JP2015003978A - Aromatic polycarbonate resin molded article with boss hole - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article, obtained from an aromatic polycarbonate resin composition whose surface hardness is improved by blending a particular (meth)acrylate copolymer (B) into an aromatic polycarbonate resin (A), excellent not only in surface hardness, but also in self-tapping strength of boss hole and in surface appearance.SOLUTION: Provided is a molded article with boss hole having a thickness at plate-like portion of 1 mm or more obtained by injection molding an aromatic polycarbonate resin composition whose resin component is composed of: 55 to 95 mass% of aromatic polycarbonate resin (A) with a mass average molecular weight of 15,000 to 40,000; and 5 to 45 mass% of (meth)acrylate copolymer (B) with a mass average molecular weight of 5,000 to 30,000 having a mass ratio of aromatic (meth)acrylate unit (b1)/methyl methacrylate unit (b2) of 5 to 80/20 to 95. The article has, at an injection speed of 5 to 100 mm/sec during the injection molding, a breakage torque in a self-tapping test with a catch percentage of 68% when a screw with a nominal diameter of 3 mm having a shape of thread portion first kind, second kind and forth kind at the thread portion of a tapping screw described in JIS B1007, of 2.10 N-m or more, and a surface pencil hardness according to JIS K-5600-5-4 standard, of F or more.

Description

  The present invention relates to an aromatic polycarbonate resin molded article having a boss hole. More specifically, the present invention relates to an aromatic polycarbonate resin molded article having high surface hardness, high self-tapping strength of boss holes, excellent appearance, and having boss holes useful for housings of various electric and electronic devices, automobile parts, and the like.

Aromatic polycarbonate resin is excellent in transparency, impact resistance, heat resistance, etc., and the resulting molded product is also excellent in dimensional stability, etc., so housings for electrical and electronic equipment, automotive parts, or It is 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., a product with high commercial value can be obtained by utilizing its beautiful appearance.
However, molded products made of aromatic polycarbonate resin alone have a lower surface hardness compared to products made of metal or glass, so they are inferior in scratch resistance, and when they are wiped with cloth or handled roughly, It has the disadvantage of being easily scratched.

  Boss holes for assembling and reinforcing products are provided in molded products used for electrical and electronic equipment casings and automotive parts. In a molded product having such a boss hole, it is required that not only the surface hardness but also the self-tap strength of the boss hole is sufficiently high. Furthermore, it is required to have an excellent appearance as a product.

Conventionally, as a technique for improving the surface hardness of an aromatic polycarbonate resin, many scratch-resistant aromatic polycarbonate resin compositions in which an aromatic polycarbonate resin is mixed with an acrylate such as methyl methacrylate or an ABS resin have been proposed. ing.
For example, Patent Document 1 describes blending a vinyl cyanide compound-aromatic vinyl compound copolymer and methyl methacrylate. Patent Document 2 describes a resin composition comprising a polyester resin and an ABS resin, a polycarbonate resin, and polymethyl methacrylate. Patent Document 3 describes blending a copolymer made of a vinyl monomer that is reactive with (meth) alkyl acrylate-aromatic vinyl-polycarbonate resin. Further, Patent Document 4 proposes blending a rubber-modified graft copolymer such as ABS resin and a vinyl monomer copolymer such as polymethyl methacrylate.

  However, it is difficult to say that the aromatic polycarbonate resin composition proposed in these patent documents has an excellent balance of physical properties such as mechanical properties, hardness, and transparency.

  An aromatic polycarbonate resin having a mass average molecular weight of 15,000 to 40,000 (A) is obtained by solving this problem and improving the surface hardness while maintaining the high heat resistance and transparency inherent in the aromatic polycarbonate resin. ), The mass ratio (b1 / b2) of the aromatic (meth) acrylate unit (b1) to the methyl methacrylate unit (b2) is 5 to 80/20 to 95, and the mass average molecular weight is 5,000 to 30,000. An aromatic polycarbonate resin composition in which a certain (meth) acrylate copolymer (B) is blended at a predetermined ratio has been proposed (Patent Document 5).

JP 2001-49072 A JP 2001-234040 A JP 2008-56798 A WO2009 / 128601 JP 2012-25790 A

  In the aromatic polycarbonate resin composition described in Patent Document 5, the aromatic polycarbonate resin (A) is blended with a specific (meth) acrylate copolymer (B) at a predetermined ratio, whereby the aromatic polycarbonate resin Although surface hardness can be improved without impairing transparency and heat resistance, Patent Document 5 does not discuss the self-tap strength of the boss hole and the appearance of the injection molded product.

  In the present invention, an aromatic polycarbonate resin composition in which a specific (meth) acrylate copolymer (B) is blended with an aromatic polycarbonate resin (A) to improve the surface hardness is injection-molded. It is another object of the present invention to provide an aromatic polycarbonate resin molded article having a high boss hole self-tap strength and excellent appearance.

