JP6794799B2 - Aromatic polycarbonate resin composition and its molded product - Google Patents

Description

The present invention relates to an aromatic polycarbonate resin composition having excellent surface hardness, transparency and heat retention stability, and a molded product obtained by molding the aromatic polycarbonate resin composition.

Aromatic polycarbonate resin is excellent in transparency, impact resistance, heat resistance, etc., and the obtained molded product is also excellent in dimensional stability, etc. Therefore, housings for electrical and electronic equipment, automobile parts, or , Widely used as a raw material resin for manufacturing precision molded products such as optical disc related parts. In particular, in the housings of home appliances, electronic devices, image display devices, etc., products with high commercial value are provided by taking advantage of their beautiful appearance.

However, the molded product of the aromatic polycarbonate resin alone has a lower surface hardness than the product made of metal or glass, and therefore has a drawback that it is inferior in scratch resistance and the surface is easily scratched.

Conventionally, in order to improve the surface hardness of an aromatic polycarbonate resin, it has been proposed to blend a (meth) acrylic copolymer, and Patent Document 1 describes 5 to 80 mass of an aromatic (meth) acrylate unit. It has been proposed to blend (meth) acrylic copolymers containing 20 to 95% by mass of% and methyl methacrylate units and having a mass average molecular weight of 5,000 to 30,000.
Further, Patent Document 2 proposes to blend a (meth) acrylic copolymer containing 5 to 85% by mass of a phenylbenzyl-based (meth) acrylate unit and 15 to 95% by mass of a methyl (meth) acrylate unit. Has been done.

JP-A-2010-116501 International Publication No. 2016/125414

The (meth) acrylic copolymers described in Patent Documents 1 and 2 are excellent in the effect of improving the surface hardness of the aromatic polycarbonate resin composition, but each has the following problems.

The aromatic polycarbonate resin composition containing the (meth) acrylic copolymer described in Patent Document 1 has a drawback that the transparency of the molded product obtained by injection molding at high speed is impaired. That is, when the (meth) acrylic copolymer described in Patent Document 1 is blended with an aromatic polycarbonate resin and injection molding is performed at a normal injection speed of about 50 mm / sec, the transparency is excellent. Although it is possible to obtain a molded product, it has been found by the present inventor that it is not possible to obtain a molded product having excellent transparency when injection molding is performed at a high speed of about 200 mm / sec. When manufacturing thin-walled, long-walled molded products or molded products with special shapes, it is necessary to perform injection molding at high speed and quickly fill the mold with resin, so transparency at normal speed Not only that, transparency in high-speed molding is also important.

Further, in the (meth) acrylic copolymer described in Patent Document 2, a molded product having excellent surface hardness and transparency can be obtained, but the retention heat stability is inferior, and it is in the cylinder during injection molding. If the residence time is long, there is a problem that the hue of the obtained molded product is inferior due to deterioration of the resin.

The present invention solves the above-mentioned conventional problems and is an aromatic polycarbonate resin composition containing a (meth) acrylic copolymer as a surface hardness improver, which has excellent surface hardness and transparency, especially at high speed. It is an object of the present invention to provide an aromatic polycarbonate resin composition having excellent transparency at the time of injection molding and also excellent heat retention stability, and a molded product obtained by molding this aromatic polycarbonate resin composition.

As a result of diligent studies to solve the above problems, the present inventor has used a specific (meth) acrylic copolymer (B1) and a (meth) acrylic copolymer (B2) in combination, and used these. By blending in a predetermined ratio, the (meth) acrylic copolymer has a good effect of improving the surface hardness, and is also excellent in transparency during injection molding at high speed and stability of retained heat. It has been found that an aromatic polycarbonate resin composition can be realized.

That is, the gist of the present invention is as follows.

[1] The following (meth) acrylic copolymer (B1) and (meth) acrylic copolymer (B2) are contained in a total of 10 to 100 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin, and (meth). The content ratio of the acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) is the mass ratio of the (meth) acrylic copolymer (B1): (meth) acrylic copolymer (B2). = 80 to 20:20 to 80. An aromatic polycarbonate resin composition.
(Meta) Acrylic Copolymer (B1): Contains 5 to 80% by mass of aromatic (meth) acrylate unit (b1-1) and 20 to 95% by mass of methyl (meth) acrylate unit (b1-2). A (meth) acrylic copolymer having a mass average molecular weight of 5,000 to 30,000 (meth) Acrylic copolymer (B2): A (meth) acrylate unit (b2) represented by the following general formula (1). -1) A (meth) acrylic copolymer containing 5 to 85% by mass and a methyl (meth) acrylate unit (b2-2) 15 to 95% by mass and having a mass average molecular weight of 3,000 to 30,000.

(In the formula (1), X is a single bond, -C (R ² ) (R ³ )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O). ) A divalent group selected from the group consisting of O-, -S-, -SO-, -SO _2- and any combination thereof, where R ¹ is a hydrogen atom or a methyl group and R ² And R ³ independently have a hydrogen atom, 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 1 to 10 carbon atoms. linear alkoxy groups, branched alkoxy group having 3 to 10 carbon atoms, cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group, or a phenyl group, or, R ² and R ³ are connected to each other Then, a ring having 3 to 10 carbon atoms may be formed together with the carbon atom to which these are bonded, and R ⁴ and R ⁵ are independently linear alkyl groups having 1 to 10 carbon atoms and carbon atoms. Branched alkyl groups of 3 to 10, cyclic alkyl groups of 3 to 10 carbons, linear alkoxy groups of 1 to 10 carbons, branched alkoxy groups of 3 to 10 carbons, cyclic alkoxys of 3 to 10 carbons A group, a halogen atom, a phenyl group or a phenylphenyl group, m is an integer of 1 to 10, p is an integer of 0 to 4, and q is an integer of 0 to 5.)

[2] The aromatic polycarbonate resin composition according to [1], wherein the molded product of the aromatic polycarbonate resin composition has a pencil hardness of F or more measured in accordance with JIS K5400.

[3] A plate test piece having a thickness of 1.5 mm obtained by injection molding the aromatic polycarbonate resin composition at an injection speed of 200 mm / sec has a Haze of 2 or less measured in accordance with JIS K7105 [1]. ] Or [2]. The aromatic polycarbonate resin composition.

[4] When the aromatic polycarbonate resin composition was injection-molded into a plate test piece having a thickness of 3 mm at a cylinder temperature of 280 ° C. and a cycle time of 180 seconds, it was obtained in the first shot calculated by the following formula (2). Described in any one of [1] to [3], wherein the difference ΔYI between the YI value (YI ₁ ) of the plate test piece and the YI value (YI ₁₀ ) of the plate test piece obtained on the 10th shot is 1 or less. Aromatic polycarbonate resin composition.
ΔYI = YI ₁₀ −YI ₁ … (2)

[5] A molded product obtained by molding the aromatic polycarbonate resin composition according to any one of [1] to [4].

According to the present invention, it is possible to provide an aromatic polycarbonate resin composition which is excellent in surface hardness, transparency at the time of injection molding at high speed, and also excellent in retention heat stability.

