according to JIS K5600-5-4.

[transparency]
Using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the haze of a 1.5 mm-thick flat plate test piece was measured according to JIS K7136.

[Yellowness]
Using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.), a 2.0 mm-thick flat plate was measured for yellowness according to JIS K7136.

[Weather resistance test]
Using a sunshine weather meter S80 (manufactured by Suga Test Instruments Co., Ltd.), a 1.5 mm-thick flat plate test piece was put into a tester for 500 hours under a condition of no rain at 85 ° C. to perform a weather resistance test. Thereafter, the yellowness was measured by the above-mentioned method for measuring the yellowness.

[appearance]
The appearance of the molded article after 500 shot molding was visually evaluated by a molded article production method described later.
×: Surface roughness ○: Good appearance

<Synthesis Example 1: Synthesis of polymer (A) -a>
200 parts by mass of deionized water, 0.5 parts by mass of tribasic calcium phosphate as a suspension stabilizer, and 0.01% sodium dodecylbenzenesulfonate as a surfactant in a warmable high-pressure reactor equipped with a stirrer. After adding the mass part, it stirred. Separately, 97 parts by mass of phenyl methacrylate, 3 parts by mass of methyl acrylate, 0.3 parts by mass of perbutyl E as an initiator (manufactured by NOF CORPORATION), and 0.001 mass of normal-octyl mercaptan (nOM) as a chain transfer agent The monomer solution was prepared by mixing the parts to make a uniform solution, and the solution was added into the reaction vessel. The reaction vessel was filled with nitrogen and pressurized to 0.1 MPa. The reaction was carried out at 110 ° C. for 1 hour and then at 120 ° C. for 2 hours to complete the polymerization reaction. The obtained beaded polymer was washed with water and dried to obtain a polymer (A) -a.

<Synthesis Example 2: Synthesis of polymer (A) -b>
Polymer (A) -b was obtained in the same manner as in Synthesis Example 1 except that 0.01 part by mass of normal-octyl mercaptan (nOM) as a chain transfer agent was used.

<Synthesis Example 3: Synthesis of polymer (A) -c>
(Meth) acrylic copolymer (A) -c was obtained in the same manner as in Synthesis Example 2, except that 50 parts by mass of phenyl methacrylate and 47 parts by mass of methyl methacrylate were used.

<Synthesis Example 4: Synthesis of polymer (A) -d>
(Meth) acrylic copolymer (A) -d was obtained in the same manner as in Synthesis Example 2 except that 4-phenylphenyl methacrylate was used instead of phenyl methacrylate.

<Synthesis Example 5: Synthesis of Polymer (B) -a>
(Meth) acrylic copolymer (B) was produced in the same manner as in Synthesis Example 1 except that methyl methacrylate was used instead of phenyl methacrylate, and 2.5 parts by mass of normal-octyl mercaptan (nOM) as a chain transfer agent was used. ) -A was obtained.

<Synthesis Example 6: Synthesis of Polymer (B) -b>
Polymer (B) -b was obtained in the same manner as in Synthesis Example 5, except that 1.25 parts by mass of normal-octyl mercaptan (nOM) as a chain transfer agent was used.

<Synthesis Example 7: Synthesis of Polymer (B) -c>
Polymer (B) -c was obtained in the same manner as in Synthesis Example 5, except that 0.75 parts by mass of normal-octyl mercaptan (nOM) as a chain transfer agent was used.

Table 1 summarizes the compositions of the above Synthesis Examples 1 to 7. Table 2 summarizes the physical properties of the (meth) acrylic copolymers obtained in the above Synthesis Examples 1 to 7.

<Manufacture of resin pellets>
(Meth) acrylic copolymer obtained in the above synthesis example, Iupilon® S-3000 (manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight: 22,000) as a polycarbonate resin, and an ultraviolet absorber Of Seesorb 709 (manufactured by Cipro Kasei Co., Ltd.), ADK STAB AO-60 (manufactured by ADEKA) as a phenolic antioxidant, and ADK STAB 2112 as a phosphite antioxidant are compounded in the mass ratios shown in Table 3 below. did. After mixing with a tumbler for 20 minutes, the mixture was supplied to “TEX30HSST” manufactured by Nippon Steel Works equipped with 1 vent, and kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 260 ° C. The molten resin extruded into a strand was quenched in a water bath, and pelletized using a pelletizer to obtain pellets of the resin composition.