  As a result of intensive studies to solve the above problems, the present inventors have improved the surface hardness by blending a specific (meth) acrylate copolymer (B) in a predetermined ratio with the aromatic polycarbonate resin (A). In injection molding of a molded product having a boss hole using the aromatic polycarbonate resin composition, it is possible to obtain an injection molded product excellent in self-tapping strength and appearance of the boss hole by controlling the injection speed. I found it.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] 55 to 95% by mass of an aromatic polycarbonate resin (A) having a mass average molecular weight of 15,000 to 40,000, and a mass ratio of the aromatic (meth) acrylate unit (b1) to the methyl methacrylate unit (b2) ( aroma containing a resin component consisting of (meth) acrylate copolymer (B) having a mass average molecular weight of 5 to 80/20 to 95 and a mass average molecular weight of 5,000 to 30,000 (B). An aromatic polycarbonate resin molded product formed by integrally molding a plate-like portion having a thickness of 1 mm or more and a boss hole projecting from the plate-like portion by injection molding an aromatic polycarbonate resin composition, The injection speed at the time of the injection molding is 5 to 100 mm / sec, and the nominal diameter of 3 m having the shape of the thread portion of the tapping screw in JIS B1007 is 1 type, 2 types and 4 types. The fracture torque in the self-tapping test with a hook rate of 68% when using a screw of m is 2.10 N · m or more, and the surface pencil hardness according to JIS K-5600-5-4 standard is F or more. An aromatic polycarbonate resin molded product having a characteristic boss hole.

[2] In [1], the height of the boss hole is 8 to 12 mm, the outer diameter is 7.27 to 7.83 mm, the inner diameter is 2.42 to 2.73 mm, and the wall thickness is 2.270 to. 2. An aromatic polycarbonate resin molded article having a boss hole characterized by being 705 mm.

[3] In [1] or [2], the aromatic polycarbonate resin molded product is a casing of an electric / electronic device, a part for an automobile, a part for a lighting device, an information terminal device, a home appliance, a leisure article, or miscellaneous goods. An aromatic polycarbonate resin molded article having a boss hole.

[4] 55 to 95% by mass of the aromatic polycarbonate resin (A) having a mass average molecular weight of 15,000 to 40,000, and the mass ratio of the aromatic (meth) acrylate unit (b1) to the methyl methacrylate unit (b2) ( aroma containing a resin component consisting of (meth) acrylate copolymer (B) having a mass average molecular weight of 5 to 80/20 to 95 and a mass average molecular weight of 5,000 to 30,000 (B). A method for integrally molding a molded product having a plate-like portion having a thickness of 1 mm or more and a boss hole projecting from the plate-like portion by injection molding a group polycarbonate resin composition, the injection molding When an injection speed of 5 to 100 mm / sec is used, and a screw with a nominal diameter of 3 mm having 1 type, 2 type, and 4 types of screw parts is used in the screw part of the tapping screw in JIS B1007 An aromatic polycarbonate resin molded article having a breaking torque of 2.10 N · m or more in a self-tap test with a catch rate of 68% and a surface pencil hardness according to JIS K-5600-5-4 standard of F or more is obtained. A method for producing an aromatic polycarbonate resin molded article having a boss hole.

According to the present invention, an aromatic polycarbonate resin composition having a surface hardness improved by blending a specific (meth) acrylate copolymer (B) with an aromatic polycarbonate resin (A) is injected under specific conditions. By molding, an aromatic polycarbonate resin molded product having a high surface hardness, a high self-tapping strength of the boss hole, and an excellent appearance can be provided.
The aromatic polycarbonate resin molded product having a boss hole according to the present invention has an excellent appearance, surface hardness, self-tap strength, electrical / electronic equipment casing, automotive parts, lighting equipment parts, information terminal equipment, Useful for home appliances, leisure goods, miscellaneous goods, etc.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to

〔Overview〕
The present invention relates to an aromatic polycarbonate resin composition (hereinafter referred to as “the present invention”) containing at least an aromatic polycarbonate resin (A) and a specific (meth) acrylate copolymer (B) at a specific ratio. It may be referred to as “aromatic polycarbonate resin composition”.) Is injection molded under specific conditions to form an aromatic polycarbonate resin molded article having a boss hole.
Below, the injection molding method and molded article which concern on this invention are demonstrated first, and then the aromatic polycarbonate resin composition of this invention is demonstrated.

[Injection molding method / molded product]
In the present invention, when producing a molded article having a boss hole by injection molding the aromatic polycarbonate resin composition of the present invention described later, the injection speed of the resin composition is 5 to 100 mm / sec, To do. When the injection speed at the time of injection molding is higher than 100 mm / sec, a boss hole having a high self-tap strength cannot be formed, and the appearance of the molded product is inferior. The slower the injection speed, the better the self-tap strength and the better the appearance of the molded product. However, if the injection rate is too slow, the resin will not be fluid enough to fill the resin to the end of the molded product. Therefore, the injection speed needs to be 5 mm / sec or more.

In the present invention, the details of the action mechanism that improves the self-tap strength of the boss hole and the appearance of the molded product by controlling the injection speed are not clear, but are estimated as follows.
That is, the resin composition is subjected to shear stress due to friction with the inner wall of the mold when flowing in the mold during injection molding, and the aromatic polycarbonate resin (A) and (meta) are caused by the shear stress. ) Adhesiveness at the interface with the acrylate copolymer (B) is lowered to cause partial phase separation, the mechanical strength of the resulting molded product is lowered, and pearly luster is generated to reduce the appearance. .
The aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) used in the present invention are excellent in compatibility and hardly cause phase separation. As a result of applying the shear stress, the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) are phase-separated.
On the other hand, by setting the injection speed to 5 to 100 mm / sec and setting the injection conditions slower than the injection speed in normal injection molding, the shear stress is weakened, and the aromatic polycarbonate resins (A) and (meta) A decrease in self-tap strength and a decrease in appearance due to separation from the acrylate copolymer (B) can be prevented.