Since the aromatic polycarbonate resin composition of the present invention does not lose its transparency even when it is molded at high speed, it is transparent by high-speed molding even if it is a thin-walled, long molded product or a molded product having an irregular shape. Molded products with excellent properties can be molded with good yield. Moreover, since it is also excellent in heat retention stability, for example, restrictions on the residence time in the cylinder during injection molding are alleviated, workability is improved, and product yield is also improved.

Due to its excellent surface hardness and transparency, the aromatic polycarbonate resin molded product of the present invention can be used as a housing for electrical / electronic equipment and image display equipment, automobile parts, lighting equipment parts, information terminal equipment, home appliances, and leisure. It is useful for supplies and miscellaneous goods.

Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not limited to the embodiments and examples shown below, and is arbitrary as long as it does not deviate from the gist of the present invention. Can be changed to.

[Aromatic Polycarbonate Resin Composition]
In the aromatic polycarbonate resin composition of the present invention, a total of 10 specific (meth) acrylic copolymers (B1) and (meth) acrylic copolymers (B2) are added to 100 parts by mass of the aromatic polycarbonate resin. The content ratio of the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) is the mass ratio of the (meth) acrylic copolymer (B1): (meth). ) Acrylic copolymer (B2) = 80 to 20:20 to 80.

In the present invention, "(meth) acrylate" refers to one or both of "acrylate" and "methacrylate". Further, the “unit” refers to a structural portion derived from a raw material monomer used when a (meth) acrylate copolymer is produced by copolymerizing a monomer.

[mechanism]
Both the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) are effective in improving the surface hardness.
In the present invention, the mechanism of the effect of improving transparency and retained heat stability during high-speed molding by using the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) in combination. The details are not clear or are presumed to be as follows.
When only the (meth) acrylic copolymer (B1) is used, the compatibility between the polycarbonate and the (meth) acrylic copolymer (B1) is slightly low, so that the phase is separated during high-speed molding and the transparency is lowered. However, by using the (meth) acrylic copolymer (B2) in combination, the compatibility with polycarbonate can be improved and the transparency can be improved.
On the contrary, when only the (meth) acrylic copolymer (B2) is used, the retention heat stability is impaired, but by using the (meth) acrylic copolymer (B1) together, discoloration due to heat is suppressed. Therefore, the retention heat stability can be improved.

<Aromatic Polycarbonate Resin (A)>
The aromatic polycarbonate resin (A) is an aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with a diester of phosgene or carbonic acid. The aromatic polycarbonate polymer may have a branch. The method for producing the aromatic polycarbonate resin is not particularly limited, and conventional methods such as a phosgene method (interfacial polymerization method) and a melting method (transesterification method) can be used.

Typical examples of aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy-3-methylphenyl). ) Propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy) -3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxybiphenyl, 3,3', 5 , 5'-Tetramethyl-4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone And so on.

Among the aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable.
The aromatic dihydroxy compound may be used alone or in combination of two or more.

When producing the aromatic polycarbonate resin (A), a small amount of polyhydric phenol or the like having 3 or more hydroxy groups in the molecule may be added in addition to the aromatic dihydroxy compound. In this case, the aromatic polycarbonate resin (A) has a branch.

Examples of the polyhydric phenol having three or more hydroxy groups include fluoroglucolcin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4. , 6-Tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, Polyhydroxy compounds such as 1,1,1-tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxyindole (= isatin bisphenol), 5-chloruisatin, 5,7-dichlorousatin , 5-Bromisatin and the like. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane or 1,3,5-tris (4-hydroxyphenyl) benzene is preferable. The amount of the polyhydric phenol used is preferably 0.01 to 10 mol%, more preferably 0.1 to 2 mol%, based on the aromatic dihydroxy compound (100 mol%). Is.

In polymerization by the transesterification method, a carbonic acid diester is used as a monomer instead of phosgene. Typical examples of carbonic acid diesters include substituted diaryl carbonates typified by diphenyl carbonate, ditril carbonate and the like, dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable.

Further, the above-mentioned carbonic acid diester may be replaced with a dicarboxylic acid or a dicarboxylic acid ester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less. Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate and the like. When a part of the carbonic acid diester is replaced with such a dicarboxylic acid or a dicarboxylic acid ester, a polyester carbonate is obtained.

When producing an aromatic polycarbonate resin by the transesterification method, a catalyst is usually used. The catalyst type is not limited, but generally, basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds are used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferable. These may be used alone or in combination of two or more. In the transesterification method, it is common to inactivate the catalyst with a p-toluenesulfonic acid ester or the like.

A polymer or oligomer having a siloxane structure can be copolymerized with the aromatic polycarbonate resin (A) for the purpose of imparting flame retardancy or the like.

The molecular weight of the aromatic polycarbonate resin (A) is arbitrary depending on the intended use and may be appropriately selected and determined. However, from the viewpoint of moldability, strength, etc., the molecular weight of the aromatic polycarbonate resin (A) is methylene chloride as a solvent. The viscosity average molecular weight obtained by converting from the solution viscosity measured at a temperature of 20 ° C. is 14,000 to 30,000, preferably 15,000 to 28,000. By setting the viscosity average molecular weight to 14,000 or more, the mechanical strength tends to be further improved, which is preferable when used in applications with high mechanical strength requirements. On the other hand, when the viscosity average molecular weight is set to 30,000 or less, the decrease in fluidity tends to be suppressed and improved, which is preferable from the viewpoint of molding processability.

The viscosity average molecular weight of the aromatic polycarbonate resin (A) is preferably 16,000 to 26,000. Further, two or more kinds of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed, and in this case, aromatic polycarbonate resins having a viscosity average molecular weight outside the above preferable range may be mixed. In this case, the viscosity average molecular weight of the mixture is preferably in the above range.

[(Meta) acrylic copolymer (B1)]
The (meth) acrylic copolymer (B1) contains 5 to 80% by mass of an aromatic (meth) acrylate unit (b1-1) and 20 to 95% by mass of a methyl (meth) acrylate unit (b1-2). , A (meth) acrylic copolymer having a mass average molecular weight of 5,000 to 30,000.

The aromatic (meth) acrylate constituting the aromatic (meth) acrylate unit (b1-1) is a (meth) acrylate having an aromatic group in the ester portion, and the aromatic (meth) acrylate includes, for example, Examples thereof include phenyl (meth) acrylate and benzyl (meth) acrylate. These can be used alone or in combination of two or more. Of these, phenyl methacrylate and benzyl methacrylate are preferable, and phenyl methacrylate is more preferable. When the (meth) acrylic copolymer (B1) has an aromatic (meth) acrylate unit (b1-1), the transparency of the aromatic polycarbonate resin composition can be improved.

The monomers constituting the methyl (meth) acrylate unit (b1-2) are methyl methacrylate and / or methyl acrylate. The methyl (meth) acrylate unit (b1-2) has the effect of dispersing well with the aromatic polycarbonate resin (A), and the (meth) acrylic copolymer (B1) is transferred to the surface of the molded product to transfer the surface of the molded product. It has the effect of improving hardness.
The methyl (meth) acrylate unit (b1-2) is preferably a methyl methacrylate unit or a combination of a methyl methacrylate unit and a methyl acrylate unit.