<Preparation of molded body>
After the pellets obtained by the above-described production method were dried at 100 ° C. for 5 hours, the injection temperature was adjusted using an injection molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) using a steel material mold. Injection molding was performed at 300 ° C., an injection speed of 300 mm / sec, and a mold temperature of 80 ° C. to obtain a 50 × 90 × 1.5 mm thick flat plate test piece.

  Table 3 shows the composition of the resin and the composition of the additive at the time of preparing each flat plate test piece. Furthermore, the pencil hardness, transparency and yellowness after injection molding, yellowness after weather resistance test, and appearance of each flat plate specimen were measured as described above. The results are shown in Table 4 below.

As shown in Tables 3 and 4, when the requirements of the present invention are satisfied (Examples 1 to 7), the surface hardness is high, the transparency is high, the yellowness after molding is low, and the yellowness after the weather resistance test is low. It can be seen that the change is small. Furthermore, the appearance of the molded piece after 500 shots is also good.
On the other hand, when the amount of the ultraviolet absorber is 1.5 parts by mass or more with respect to 100 parts by mass of the resin component obtained by blending the polymer and the polycarbonate (Comparative Example 1), although the weather resistance of the molded article after molding is improved. In addition, since the yellowness is high and the amount of the additive is large, the appearance of the molded article due to mold contamination becomes poor.
When the amount of the ultraviolet absorber is 0.05 parts by mass or less based on 100 parts by mass of the resin component in which the polymer and the polycarbonate are blended (Comparative Example 2), the yellowness of the molded article after the weather resistance test increases.
When the antioxidant is 0.05 parts by mass or less or 1.0 parts by mass or more with respect to 100 parts by mass of the resin component in which the polymer and the polycarbonate are blended, (Comparative Examples 3 and 4), Yellowness increases.
Further, when a methyl (meth) acrylic copolymer having a mass average molecular weight of 20,000 or more like (B) -c is used (Comparative Example 5), the transparency is lowered.

Claims (6)

Represented by the following formula (1) (meth) acrylate units (a) having 60 wt% or more containing, polymer weight average molecular weight of 100,000～2,000,000 (A) and methyl (meth A) a (meth) acrylic copolymer component comprising only a polymer (B ) having an acrylate unit (b) of 90 % by mass or more and a weight average molecular weight of 7,000 to 20,000 ; ), An ultraviolet absorber (D) and an antioxidant (E),
In the resin component consisting of (A), (B) and (C), the total content of the polymer (A) and the polymer (B) is 5 to 60% by mass, and the polycarbonate resin ( C) content of 40 to 95% by mass,
The mass ratio ((A) / (B)) of the polymer (A) and the polymer (B) is 0.5 / 99.5 to 30/70,
0.6 to 1.5 parts by mass of (D) and 0.15 to 1.0 parts by mass of (E) based on 100 parts by mass of the resin component containing (A), (B) and (C). Resin composition.
(In equation (1),
R ₁ is a hydrogen atom or a methyl group;
R ₂ is each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkyl group having 1 to 10 carbon atoms. Alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group which may have a substituent or a phenyl which may have a substituent A phenyl group;
n is an integer of 0-5. ) Having an ultraviolet absorber (D) Gabe benzotriazole structure, the resin composition of claim 1. The resin composition according to claim 1, wherein the antioxidant (E) includes a phenolic antioxidant. The resin composition according to claim 3, wherein the antioxidant (E) further includes a phosphite-based antioxidant. The resin composition according to any one of claims 1 to 4, wherein a compounding amount of the antioxidant (E) is 0.2 to 0.4 parts by mass based on 100 parts by mass of the resin component. A molded article obtained by molding the resin composition according to claim 1.