  In the present invention, the preferred injection speed varies depending on the blending composition of the aromatic polycarbonate resin (A) and (meth) acrylate copolymer (B) of the aromatic polycarbonate resin composition used for molding, and other component compositions. Usually, 5 to 100 mm / sec, particularly 5 to 60 mm / sec is preferable.

  In the present invention, other injection molding conditions are not particularly limited, but the cylinder temperature during injection molding is 240 to 280 ° C. and the mold temperature is 80 to 120 ° C., depending on the component composition of the resin composition. It is preferable to adjust appropriately to obtain an injection molded product excellent in self-tap strength and appearance.

The aromatic polycarbonate resin molded product having a boss hole according to the present invention is formed by integrally molding a plate-like portion having a thickness of 1 mm or more and a boss hole protruding from the plate-like portion by the injection molding as described above. is there.
The thickness of the plate-like portion may be 1 mm or more, and is not particularly limited and is appropriately determined according to the use of the molded product. In order to obtain the required strength after reducing the thickness of the product. In addition, the thickness of the plate-like portion is preferably about 1 to 3 mm. However, the thickness of the plate-like portion is not limited to this range.

  In addition, if the thickness of the plate-shaped part is less than 1 mm, the fluidity is insufficient and it becomes impossible to fill the resin to the end of the molded product, or the shear rate of the resin passing through the thin-walled part becomes high, and the appearance such as whitening Since defects occur, it is difficult to obtain a good injection-molded product under injection molding conditions at an injection speed of 5 to 100 mm / sec.

  The dimensions of the boss hole formed in the molded product of the present invention are appropriately determined according to the use of the molded product. For example, the height is 8 to 12 mm and the outer diameter is 7.27 to 7.83 mm. And a boss hole having an inner diameter of 2.42 to 2.73 mm and a wall thickness (= (outer diameter−inner diameter) / 2) of 2.27 to 2.705 mm. If the thickness of the boss hole is too thin, it is not possible to perform threading by self-tapping according to the present invention, and it may not be possible to obtain sufficient self-tapping strength even by performing injection molding according to the present invention. In addition, the strength of the boss hole in a product may be insufficient. On the other hand, increasing the thickness of the boss hole more than necessary is not preferable because, for example, in the case of a housing, the accommodation volume of other components is reduced, and the weight of the product is increased.

  In addition, there is no restriction | limiting in particular in the number of the boss holes formed in a plate-shaped part, A required number of boss holes is formed according to a use. Moreover, when the some boss hole is formed in the plate-shaped part, these do not need to be the same dimension and may differ individually.

The boss hole of the aromatic polycarbonate resin molded product of the present invention has a hook ratio when a screw with a nominal diameter of 3 mm having one, two, and four types of shapes is used in the thread portion of the tapping screw in JIS B1007. The fracture torque in a self-tap test of 68% is 2.10 N · m or more.
In the screw part of the tapping screw in JIS B1007, the strength as a boss hole is not good when the breaking torque is less than 2.10 N · m when using a screw with a nominal diameter of 3 mm having one, two or four types of thread. It is enough.
The breaking torque may be 2.10 N · m or more, preferably 2.15 N · m or more.

Further, the aromatic polycarbonate resin molded product of the present invention is characterized in that the surface hardness is F or more, that is, F or harder than F in terms of surface pencil hardness according to JIS K-5600-5-4 standard.
The surface hardness of the molded article may be F or more, but preferably H or more.

In order to obtain a molded product satisfying both the breaking torque and the surface hardness, the mixing ratio of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) of the aromatic polycarbonate resin composition of the present invention is used. Accordingly, the injection speed at the time of injection molding may be appropriately adjusted so as to satisfy the breaking torque and the surface hardness in the range of 5 to 100 mm / sec.
That is, for example, in the range of the blending ratio of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) of the aromatic polycarbonate resin composition of the present invention, the (meth) acrylate copolymer (B) The surface hardness increases as the amount increases, but the self-tap strength tends to decrease. In this case, it is preferable to decrease the injection speed in the range of 5 to 100 mm / sec.

  Examples of application of the aromatic polycarbonate resin molded product of the present invention include: electric / electronic equipment, OA equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, lighting Examples include parts such as equipment. Among these, the molded product of the present invention has a molded product appearance having excellent transparency, surface hardness, and self-tap strength, so that it is a housing for electrical and electronic equipment, parts for automobiles, parts for lighting equipment, and information terminals. Useful for equipment, home appliances, leisure goods, miscellaneous goods, etc.

  Examples of the electric / electronic devices include display devices such as personal computers, game machines, televisions, car navigation systems, and electronic paper, printers, copy machines, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, and cameras. Video cameras, mobile phones, battery packs, recording medium drives and reading devices, portable radio / audio players, and the like. Especially, it can use suitably for the designable parts of housing | casings, such as a television, a personal computer, a car navigation system, and electronic paper.

As a component of the above-mentioned lighting device, it can be suitably used for a cover of LED lighting, EL lighting or the like.
Examples of the automobile parts include car audio, car navigation, meters, and a front panel housing.

[Aromatic polycarbonate resin composition]
Next, the aromatic polycarbonate resin composition of the present invention containing the aromatic polycarbonate resin (A) and the specific (meth) acrylate copolymer (B) at a specific ratio will be described.
The aromatic polycarbonate resin composition of the present invention may contain other components as necessary in addition to the aromatic polycarbonate resin (A) and the specific (meth) acrylate copolymer (B).