The (meth) acrylate copolymer (B1) contains 5 to 80% by mass of an aromatic (meth) acrylate unit (b1-1) and 20 to 95% by mass of a methyl (meth) acrylate unit (b1-2). Preferably, it contains 20 to 70% by mass of an aromatic (meth) acrylate unit (b1-1) and 30 to 80% by mass of a methyl (meth) acrylate unit (b1-2) (however, (b1-1) and ( The total of b1-2) is 100% by mass). When the content of the aromatic (meth) acrylate unit (b1-1) in the (meth) acrylate copolymer (B1) is 5% by mass or more, the high addition region of the (meth) acrylate copolymer (B1) If the transparency is maintained at 80% by mass or less, the compatibility with the aromatic polycarbonate (A) is not too high, and the surface hardness becomes good when transferred to the surface of the molded product.

The (meth) acrylic copolymer (B1) is a monomer unit other than the aromatic (meth) acrylate unit (b1-1) and the methyl (meth) acrylate unit (b1-2), if necessary. b1-3) may be contained. Other monomers constituting the other monomer unit (b1-3) include, for example, methacrylates such as ethyl methacrylate, butyl methacrylate, propyl methacrylate and 2-ethylhexyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate and propyl. Acrylate such as acrylate, 2-ethylhexyl acrylate, glycidyl acrylate; vinyl cyanide monomer such as acrylonitrile and methacrylonitrile; diene monomer such as butadiene, isoprene and dimethyl butadiene; vinyl methyl ether, vinyl ethyl ether and the like Vinyl ether-based monomer; Carboxylic acid-based vinyl monomer such as vinyl acetate and vinyl butyrate; Olefin-based monomer such as ethylene, propylene and isobutylene; Ethylene-based monomer such as acrylic acid, methacrylic acid, maleic acid and itaconic acid Saturated carboxylic acid monomer; vinyl halide monomer such as vinyl chloride and vinylidene chloride; maleimide-based monomer such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide; allyl (meth) acrylate , Divinylbenzene, 1,3-butylene methacrylate and the like. Of these, methacrylate, acrylate, and vinyl cyanide monomer are preferable, and acrylate is more preferable from the viewpoint of suppressing thermal decomposition of the (meth) acrylic copolymer (B1). These monomers can be used alone or in combination of two or more.

When the other monomer unit (b1-3) is contained, the (meth) acrylic copolymer (B1) is an aromatic (meth) acrylate unit (b1-1) 5 to 79.9% by mass, methyl. It is preferable to contain 20 to 94.9% by mass of the methacrylate unit (b1-2) and 0.1 to 10% by mass of other monomer units (b1-3) (provided that (b1-1) to (b1-1) to ( The total of b1-3) is 100% by mass).

If the content of the other monomer unit (b1-3) in the (meth) acrylic copolymer (B1) is 0.1% by mass or more, thermal decomposition can be suppressed and 10% by mass. If the following, the surface hardness and transparency of the molded product are maintained.

As a method for polymerizing the monomer for obtaining the (meth) acrylic copolymer (B1), a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a massive polymerization method can be used. it can. A suspension polymerization method or a massive polymerization method is preferable, and a suspension polymerization method is more preferable. In addition, additives necessary for polymerization can be appropriately added as needed, and examples thereof include polymerization initiators, emulsifiers, dispersants, and chain transfer agents.

The mass average molecular weight of the (meth) acrylate copolymer (B1) is 5,000 to 30,000, preferably 10,000 to 25,000, and particularly preferably 13,000 to 20,000. When the mass average molecular weight is 5,000 to 30,000, the compatibility with the aromatic polycarbonate (A) is good, and the effect of improving the surface hardness is excellent. When the mass average molecular weight exceeds 30,000, the (meth) acrylic copolymer (B1) tends to aggregate during shearing during molding, and as a result, the transparency of the obtained molded product tends to decrease. is there. When the mass average molecular weight is less than 5,000, it tends to be accompanied by a decrease in mechanical properties such as impact resistance and pencil hardness of the obtained molded product.

The mass average molecular weight (Mw) of the (meth) acrylate copolymer (B1) and the (meth) acrylic copolymer (B2) described later is determined by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. It is a value in terms of polystyrene (PS) measured using.

[(Meta) acrylic copolymer (B2)]
The (meth) acrylic copolymer (B2) has a (meth) acrylate unit (b2-1) of 5 to 85% by mass and a methyl (meth) acrylate unit (b2-2) represented by the following general formula (1). It is a (meth) acrylic copolymer containing 15 to 95% by mass and having a mass average molecular weight of 3,000 to 30,000.

(In equation (1), X is a single bond, -C (R ² ) (R ³ )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O). ) A divalent group selected from the group consisting of O-, -S-, -SO-, -SO _2- and any combination thereof.
R ¹ is a hydrogen atom or a methyl group and
R ² and R ³ each independently have a hydrogen atom, 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 1 carbon atom. It is a linear alkoxy group of 10 to 10, a branched alkoxy group of 3 to 10 carbon atoms, a cyclic alkoxy group of 3 to 10 carbon atoms, a phenyl group, or a phenylphenyl group, or R ² and R ³ are mutual. It may be linked to to form a ring having 3 to 10 carbon atoms together with the carbon atom to which these are bonded.
R ⁴ and R ⁵ independently have 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 1 to 10 carbon atoms. It is a linear 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.
m is an integer from 1 to 10
p is an integer from 0 to 4 and
q is an integer from 0 to 5. )

The (meth) acrylate unit (b2-1) represented by the general formula (1) has two or more benzene rings in the ester portion, and the oxygen atom in the ester moiety and the benzene ring are not directly bonded. It has structural features. Since the (meth) acrylate unit (b2-1) has excellent compatibility with the aromatic polycarbonate resin (A), it contributes to improving the transparency of the obtained molded product.

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

X is a single bond, -C (R ² ) (R ³ )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O) O-, -S- , -SO-, -SO _2-, and any combination thereof are divalent groups selected from the group, and R ² and R ³ are independently hydrogen atoms and directly having 1 to 10 carbon atoms. Chain alkyl group, branched alkyl group having 3 to 10 carbon atoms, cyclic alkyl group having 3 to 10 carbon atoms, linear alkoxy group having 1 to 10 carbon atoms, branched alkoxy group having 3 to 10 carbon atoms, carbon The number is 3 to 10 cyclic alkoxy group, phenyl group or phenylphenyl group. These may have a substituent, and 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. Examples thereof include a group, 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.

X is preferably single bond, -C (R ² ) (R ³ )-, -C (= O)-, -O-, -SO-, or -SO _2-, and is preferably single bond, -C (R ^2). ) (R ³ )-, -O-, or -SO ₂ --is more preferable. R ² and R ³ are preferably independently selected from a hydrogen atom, a methyl group, a methoxy group, a phenyl group and a phenylphenyl group, and more preferably a hydrogen atom.
R ² and R ³ may be linked to each other to form a ring having 3 to 10 carbon atoms together with the carbon atom to which they are bonded.

R ⁴ and R ⁵ independently have 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 1 to 10 carbon atoms. It is a linear 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, and 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. Examples thereof include a group, 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 ⁴ and R ⁵ are preferably independently selected from a methyl group, a methoxy group, a chloro group, a bromo group and a phenyl group, and more preferably a phenyl group.

m is an integer of 1 to 10, preferably an integer of 1 to 3, and more preferably 1.

p is an integer of 0 to 4, preferably an integer of 0 to 1, and more preferably 0.

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

Examples of the (meth) acrylate compound constituting the (meth) acrylate unit represented by the general formula (1) include 4-phenylbenzyl (meth) acrylate, 3-phenylbenzyl (meth) acrylate, and 2-phenylbenzyl. (Meta) acrylate, 4-biphenylbenzyl (meth) acrylate, 3-biphenylbenzyl (meth) acrylate, 2-biphenylbenzyl (meth) acrylate, 4-benzylbenzyl (meth) acrylate, 3-benzylbenzyl (meth) acrylate, 2-Benzylbenzyl (meth) acrylate, 4-phenylbenzyl (meth) acrylate, 3-phenylbenzyl (meth) acrylate, 2-phenylbenzyl (meth) acrylate, 4-phenethylphenethyl (meth) acrylate, 3-phenethylphenethyl ( Meta) acrylate, 2-phenethylphenethyl (meth) acrylate, 4- (4-methylphenyl) benzyl (meth) acrylate, 3- (4-methylphenyl) benzyl (meth) acrylate, 2- (4-methylphenyl) benzyl (Meta) acrylate, 4- (4-methoxyphenyl) benzyl (meth) acrylate, 3- (4-methoxyphenyl) benzyl (meth) acrylate, 2- (4-methoxyphenyl) benzyl (meth) acrylate, 4-( 4-Bromophenyl) benzyl (meth) acrylate, 3- (4-bromophenyl) benzyl (meth) acrylate, 2- (4-bromophenyl) benzyl (meth) acrylate, 4-benzoylbenzyl (meth) acrylate, 3- Benzoylbenzyl (meth) acrylate, 2-benzoylbenzyl (meth) acrylate, 4- (phenylsulfinyl) benzyl (meth) acrylate, 3- (phenylsulfinyl) benzyl (meth) acrylate, 2- (phenylsulfinyl) benzyl (meth) Acrylate, 4- (phenylsulfonyl) benzyl (meth) acrylate, 3- (phenylsulfonyl) benzyl (meth) acrylate, 2- (phenylsulfonyl) benzyl (meth) acrylate, 4-((phenoxycarbonyl) oxy) benzyl (meth) ) Acrylate, 3-((phenoxycarbonyl) oxy) benzyl (meth) acrylate, 2-((phenoxycarbonyl) oxy) benzyl (meth) acrylate, 4-(((meth) acryloxy) methyl) phenylbe Nzoate, 3-(((meth) acryloxy) methyl) phenylbenzoate, 2-(((meth) acryloxy) methyl) phenylbenzoate, phenyl4-(((meth) acryloxy) methyl) benzoate, phenyl3-(((() Meta) acryloxy) methyl) benzoate, phenyl2-(((meth) acryloxy) methyl) benzoate, 4- (1-phenylcyclohexyl) benzyl (meth) acrylate, 3- (1-phenylcyclohexyl) benzyl (meth) acrylate, 2- (1-Phenylcyclohexyl) benzyl (meth) acrylate, 4-phenoxybenzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, 4- (phenylthio) benzyl (meth) Examples thereof include acrylate, 3- (phenylthio) benzyl (meth) acrylate, 2- (phenylthio) benzyl (meth) acrylate, and 3-methyl-4- (2-methylphenyl) benzyl methacrylate. These can be used alone or in combination of two or more.

Of these, preferably 4-phenylbenzyl (meth) acrylate, 3-phenylbenzyl (meth) acrylate, 2-phenylbenzyl (meth) acrylate, 4-biphenylbenzyl (meth) acrylate, 3-biphenylbenzyl (meth) acrylate , 2-Biphenylbenzyl (meth) acrylate, more preferably 4-phenylbenzyl (meth) acrylate, 3-phenylbenzyl (meth) acrylate, 2-phenylbenzyl (meth) acrylate, 4-benzylbenzyl (meth) acrylate. , 4-Phenyloxybenzyl (meth) acrylate, 4- (Phenylsulfonyl) benzyl (meth) acrylate.

The monomer constituting the methyl (meth) acrylate unit (b2-2) of the (meth) acrylic copolymer (B2) is methyl methacrylate and / or methyl methacrylate. Since the methyl (meth) acrylate unit (b2-2) has excellent dispersibility in the aromatic polycarbonate resin (A), it has an effect of improving the surface hardness of the molded product.
The methyl (meth) acrylate unit (b2-2) is preferably a methyl methacrylate unit or a combination of a methyl methacrylate unit and a methyl acrylate unit.

The (meth) acrylic copolymer (B2) contains 5 to 85% by mass of the (meth) acrylate unit (b2-1) represented by the general formula (1) and the methyl (meth) acrylate unit (b2-2). ) Is included in an amount of 15 to 95% by mass (however, the total of (b2-1) and (b2-2) is 100% by mass). From the viewpoint of transparency, it is preferable that the proportion of the (meth) acrylate unit (b2-1) in the (meth) acrylic copolymer (B2) is 5% by mass or more. Copolymerization of a (meth) acrylate unit (b2-1) having a benzene ring in the ester portion tends to reduce the surface hardness, but the proportion of the methyl (meth) acrylate unit (b2-2) is 15% by mass or more. If this is the case, the effect of improving the surface hardness of the (meth) acrylic copolymer (B2) is good.

The (meth) acrylic copolymer (B2) has a (meth) acrylate unit (b2-1) ratio of 5 to 80% by mass and a methyl (meth) acrylate unit (b2-2) ratio of 20 to 95%. It is preferably mass%, with the proportion of the (meth) acrylate unit (b2-1) being 10-40% by mass and the proportion of the methyl (meth) acrylate unit (b2-2) being 60-90% by mass. Is more preferable.

The (meth) acrylic copolymer (B2) is a monomer unit other than the aromatic (meth) acrylate unit (b2-1) and the methyl (meth) acrylate unit (b2-2), if necessary. b2-3) may be contained. As the other monomer constituting the other monomer unit (b2-3), the (meth) acrylic copolymer (B1) may be contained in the other monomer unit (b1-3). Examples of the other monomers constituting the above include those similar to those exemplified above, preferably methacrylate, acrylate, and vinyl cyanide monomers, which can thermally decompose the (meth) acrylic copolymer (B2). From the viewpoint of suppressing, acrylate is more preferable. These monomers can be used alone or in combination of two or more.