[Aromatic polycarbonate resin (A)]
The aromatic polycarbonate resin (A) used in the present invention (hereinafter sometimes referred to as “component (A)”) reacts an aromatic dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester. It is the thermoplastic polymer or copolymer which may be branched and is obtained by making it. The production method of the aromatic polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or melting method (transesterification method) can be used. Moreover, when the melting method is used, an aromatic polycarbonate resin in which the amount of OH groups in the terminal groups is adjusted can be used.

  As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like, preferably bisphenol A. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  In order to obtain a branched aromatic polycarbonate resin, a part of the above-mentioned aromatic dihydroxy compound is mixed with the following branching agents, that is, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl). Heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1, Polyhydroxy compounds such as 3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) oxindole (= isa) Tin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. Dose, the aromatic dihydroxy compound is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

  As aromatic polycarbonate resin (A), among the above-mentioned, polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other Polycarbonate copolymers derived from aromatic dihydroxy compounds are preferred. Further, it may be a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure.

  The aromatic polycarbonate resin mentioned above may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. Examples of the monovalent aromatic hydroxy compound include m- and p-methylphenol, m- and p-. And propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenol and the like.

  The molecular weight of the aromatic polycarbonate resin (A) used in the present invention is arbitrary depending on the use and may be appropriately selected and determined. From the viewpoint of moldability, strength, etc., the molecular weight of the aromatic polycarbonate resin (A) is a gel. The mass average molecular weight [Mw] in terms of polycarbonate (PC) measured by permeation chromatography is 15,000 to 40,000, preferably 15,000 to 30,000. As described above, when the mass average molecular weight is 15,000 or more, the mechanical strength tends to be further improved, which is more preferable in the case of use in applications requiring high mechanical strength. On the other hand, when the mass average molecular weight is 40,000 or less, a decrease in fluidity tends to be suppressed and improved, which is more preferable from the viewpoint of easy molding processability.

  The weight average molecular weight of the aromatic polycarbonate resin (A) is preferably 17,000 to 30,000, particularly preferably 19,000 to 27,000. Further, two or more types of aromatic polycarbonate resins having different mass average molecular weights may be mixed. In this case, an aromatic polycarbonate resin having a mass average molecular weight outside the above preferred range may be mixed. In this case, the mass average molecular weight of the mixture is preferably within the above range.

[(Meth) acrylate copolymer (B)]
The (meth) acrylate copolymer (B) used in the present invention (hereinafter sometimes referred to as “component (B)”) is composed of an aromatic (meth) acrylate unit (b1) and a methyl methacrylate unit (b2). Containing.
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 monomers.

  The aromatic (meth) acrylate which is a monomer constituting the aromatic (meth) acrylate unit (b1) refers to a (meth) acrylate having an aromatic group in the ester portion. Examples of the aromatic (meth) acrylate include phenyl (meth) acrylate and benzyl (meth) acrylate. These may 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) acrylate copolymer (A) has the aromatic (meth) acrylate unit (b1), the transparency of the resin composition obtained by mixing with the aromatic polycarbonate resin (A) can be improved. it can.

  The monomer constituting the methyl methacrylate unit (b2) is methyl methacrylate. The methyl methacrylate unit (b2) has an effect of well dispersing the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B), and can improve the surface hardness of the molded product.

  The (meth) acrylate copolymer (B) according to the present invention has a mass ratio (b1 / b2) of the aromatic (meth) acrylate unit (b1) to the methyl methacrylate unit (b2) of 5 to 80/20 to 95. That is, an aromatic (meth) acrylate unit (b1) 5 to 80% by mass and a methyl methacrylate unit (b2) 20 to 95% by mass (however, the sum of (b1) and (b2) Is 100% by mass). If the content of the aromatic (meth) acrylate unit (b1) in the (meth) acrylate copolymer (B) is 5% by mass or more and the content of the methyl methacrylate unit (b2) is 95% by mass or less, Transparency is maintained in the high addition region of the (meth) acrylate copolymer (B), the content of the aromatic (meth) acrylate unit (b1) is 80% by mass or less, and the content of the methyl methacrylate unit (b2) is 20%. If it is at least mass%, the compatibility with the aromatic polycarbonate resin (A) is not too high, and the migration to the surface of the molded product does not decrease, so the surface hardness does not decrease.

  Moreover, in the high addition area | region of (meth) acrylate copolymer (B), since it expresses high surface hardness, maintaining further transparency, (meth) acrylate copolymer (B) is aromatic ( It is preferable to contain 20-70 mass% of (meth) acrylate units (b1) and 30-80 mass% of methyl methacrylate units (b2) (however, the sum total of (b1) and (b2) is 100 mass%).

  If the content of the aromatic (meth) acrylate unit (b1) in the (meth) acrylate copolymer (B) is 20% by mass or more and the content of the methyl methacrylate unit (b2) is 80% by mass or less, the fragrance Since the compatibility with the aromatic polycarbonate resin (A) is not too high and the transferability to the surface of the molded product is not lowered, the surface hardness is not lowered, and the content of the aromatic (meth) acrylate unit (b1) is 70. When the content of the methyl methacrylate unit (b2) is 30% by mass or less at a mass% or less, the transparency is maintained in the high addition region of the (meth) acrylate copolymer (B).