When the (meth) acrylic copolymer (B2) contains another monomer unit (b2-3), the other monomer unit (b2-3) is the (meth) acrylic copolymer (B2). ), It is preferably contained in an amount of 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass. In this case, the (meth) acrylate unit (b2-1) 5 to 79.9% by mass, the methyl (meth) acrylate unit (b2-2) 20 to 94.9% by mass, and other monomer units (b2-). 3) It is preferably 0.1 to 10% by mass (however, the total of (b2-1) to (b2-3) is 100% by mass).

When the content of other monomer units is 0.1% by mass or more, the thermal decomposition of the (meth) acrylic copolymer (B2) can be suppressed, and when it is 10% by mass or less, molding is performed. Does not adversely affect the surface hardness and transparency of the product.

The polymerization method for obtaining the (meth) acrylic copolymer (B2) is not particularly limited, but for example, a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a massive polymerization method is used. be able to. A suspension polymerization method or a massive polymerization method is preferable, and a suspension polymerization method is more preferable. In addition, additives necessary for polymerization can be appropriately added as needed, and examples of the additives include polymerization initiators, emulsifiers, dispersants, and chain transfer agents.

The mass average molecular weight of the (meth) acrylic copolymer (B2) is 3,000 to 30,000, preferably 5,000 to 20,000, and more preferably 8,000 to 14,000. When the mass average molecular weight is 3,000 to 30,000, the compatibility with the aromatic polycarbonate resin (A) is good, which is preferable from the viewpoint of transparency of the molded product and also from the viewpoint of surface hardness. When the mass average molecular weight exceeds 30,000, the (meth) acrylic copolymer (B2) tends to aggregate during shearing during molding, and as a result, the transparency of the obtained molded product tends to decrease. is there. When the mass average molecular weight is less than 3,000, it tends to be accompanied by a decrease in mechanical properties such as impact resistance and pencil hardness of the obtained molded product.

[Contents of (meth) acrylic copolymer (B1) and (meth) acrylic copolymer (B2)]
In the aromatic polycarbonate resin composition of the present invention, a total of (meth) acrylic copolymer (B1) and (meth) acrylic copolymer (B2) is added to 100 parts by mass of the aromatic polycarbonate resin (A). It contains 10 to 100 parts by mass, preferably 20 to 80 parts by mass, and more preferably 30 to 75 parts by mass. If the total content of the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) is less than the above lower limit, the effect of improving the surface hardness cannot be sufficiently obtained, and the above upper limit is obtained. If it exceeds, the transparency, retention heat stability, and other physical properties tend to decrease.

Further, the aromatic polycarbonate resin composition of the present invention has transparency and retention heat stability by using the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) in combination. In order to surely obtain the effect of obtaining good surface hardness while maintaining the above, the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) are mixed in a mass ratio of (meth). ) Acrylic copolymer (B1): (meth) Acrylic copolymer (B2) = 80:20 to 20:80. Preferably, the content ratio is (meth) acrylic copolymer (B1): (meth) acrylic copolymer (B2) = 70:30 to 30:70, and more preferably 60:40 to 40: It is 60, particularly preferably 55:45 to 45:55.

[Other resins]
The aromatic polycarbonate resin composition of the present invention contains the aromatic polycarbonate resin (A), the (meth) acrylic copolymer (B1) and the (meth) acrylic as resin components as long as the object of the present invention is not impaired. It may contain a transparent resin component other than the copolymer (B2). Examples of other transparent resin components that can be blended include polystyrene resin, high-impact polystyrene resin, hydrogenated polystyrene resin, polyacrylic styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, and polyalkyl methacrylate resin. , Polymethacryl methacrylate resin, polyphenyl ether resin, polycarbonate resin other than component (A), amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, Thermoplastic elastomers such as amorphous polyarylate resin, polyether sulfone, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer are listed. Preferably, polystyrene resin, ABS resin, AS resin, AES resin, ASA resin, polyphenylene ether resin, polymethacrylic methacrylate resin, polyester resin and the like can be mentioned.

One of these may be used alone, or two or more thereof may be mixed and used, but the aromatic polycarbonate resin (A) and the (meth) acrylic copolymer (B1) and the (meth) acrylic are used. In order to obtain the effect of the present invention by using the copolymer (B2) in a specific ratio, when these other transparent resin components are contained, the contents thereof are the aromatic polycarbonate resin (A) and (meth). ) It is preferable that the total amount is 20 parts by mass or less with respect to 100 parts by mass in total of the acrylic copolymer (B1) and the (meth) acrylic copolymer (B2).

[Other additives]
The aromatic polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such an additive include a phosphorus-based heat stabilizer, a mold release agent, a glass strengthening material, an antioxidant, an ultraviolet absorber, a dye pigment, an antistatic agent, a flame retardant, and a drip inhibitor.

<Phosphorus heat stabilizer (C)>
The phosphorus-based heat stabilizer (C) is generally effective in improving the retention stability at high temperatures and the heat resistance stability when using a resin molded product when the resin component is melt-kneaded.

Examples of the phosphorus-based heat stabilizer (C) used in the present invention include phosphorous acid, phosphorous acid, phosphorous acid ester, phosphoric acid ester, etc. Among them, trivalent phosphorus is contained and a discoloration suppressing effect is likely to be exhibited. In that respect, phosphite esters such as phosphite and phosphonite are preferable.

Examples of phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilaurylhydrogen phosphite, triethyl phosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl) phos. Fight, Tristearyl Phosphite, Diphenyl Monodecyl Phosphite, Monophenyl Didecyl Phosphite, Diphenyl Mono (Tridecyl) Phosphite, Tetraphenyl Dipropylene Glycol Diphosphite, Tetraphenyl Tetra (Tridecyl) Pentaerythritol Tetraphosphite, Water Additive bisphenol A phenol phosphite polymer, diphenylhydrogenphosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4'-isopropi Redendiphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butyl) Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, 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) octylphosphite, bis (2,4) − Dicumylphenyl) Pentaerythritol diphosphite and the like.

As phosphonite, tetrakis (2,4-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-n-butylphenyl) -4,4'-bipheni Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphospho Nite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrax (2,6-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) Examples thereof include 2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite and tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite.

Examples of acid phosphates include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl acid. Phenyl acid, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate. , Dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate, etc. Can be mentioned.

Among the phosphites, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Ellisritol diphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred and have good heat resistance. Tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred because of its presence and resistance to hydrolysis.

These phosphorus-based heat stabilizers (C) may be used alone or in combination of two or more.

When the aromatic polycarbonate resin composition of the present invention contains a phosphorus-based heat stabilizer (C), the content thereof is usually 0.001 part by mass or more, preferably 0.001 part by mass or more, based on 100 parts by mass of the aromatic polycarbonate resin (A). Is 0.003 parts by mass or more, more preferably 0.005 parts by mass or more, and usually 0.1 parts by mass or less, preferably 0.08 parts by mass or less, and more preferably 0.06 parts by mass or less. If the content of the phosphorus-based heat stabilizer (C) is less than the lower limit of the above range, the heat-stabilizing effect may be insufficient, and the content of the phosphorus-based heat stabilizer (C) is within the above range. If it exceeds the upper limit, the effect may reach a plateau and become uneconomical.

<Antioxidant (D)>
The aromatic polycarbonate resin composition of the present invention preferably contains an antioxidant (D), if desired. By containing the antioxidant (D), deterioration of hue and deterioration of mechanical properties during heat retention can be suppressed.

Examples of the antioxidant (D) include a hindered phenolic antioxidant. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 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-butyl-a, a', a''-(mesitylen-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], hexamethylene Bis [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-triazine- 2-Ilamino) Phenol and the like can be mentioned.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. Examples of commercially available products of such phenolic antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by Ciba, "Adeka Stub AO-50" and "Adeka Stub AO-60" manufactured by Adeka Corporation. Be done.

The antioxidant (D) may contain one type or two or more types in any combination and ratio.

When the aromatic polycarbonate resin composition of the present invention contains the antioxidant (D), the content thereof is usually 0.0001 parts by mass or more, preferably 0.0001 parts by mass or more, based on 100 parts by mass of the aromatic polycarbonate resin (A). 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, still more preferably 0.3 parts by mass. It is less than a part by mass. If the content of the antioxidant (D) is less than the lower limit of the above range, the effect as the antioxidant (D) may be insufficient, and the content of the antioxidant (D) is the above. If the upper limit of the range is exceeded, the effect may reach a plateau and become uneconomical.

<Ultraviolet absorber (E)>
The aromatic polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber (E), if desired. By containing the ultraviolet absorber (E), the weather resistance of the aromatic polycarbonate resin composition of the present invention can be improved.

Examples of the ultraviolet absorber (E) include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, ogizanylide compounds, malonic acid ester compounds, and hindered amine compounds. Examples include organic ultraviolet absorbers such as. Among these, an organic ultraviolet absorber is preferable, and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the transparency and mechanical properties of the aromatic polycarbonate resin composition of the present invention can be improved.

Specific examples of the benzotriazole compound include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'-bis (α, α-dimethylbenzyl). ) 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) 3-Tetramethylbutyl) -6- (2N-benzotriazole-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-benzotriazole-2-yl) phenol] is preferred, especially 2- (2'-hydroxy-5'-tert -Octylphenyl) Benzotriazole is preferred. Specific examples of such benzotriazole compounds include "Seasorb 701", "Seasorb 705", "Seasorb 703", "Seasorb 702", "Seasorb 704", and "Seasorb 709" manufactured by Cytec Chemical Industries, Ltd. "Biosorb 520", "Biosorb 582", "Biosorb 580", "Biosorb 583" manufactured by Yakuhin Co., Ltd., "Chemisorb 71", "Chemisorb 72" manufactured by Chemipro Kasei, "Siasorb UV5411" manufactured by Cytec Industries, "Siasorb UV5411" manufactured by Cytec Industries, Ltd. LA-32 ”,“ LA-38 ”,“ LA-36 ”,“ LA-34 ”,“ LA-31 ”,“ Chinubin P ”,“ Chinubin 234 ”,“ Chinubin 326 ”, manufactured by Ciba Specialty Chemicals, Inc. Examples thereof include "Chinubin 327" and "Chinubin 328".

Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n-octoxy. Benzophenone, 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. Specific examples of such a benzophenone compound include "Seasorb 100", "Seasorb 101", "Seasorb 101S", "Seasorb 102" and "Seasorb 102" manufactured by Cipro Chemical Co., Ltd. Seasorb 103, Kyodo Yakuhin Co., Ltd. "Biosorb 100", "Biosorb 110", "Biosorb 130", ChemiPro Kasei Co., Ltd. "Chemisorb 10", "Chemisorb 11", "Chemisorb 11S", "Chemisorb 12", "Chemisorb 13" , "Chemisorb 111", BASF "Ubinul 400", BASF "Ubinul M-40", BASF "Ubinul MS-40", Cytec Industries "Siasorb UV9", "Siasorb UV284", " Examples thereof include "Siasorb UV531", "Siasorb UV24", "Adecastab 1413" manufactured by Adeca, and "Adecastab LA-51".

Specific examples of the salicylate compound include phenyl salicylate, 4-tert-butylphenyl salicylate, and the like. Specific examples of such salicylate compound include "Seasorb 201" and "Seasorb" manufactured by Cipro Kasei Co., Ltd. 202 ”,“ Chemisorb 21 ”manufactured by Chemipro Kasei Co., Ltd.,“ Chemisorb 22 ”and the like.

Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and the like, and examples of such a cyanoacrylate compound include ethyl-2-cyano-3,3-diphenylacrylate. Specifically, for example, "Sea Sorb 501" manufactured by Cipro Kasei Co., Ltd., "Biosorb 910" manufactured by Kyodo Yakuhin Co., Ltd., "Ubisolator 300" manufactured by Daiichi Kasei Co., Ltd., "Ubinuru N-35" manufactured by BASF, and "Ubinuru N-". 539 ”and the like.

Specific examples of the oxalinide compound include 2-ethoxy-2'-ethyl oxalinic acid bisarinide, and specific examples of such oxalinide compounds include "Sanduboa" manufactured by Clariant AG. "VSU" and the like.

As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such malonic acid ester compounds include "PR-25" manufactured by Clariant Japan Co., Ltd. and "B-CAP" manufactured by Ciba Specialty Chemicals Co., Ltd.

When the aromatic polycarbonate resin composition of the present invention contains an ultraviolet absorber (E), the content thereof is usually 0.001 part by mass or more, preferably 0.001 part by mass or more, based on 100 parts by mass of the aromatic polycarbonate resin (A). 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, still more preferably 0.4 parts by mass. It is less than a part by mass. If the content of the ultraviolet absorber (E) is equal to or less than the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and the content of the ultraviolet absorber (E) is the upper limit of the above range. If it exceeds the above, mold ultraviolet rays and the like may occur, causing mold contamination.
The ultraviolet absorber (E) may contain one type, or two or more types may be contained in any combination and ratio.

<Release agent (F)>
The aromatic polycarbonate resin composition of the present invention may contain a mold release agent (F), and the mold release agent (F) is preferably a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid. Used.

Examples of the aliphatic carboxylic acid constituting the fully esterified product include saturated or unsaturated aliphatic monocarboxylic acids, dicarboxylic acids and tricarboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Of these, the preferred aliphatic carboxylic acid is a mono or dicarboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monocarboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, caproic acid, lauric acid, araquinic acid, bechenic acid, lignoceric acid, cerotic acid, melissic acid, and tetratoriacontanic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

On the other hand, examples of the fatty alcohol component constituting the fully esterified product include saturated or unsaturated monohydric alcohols, saturated or unsaturated polyhydric alcohols, and the like. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol.

Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol. And so on.

The esterification rate of the full esterified product of the aliphatic alcohol and the aliphatic carboxylic acid does not necessarily have to be 100%, but may be 80% or more. The esterification rate of the full esterified product according to the present invention is preferably 85% or more, and particularly preferably 90% or more.