The (meth) acrylate copolymer (B) has a mass average molecular weight of 5,000 to 30,000, preferably 10,000 to 25,000, and particularly preferably 13,000 to 20,000. When the weight average molecular weight of the (meth) acrylate copolymer (B) is 5,000 to 30,000, the compatibility with the aromatic polycarbonate resin (A) is good, and the effect of improving the surface hardness is excellent.
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the (meth) acrylate copolymer (B) are gel permeation using chloroform or tetrahydrofuran (THF) as a solvent. Measurements can be made using an association chromatography. The molecular weight is a value in terms of polystyrene (PS).

  As a method for polymerizing the monomer for obtaining the (meth) acrylate copolymer (B) used in the present invention, a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method or the like is used. can do. A suspension polymerization method and a bulk polymerization method are preferable, and a suspension polymerization method is more preferable. In addition, additives necessary for polymerization can be appropriately added as necessary, and examples of the additive include a polymerization initiator, an emulsifier, a dispersant, a chain transfer agent and the like.

[Resin component]
The aromatic polycarbonate resin composition of the present invention contains, as a resin component, an aromatic polycarbonate resin (A) of 55 to 95% by mass and a (meth) acrylate copolymer (B) of 5 to 45% by mass (provided that (The total of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) is 100% by mass).

  The mass ratio of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) is more preferably 60 to 85% by mass of the (A) component, and 15 to 40% by mass of the (B) component. Especially preferably, it is 20-35 mass% of (B) component with respect to 65-80 mass% of (A) component.

  When the mass ratio of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) is within the above range, the (meth) acrylate copolymer (B) with respect to the aromatic polycarbonate resin (A). ), The effect of maintaining the physical property balance while improving the transparency and improving the surface hardness can be obtained with certainty. When the (meth) acrylate copolymer (B) is less than the above range, the effect of improving the surface hardness is not sufficient, and when the proportion of the (meth) acrylate copolymer (B) is larger than the above range, the self tap strength, The appearance of the molded product tends to deteriorate.

  The aromatic polycarbonate resin composition of the present invention is a resin component other than the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B), as long as the object of the present invention is not impaired. It may contain components. Other transparent resin components that can be blended include, for example, polystyrene resin, high impact polystyrene resin, hydrogenated polystyrene resin, polyacryl styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, 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 Amorphous polyarylate resin, polyether sulfone, styrene thermoplastic elastomer, olefin thermoplastic elastomer, polyamide thermoplastic elastomer, polyester thermoplastic elastomer, polyurethane Is Kyora thermoplastic elastomers such as thermoplastic elastomers, preferably, polystyrene resin, ABS resin, AS resin, AES resin, ASA resin, a polyphenylene ether resin, polymethacrylic methacrylate resins, and polyester resins.

  These may be used alone or in combination of two or more, but the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) are used in a specific ratio. In order to obtain the effect of the present invention, the other transparent resin component is 20 masses per 100 mass parts in total of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B). Part or less.

[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 additives include phosphorus-based heat stabilizers, mold release agents, glass reinforcing materials, antioxidants, ultraviolet absorbers, dyes and pigments, antistatic agents, flame retardants, and dripping inhibitors.

<Phosphorus heat stabilizer>
Phosphorus heat stabilizers are generally effective in improving the residence stability at high temperatures and the heat resistance stability when using resin molded products when melt-kneading resin components.

  Examples of the phosphorus-based heat stabilizer used in the present invention include phosphorous acid, phosphoric acid, phosphorous acid ester, phosphoric acid ester, etc. Among them, trivalent phosphorus is included, and it is easy to express a discoloration suppressing effect. Phosphites such as phosphites and phosphonites are preferred.

  Examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butyl) Ruphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4'-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphos Phyto, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) 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'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6- -Tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert) -Butylphenyl) -3,3'-biphenylenediphosphonite and the like.

  Examples of the acid phosphate 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 phosphate. Phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid Sulfate, 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 phenyl Acid phosphate, bisnonylphenyl acid phosphate, etc. are mentioned.

  Among the phosphites, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferable, and heat resistance is good. Tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred in that it is difficult to hydrolyze.

  These phosphorus heat stabilizers 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, the content thereof is based on 100 parts by mass in total of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B). Usually, 0.001 parts by mass or more, preferably 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, more preferably 0.06 parts by mass or less. If the content of the phosphorus-based heat stabilizer is less than the lower limit of the above range, the thermal stability effect may be insufficient, and if the content of the phosphorus-based heat stabilizer exceeds the upper limit of the above range , There is a possibility that the effect will reach its peak and become less economical.

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

  Examples of the aliphatic carboxylic acid constituting the fully esterified product include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicic acid, tetratriacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  On the other hand, examples of the aliphatic 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, monovalent or polyvalent 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 more 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, dipentaerythritol. Etc.

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

  The full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid used in the present invention is, in particular, one or more of a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid, and a polyhydric aliphatic alcohol. It is preferable to contain 1 type, or 2 or more types of the full esterification product of a mono-aliphatic carboxylic acid, a full esterification product of a mono-aliphatic alcohol and a mono-aliphatic carboxylic acid, Combined use with a fully esterified product with an aliphatic carboxylic acid improves the mold release effect, suppresses gas generation during melt kneading, and reduces the mold deposit.