The full esterified product of the aliphatic alcohol and the aliphatic carboxylic acid used in the present invention is particularly one or more of the full esterified products of the monoaliphatic alcohol and the monoaliphatic carboxylic acid, and the polyvalent aliphatic alcohol. It is preferable to contain one or more of a full esterified product of and a monoaliphatic carboxylic acid, a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid, and a polyvalent aliphatic alcohol and a mono. When used in combination with a full esterified product of an aliphatic carboxylic acid, the effect of improving the mold release effect, suppressing the generation of gas during melt-kneading, and reducing the mold deposit can be obtained.

As the full esterified product of monoaliphatic alcohol and monoaliphatic carboxylic acid, a full esterified product of stearyl alcohol and stearic acid (stearyl stearate) and a full esterified product of behenyl alcohol and behenic acid (behenyl behenate) are preferable. As a full esterified product of polyvalent aliphatic alcohol and monoaliphatic carboxylic acid, a full esterified product of glycerin serine and stearic acid (glycerin tristearylate) and a full esterified product of pentaerythritol and stearic acid (pentaerythritol tetra). Stearate) is preferable, and pentaerythritol tetrastearilate is particularly preferable.

The full esterified product of the aliphatic alcohol and the aliphatic carboxylic acid may contain the aliphatic carboxylic acid and / or the alcohol as an impurity, or may be a mixture of a plurality of compounds.

When the aromatic polycarbonate resin composition of the present invention contains a mold release agent (F) such as a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid, the content thereof is the aromatic polycarbonate resin (A) 100. It is usually 2 parts by mass or less, preferably 1 part by mass or less with respect to the mass part. If the content of the release agent (F) is too large, there are problems such as deterioration of hydrolysis resistance and mold contamination during injection molding.

When a full esterified product of a monofatty alcohol and a monoaliphatic carboxylic acid and a full esterified product of a polyhydric fatty alcohol and a monoaliphatic carboxylic acid are used in combination as the release agent (F), these are used. The ratio (mass ratio) may be a full esterified product of a monofatty alcohol and a monoaliphatic carboxylic acid: a full esterified product of a polyhydric aliphatic alcohol and a monoaliphatic carboxylic acid = 1: 1-10. It is preferable to use these in combination to ensure that the above effects are obtained.

[Dyeing pigment]
The aromatic polycarbonate resin composition of the present invention may contain a dye pigment if desired. By containing a dye pigment, the hiding property and weather resistance of the aromatic polycarbonate resin composition of the present invention can be improved, and the design of the molded product obtained by molding the aromatic polycarbonate resin composition of the present invention is improved. Can be made to.

Examples of dyeing pigments include inorganic pigments, organic pigments, and organic dyes.

Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc flower, petals, chromium oxide, iron black, titanium yellow, and zinc-. Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chrome acid pigments such as chrome yellow and molybdate orange; Russian pigments and the like can be mentioned.

Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and iso. Condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like can be mentioned.

Among these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, phthalocyanine-based compounds and the like are preferable from the viewpoint of thermal stability.

In addition, 1 type may be contained in the dye pigment, and 2 or more types may be contained in arbitrary combinations and ratios.
Further, the dyeing pigment may be master-batched with polystyrene-based resin, polycarbonate-based resin, or acrylic-based resin for the purpose of improving handleability at the time of extrusion and improving dispersibility in the resin composition. Good.

When the aromatic polycarbonate resin composition of the present invention contains a dye pigment, the content thereof may be appropriately selected according to the required design property, but with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and usually 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass. Hereinafter, it is more preferably 0.5 parts by mass or less. If the content of the dyeing pigment is less than the lower limit of the above range, the coloring effect may not be sufficiently obtained, and if the content of the dyeing pigment exceeds the upper limit of the above range, mold devogit etc. may occur. , May cause mold contamination.

<Other ingredients>
The aromatic polycarbonate resin composition of the present invention may contain other components in addition to those described above, if necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include various resin additives such as antifogging agents, antiblocking agents, fluidity improving agents, sliding modifiers, plasticizers, dispersants, and antibacterial agents. One of these resin additives may be contained, or two or more of these resin additives may be contained in any combination and ratio.

[Manufacturing method of aromatic polycarbonate resin composition]
The method for producing the aromatic polycarbonate resin composition of the present invention is not limited, and a known method for producing an aromatic polycarbonate resin composition can be widely adopted.

Specific examples thereof include the aromatic polycarbonate resin (A), the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) according to the present invention, and if necessary, blended. Other components are premixed using various mixers such as tumblers, henschel mixers, and super mixers, and then vanbury mixers, rolls, brabenders, single-screw kneading extruders, twin-screw kneading extruders, kneaders, etc. Examples thereof include a method of melt-kneading with a mixer.

Further, for example, the aromatic polycarbonate resin composition of the present invention is obtained by premixing each component without premixing or mixing only a part of the components in advance and supplying the composition to an extruder using a feeder for melt kneading. It can also be manufactured.

Further, for example, a resin composition obtained by mixing some components in advance, supplying them to an extruder, and melt-kneading the resin composition is used as a masterbatch, and the masterbatch is mixed with the remaining components again and melt-kneaded. The aromatic polycarbonate resin composition of the present invention can also be produced.
Further, for example, when a component that is difficult to disperse is mixed, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance and kneaded with the solution or dispersion to disperse. It can also enhance the sex.

Examples of the method of melt-kneading after mixing each component in advance by the above method include a method using a Banbury mixer, a roll, a lavender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader and the like.

[Molding]
The molded product of the present invention is obtained by molding the above-mentioned aromatic polycarbonate resin composition of the present invention.
The shape, pattern, color, size, etc. of the molded product of the present invention are not limited and may be arbitrarily set according to the intended use of the molded product.

Examples of molded products include electrical and electronic equipment, OA equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts such as automobiles, building materials, various containers, leisure goods / miscellaneous goods, and parts such as lighting equipment. Be done. Among these, it is particularly suitable for parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, lighting equipment, and automobile parts, and is particularly suitable for automobile parts.

The method for producing the molded product is not particularly limited, and any molding method generally used for the aromatic polycarbonate resin composition can be adopted. For example, an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method, etc. Can be mentioned. Further, a molding method using a hot runner method can also be used.
In the case of the injection molding method, the injection speed can be 20 to 300 mm / sec. In particular, the effect of the present invention for improving transparency during high-speed molding is effectively exhibited in an injection molding method at an injection speed of 50 mm / sec, particularly at a high speed exceeding 100 mm / sec.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, [part] represents "part by mass" based on the mass standard.

The compounding components used in the preparation of the aromatic polycarbonate resin composition in the following Examples and Comparative Examples are as shown in Table 1 below.

[Examples 1 to 11, Comparative Examples 1 to 9]
<Manufacturing of resin pellets>
Each component shown in Table 1 is blended in the ratios shown in Tables 2 and 3, mixed in a tumbler for 20 minutes, and then supplied to a twin-screw extruder (TEM26SX manufactured by Toshiba Machine Co., Ltd.) equipped with one vent to rotate the screw. It was kneaded and extruded under the conditions of several 200 rpm, a discharge rate of 20 kg / hr, and a barrel temperature of 260 ° C. The extruded strand-shaped molten resin was rapidly cooled in a water tank and then cut using a pelletizer to obtain pellets of an aromatic polycarbonate resin composition.

<Preparation of 1.5 mm thick plate test piece>
After drying the obtained pellets at 100 ° C. for 5 hours, a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. were used in an injection molding machine (“SE50DUZ” manufactured by Sumitomo Heavy Industries, Ltd.) using a steel mold. Injection molding was performed under the condition of an injection speed of 200 mm / sec to prepare a plate test piece having a thickness of 90 × 50 × 1.5 mm.

<Transparency evaluation>
The haze value (unit:%) of the produced 1.5 mm thick plate test piece was measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K 7105. The haze is a value used as a measure of the turbidity of the resin, and the smaller the number, the higher the transparency, and the haze is preferably 2 or less, particularly preferably 1.5 or less. The results are shown in Tables 2 and 3. In addition, it is described as "Haze" in the table.

<Surface hardness evaluation>
The hardness of the 1.5 mm-thick plate test piece produced was evaluated by performing a scratch test five times according to JIS K5400. The results are shown in Tables 2 and 3. In addition. Indicated as "pencil hardness" in the table. The pencil hardness is preferably F or higher, and more preferably H or higher.

<Preparation of retention molded plate test piece>
After the obtained pellets are dried at 100 ° C. for 5 hours, a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and an injection speed are used in an injection molding machine (“ROBOSHOT S2000i” manufactured by FANUC) using a steel mold. Injection molding was performed at 50 mm / sec and a cycle time of 180 seconds to prepare a three-stage plate test piece having a thickness of 90 × 60 × 1, 2, and 3 mm.

<Hue evaluation during residence>
Of the prepared residence-molded plate test pieces, the hue of the 3 mm-thick portion of the test pieces of the 1st and 10th shots was measured using a SE6000 type color difference meter manufactured by Nippon Denshoku Kogyo Co., Ltd., and 1 The difference ΔYI between the YI value (YI ₁ ) of the plate test piece obtained on the shot and the YI value (YI ₁₀ ) of the plate test piece obtained on the 10th shot was calculated by the following formula (2), and the hue at the time of residence was obtained. Was evaluated. The smaller ΔYI is, the more excellent the retention heat stability is, and the ΔYI is preferably 1 or less, more preferably 0.8 or less.
ΔYI = YI ₁₀ −YI ₁ … (2)

From Table 1, the aromatic polycarbonate resin composition of the present invention containing the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) in a predetermined ratio has a high surface hardness. It can be seen that it is excellent in transparency (transparency during high-speed molding) and retention heat stability.
In Comparative Examples 1, 5 and 7, which contained only the (meth) acrylic copolymer (B1) and did not contain the (meth) acrylic copolymer (B2), the transparency was inferior, and in particular, (meth) acrylic. When the blending amount of the system copolymer (B1) is increased, the transparency is remarkably lowered.
On the other hand, in Comparative Examples 2, 6 and 8 containing only the (meth) acrylic copolymer (B2) and not containing the (meth) acrylic copolymer (B1), the retention heat stability was poor, and particularly (meth). ) If the amount of the acrylic copolymer (B2) is large, the retention heat stability is poor.
Comparative Example 9 containing neither the (meth) acrylic copolymer (B1) nor the (meth) acrylic copolymer (B2) has good transparency and heat retention stability, but its surface hardness is significantly inferior. It becomes a thing.
Even if the (meth) acrylic copolymer (B1) and the (meth) acrylic copolymer (B2) are contained, they are transparent in Comparative Examples 3 and 4 in which the content ratio thereof is outside the scope of the present invention. It is not possible to achieve both property and heat retention stability.

Regarding the aromatic polycarbonate resin composition of Comparative Example 1, a plate test piece was prepared in the same manner as the above-mentioned method for producing a plate test piece having a thickness of 1.5 mm, except that the injection molding speed was set to 50 mm / sec. As a result of evaluating the transparency in the same manner, a good result was obtained with Haze of 1.2. From this, the (meth) acrylic copolymer (B1) can obtain a molded product having excellent transparency at an injection speed of about 50 mm / sec, but the transparency is impaired when high-speed molding is performed. It turns out that

Claims (2)

The following (meth) acrylic copolymer (B1) and (meth) acrylic copolymer (B2) are contained in a total of 10 to 100 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin, and both (meth) acrylic The content ratio of the polymer (B1) and the (meth) acrylic copolymer (B2) is the mass ratio of the (meth) acrylic copolymer (B1): (meth) acrylic copolymer (B2) = 80 to 20: a 20-80 der Ru aromatic polycarbonate resin composition,
A 1.5 mm thick plate test piece obtained by injection molding the aromatic polycarbonate resin composition at an injection speed of 200 mm / sec had a haze of 2 or less measured in accordance with JIS K7105.
When a plate test piece having a thickness of 3 mm was injection-molded from the aromatic polycarbonate resin composition at a cylinder temperature of 280 ° C. and a cycle time of 180 seconds, the plate test piece obtained in the first shot calculated by the following formula (2). An aromatic polycarbonate resin composition, wherein the difference ΔYI between the YI value (YI ₁ ) of _{No. 1} and the plate test piece YI value (YI ₁₀ ) obtained at the 10th shot is 0.8 or less.
ΔYI = YI ₁₀ −YI ₁ … (2)
(Meta) Acrylic Copolymer (B1): Aromatic (meth) acrylate unit (b1-1) 5 to 80% by mass and methyl (meth) acrylate, which are phenyl (meth) acrylate and / or benzyl (meth) acrylate. (Meta) Acrylic Copolymer (Meta) Acrylic Copolymer (B2) containing 20 to 95% by mass of the unit (b1-2) and having a mass average molecular weight of 5,000 to 30,000: The following general It contains 5 to 85% by mass of the (meth) acrylate unit (b2-1) represented by the formula (1) and 15 to 95% by mass of the methyl (meth) acrylate unit (b2-2), and has a mass average molecular weight of 3,. 000-30,000 (meth) acrylic copolymers

(In equation (1), X is a single bond, -C (R ² ) (R ³ )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O). ) A divalent group selected from the group consisting of O-, -S-, -SO-, -SO _2- and any combination thereof.
R ¹ is a hydrogen atom or a methyl group and
R ² and R ³ each independently have a hydrogen atom, 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 1 carbon atom. It is a linear alkoxy group of 10 to 10, a branched alkoxy group of 3 to 10 carbon atoms, a cyclic alkoxy group of 3 to 10 carbon atoms, a phenyl group, or a phenylphenyl group, or R ² and R ³ are mutual. It may be linked to to form a ring having 3 to 10 carbon atoms together with the carbon atom to which these are bonded.
R ⁴ and R ⁵ independently have 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 1 to 10 carbon atoms. It is a linear 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.
m is an integer from 1 to 10
p is an integer from 0 to 4 and
q is an integer from 0 to 5. ) The aromatic polycarbonate resin composition according to claim 1, wherein the molded product of the aromatic polycarbonate resin composition has a pencil hardness of F or more measured in accordance with JIS K5400.