  As a full esterified product of monoaliphatic alcohol and monoaliphatic carboxylic acid, a full esterified product of stearyl alcohol and stearic acid (stearyl stearate), a full esterified product of behenyl alcohol and behenic acid (behenyl behenate) is preferable. As a full esterified product of a polyaliphatic alcohol and a monoaliphatic carboxylic acid, a full esterified product of glycerol serine and stearic acid (glycerol tristearate), a full esterified product of pentaerythritol and stearic acid (pentaerythritol tetra) Stearylate) is preferred, and pentaerythritol tetrastearate is particularly preferred.

  The full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid may contain an aliphatic carboxylic acid and / or 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 release agent such as a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid, the content thereof is the aromatic polycarbonate resin (A) and (meth). It is 2 mass parts or less normally with respect to a total of 100 mass parts of an acrylate copolymer (B), Preferably it is 1 mass part or less. When there is too much content of a mold release agent, there exist problems, such as a fall of hydrolysis resistance and mold contamination at the time of injection molding.

  When a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid and a full esterified product of a polyaliphatic alcohol and a monoaliphatic carboxylic acid are used in combination as a mold release agent, the use ratio (mass) Ratio) is a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid: a full esterified product of a polyaliphatic alcohol and a monoaliphatic carboxylic acid = 1: 1 to 10 in combination. It is preferable to obtain the above-mentioned effect with certainty.

<Antioxidant>
The aromatic polycarbonate resin composition of the present invention preferably contains an antioxidant as desired. By containing the antioxidant, it is possible to suppress hue deterioration and deterioration of mechanical properties during heat retention.

  Examples of the antioxidant include hindered phenol-based antioxidants. Specific examples thereof 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-butyl-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.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Examples of such commercially available phenolic antioxidants include “Irganox 1010”, “Irganox 1076” manufactured by Ciba, “Adekastab AO-50”, “Adekastab AO-60” manufactured by Adeka, and the like. It is done.

  In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  When the aromatic polycarbonate resin composition of the present invention contains an antioxidant, the content thereof is based on a total of 100 parts by mass of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B). Usually 0.0001 parts by mass or more, preferably 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. It is not more than mass parts, more preferably not more than 0.3 mass parts. When the content of the antioxidant is less than the lower limit of the above range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the above range, There is a possibility that the effect reaches its peak and is not economical.

<Ultraviolet absorber>
The aromatic polycarbonate resin composition of the present invention preferably contains a UV absorber as desired. By containing the ultraviolet absorber, the weather resistance of the aromatic polycarbonate resin composition of the present invention can be improved.

  Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, and hindered amine compounds. Examples include ultraviolet absorbers. In 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 are improved.

  Specific examples of the benzotriazole compound include, for example, 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-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others 2- (2'-hydroxy- 5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] are preferred. In particular, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is preferred. Specific examples of such a benzotriazole compound include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Yakuhin Kagaku Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, Inc. “ “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinuvin P”, “Tinubin 234”, “Tinubin 326” manufactured by Ciba Specialty Chemicals, “Tinuvin 327”, “Tinuvin 328” and the like can be mentioned.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 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 4,4′-dimethoxybenzophenone and the like. Specific examples of such a benzophenone compound include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cypro Kasei Co., Ltd. Seesorb 103 ", joint medicine “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 "," ADEKA STAB 1413 "," ADEKA STAB LA-51 "manufactured by Adeka Corporation and the like.

  Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such a salicylate compound include, for example, “Seesorb 201” and “Seesorb” manufactured by Sipro Kasei Co., Ltd. 202 ”,“ Kemisorb 21 ”,“ Kemisorb 22 ”manufactured by Chemipro Kasei Co., Ltd., and the like.

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Specifically, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Pharmaceutical Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35” manufactured by BASF, 539 "and the like.

  Specific examples of the oxanilide compound include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide and the like. Specific examples of such an oxalinide compound include “Sanduboa VSU "etc. are mentioned.

  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 a malonic ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.

When the aromatic polycarbonate resin composition of the present invention contains an ultraviolet absorber, the content thereof is based on a total of 100 parts by mass of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B). 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 1 part by mass or less, more preferably 0.5 parts by mass. It is not more than part by mass, more preferably not more than 0.4 part by mass. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination.
In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

[Dye and pigment]
The aromatic polycarbonate resin composition of the present invention may contain a dye / pigment if desired. By containing the dye / pigment, the concealability 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.

  Examples of the dye / pigment 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 white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  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, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

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

In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.
In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during 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 may be appropriately selected according to the required design properties, but the aromatic polycarbonate resin (A) and the (meth) acrylate co-polymerize. It is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, with respect to 100 parts by mass of the combined (B). Preferably it is 2 mass parts or less, More preferably, it is 1 mass part or less, More preferably, it is 0.5 mass part or less. When the content of the dye / pigment is less than or equal to the lower limit of the above range, the coloring effect may not be sufficiently obtained, and when the content of the dye / pigment exceeds the upper limit of the above range, a mold deposit or the like occurs. , 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 as needed, as long as the desired physical properties are not significantly impaired. Examples of other components include other flame retardants such as silicon flame retardants other than the above flame retardants, antifogging agents, antiblocking agents, fluidity improvers, sliding property modifiers, plasticizers, and dispersants. And various resin additives such as antibacterial agents. One of these resin additives may be contained, or two or more thereof may be contained in any combination and ratio.

<Method for producing aromatic polycarbonate resin composition>
There is no restriction | limiting in the manufacturing method of the aromatic polycarbonate resin composition of this invention, The manufacturing method of a well-known aromatic polycarbonate resin composition can be employ | adopted widely.

  Specific examples thereof include the aromatic polycarbonate resin (A) and (meth) acrylate copolymer (B) according to the present invention, and other components blended as necessary, such as a tumbler or Henschel mixer, Examples thereof include a method of pre-mixing using various mixers such as a super mixer and then melt-kneading with a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader.

  Also, for example, without mixing each component in advance, or only a part of the components are mixed in advance, and fed to an extruder using a feeder, and melt-kneaded, the aromatic polycarbonate resin composition of the present invention It can also be manufactured.

Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The aromatic polycarbonate resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, 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 the dispersion. It can also improve sex.

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

  Hereinafter, the present invention will be described more specifically 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, “parts” means “parts by mass” based on mass standards unless otherwise specified.

  Measurement / evaluation methods and materials used in the following Examples and Comparative Examples are as follows.

[Measurement and evaluation method]
<Measurement and calculation of mass average molecular weight (Mw)>
First, the average molecular weight was measured under the following conditions by gel permeation chromatography (GPC) using polystyrene (PS) as a standard polymer.
Apparatus: Alliance made by Waters
Column: Showa Denko "Shodex K-805L" (two)
Detector; UV detector 254 nm
Eluent: Chloroform Then, after GPC measurement, the relationship between the elution time and the molecular weight of polycarbonate (PC) was determined by a universal calibration method to obtain a calibration curve. The elution curve (chromatogram) of PC was measured under the same conditions as in the calibration curve, and the mass average molecular weight was determined from the elution time (molecular weight) and the peak area (number of molecules) of the elution time.
The mass average molecular weight (Mw) is Mw = Σ (NiMi ² ) / Σ (NiMi) where Ni is the number of molecules of the molecular weight Mi.
It is represented by
The following formula was used as the conversion formula. In the calculation formula, MPC represents the molecular weight of PC, and MPS represents the molecular weight of PS. The calculation formula is obtained from the following Mark-Houwink formula representing the relationship between the intrinsic viscosity [η] and the molecular weight M. However, the values of K and α are values of K: 1.11 × 10 ⁻⁴ and α: 0.725 in the case of PS and K: 3.89 × 10 ⁻⁴ and α: 0.700 in the case of PC. It was used.
MPC = 0.47822MPS ^1.01470
MPS = 2.0689 ^{MPC 0.98551}
[Η] = KM ^α
The elution curve (chromatogram) of the polycarbonate was measured under the same conditions as in the calibration curve, and the mass average molecular weight was determined from the elution time (molecular weight) and the peak area (number of molecules) of the elution time.
The (meth) acrylate copolymer was calculated from a PS calibration curve using THF as an eluent and “TSKgel SuperHZM-M (4)” manufactured by Tosoh as a column.

<Measurement of breaking torque>
Screw a screw (M3 * 6mm P type pan screw thread diameter 3.02mm, thread root diameter 2.17mm) with a torque driver into the boss hole of the obtained test piece, and crack the boss hole The torque that led to destruction was measured and used as the breaking torque.

<Surface hardness evaluation>
The plate-like portion of the obtained test piece was subjected to a scratch test 5 times in accordance with JIS K-5600-5-4 to evaluate the surface pencil hardness.

<Appearance evaluation>
The external appearance of the obtained test piece was visually observed, and the presence or absence of transparency, whitening or pearly luster was confirmed and evaluated according to the following criteria.
○: Transparent, no whitening, no pearly luster, and excellent appearance.
X-1: There is whitening and the appearance is inferior.
X-2: There is pearl luster and the appearance is inferior.

[Materials used]
<Aromatic polycarbonate resin (A)>
Product name “Iupilon (registered trademark) S-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., mass average molecular weight: 26,800, pencil hardness: 2B

<(Meth) acrylate copolymer (B)>
In a heatable reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer, 200 parts of deionized water, 0.3 part of the following dispersant, 0.5 part of sodium sulfate, 2, 80 parts of 2′-azobisisobutyronitrile, 15 parts of phenyl methacrylate, 84 parts of methyl methacrylate, 1 part of methyl acrylate and 1.8 parts of n-octyl mercaptan were charged, and the inside of the reaction vessel was replaced with nitrogen. The temperature was raised to ° C. After stirring for 4 hours, the obtained bead polymer was washed with water and dried to obtain a (meth) acrylate copolymer (B). The (meth) acrylate copolymer (B) had a pencil hardness of 2H and a mass average molecular weight of 14,000.

  Dispersant: A mass ratio of a polymer obtained by copolymerizing 70 parts of potassium methacrylate and 30 parts of methyl methacrylate and a polymer obtained by copolymerizing 65 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate, and 25 parts of methyl methacrylate. The mixture was mixed 1: 1 and a 10% aqueous solution of the mixed polymer was used as a dispersant.

<Phosphorus heat stabilizer>
Tris (2,4-di-tert-butylphenyl) phosphite: product name “Adeka Stub 2112” manufactured by Adeka Company

<Release agent>
(R-1) Stearyl stearate: product name "Unistar M9676" manufactured by NOF Corporation
(R-2) Pentaerythritol tetrastearate: Cognis Japan, trade name “Roxyol VPG861”

<Antioxidant>
Pentaerystole-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]: trade name “Irganox 1010” manufactured by Ciba

<Ultraviolet absorber>
2- (2′-hydroxy-5′-tert-octylphenyl) -2H-benzotriazole: manufactured by Cypro Kasei Co., Ltd., trade name “Seesorb 709”

<Acrylic resin>
Polymethylmethacrylate: manufactured by Mitsubishi Rayon Co., Ltd. Trade name “Acrypet VH-001”, pencil hardness: 2H, mass average molecular weight: 60,000

  The pencil hardness of each material used as the aromatic polycarbonate resin (A), the (meth) acrylate copolymer (B), and the acrylic resin is a value measured in the same manner as in the above <Surface hardness evaluation>.

[Examples 1-6, Comparative Examples 1-9]
<Manufacture of resin pellets>
The above components were blended in the mass ratios shown in Tables 1 and 2 and mixed for 20 minutes with a tumbler, then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent, screw rotation speed 200 rpm, discharge The molten resin kneaded under the conditions of an amount of 20 kg / hour and a barrel temperature of 250 ° C. and extruded into a strand was quenched in a water tank and pelletized using a pelletizer to obtain a pellet of a polycarbonate resin composition.

<Preparation of test piece>
After drying the pellets obtained by the above manufacturing method at 100 ° C. for 5 hours, the injection shown in Tables 1 and 2 using a steel mold with an injection molding machine (“J-85AD” manufactured by JSW). The injection molding was performed under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. at a speed, and an outer diameter of 7.27 mm, an inner diameter of 2.44 mm, and a wall thickness of 2.70 mm × 44 mm × thickness of 3 mm. A test piece having a boss hole of 415 mm and a height of 10 mm was integrally molded.
The evaluation results of each test piece are shown in Tables 1 and 2.

[Evaluation results]

[Discussion]
As is apparent from Table 1, an aromatic polycarbonate resin composition containing an aromatic polycarbonate resin (A) and a (meth) acrylate copolymer (B) at a predetermined ratio as a resin component is injected at an injection speed of 5 to 100 mm / A molded product obtained by injection molding within a range of sec has high self-tapping strength of the boss hole, high surface hardness, and excellent appearance.
On the other hand, even if the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) are included within the scope of the present invention, Comparative Example 1 in which the injection speed is large exceeding the scope of the present invention. In ˜5, the breaking torque of 2.10 N · m or more cannot be achieved, and the appearance of the molded product is inferior.
On the other hand, in Comparative Examples 6 and 7 using an acrylic resin different from the (meth) acrylate copolymer (B) used in the present invention, the self-tap strength is obtained even when injection molding is performed at an injection speed within the range of the present invention. Inferior in appearance and inferior in appearance
In Comparative Examples 8 and 9 using only the aromatic polycarbonate resin (A) without using the (meth) acrylate copolymer (B) as the resin component, the appearance is good, but the injection is within the scope of the present invention. Even when injection molding is performed at a high speed, the self-tap strength is low and the surface hardness is low.

Looking at the relationship between the injection speed and the breaking torque, when only the aromatic polycarbonate resin (A) is used as the resin component (Comparative Examples 8 and 9), the breaking torque does not depend on the injection speed and is almost a low value. It is constant.
Even when an acrylic resin different from the (meth) acrylate copolymer (B) is used (Comparative Examples 6 and 7), there is no great difference in the breaking torque even if the injection speed is changed. This is because, originally, the compatibility between the aromatic polycarbonate resin (A) and the acrylic resin is poor, so even if the injection speed is lowered, the state of poor compatibility is not changed, and the breaking torque is not improved.
On the other hand, from the comparison between Examples 1 to 6 and Comparative Examples 1 to 5, the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) as resin components are within the scope of the present invention. In the case where it is included, phase separation occurs between the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B), which are sufficiently compatible when the injection speed is increased. It is understood that it is preferable to set the injection speed to a predetermined value or less because the appearance and the appearance are also inferior.

Claims (3)

A mass ratio (b1 / b2) of 55 to 95% by mass of an aromatic polycarbonate resin (A) having a mass average molecular weight of 15,000 to 40,000 and an aromatic (meth) acrylate unit (b1) and a methyl methacrylate unit (b2). ) Is 5 to 80/20 to 95, and the weight average molecular weight is 5,000 to 30,000 (meth) acrylate copolymer (B) and an aromatic polycarbonate resin containing a resin component consisting of 5 to 45% by mass By molding the composition by injection molding, an aromatic polycarbonate resin molded product formed by integrally molding a plate-like portion having a thickness of 1 mm or more and a boss hole projecting from the plate-like portion,
The injection speed during the injection molding is 5 to 100 mm / sec,
The breaking torque in the self-tapping test with a catch rate of 68% when using a screw with a nominal diameter of 3 mm with one, two, and four types of thread in the screw part of the tapping screw in JIS B1007 is 2.10 N · m or more,
An aromatic polycarbonate resin molded article having a boss hole, wherein the surface pencil hardness according to JIS K-5600-5-4 standard is F or more.   2. The height of the boss hole according to claim 1, wherein the height of the boss hole is 8 to 12 mm, the outer diameter is 7.27 to 7.83 mm, the inner diameter is 2.42 to 2.73 mm, and the wall thickness is 2.270 to 2.705 mm. An aromatic polycarbonate resin molded article having a boss hole.   The aromatic polycarbonate resin molded product according to claim 1 or 2 is a casing of an electric / electronic device, a part for an automobile, a part of a lighting device, an information terminal device, a household appliance, a leisure article, or a miscellaneous product. An aromatic polycarbonate resin molded product having a boss hole.