JP6787731B2 - Polycarbonate resin composition and molded product - Google Patents

Description

The present invention relates to a polycarbonate resin composition and a molded product, and more particularly to a polycarbonate resin composition and a molded product thereof, which have high hardness and are excellent in impact resistance at room temperature and impact resistance at low temperature.

Polycarbonate resin has excellent mechanical strength, electrical properties, transparency, etc., and is widely used as an engineering plastic in various fields such as electrical and electronic equipment fields and automobile fields.

However, the bisphenol A type polycarbonate resin has a problem that the melt viscosity is high and the molding processability is inferior, and the polymer alloy with the acrylonitrile-butadiene-styrene resin (ABS resin) has a moldability as compared with the case where the polycarbonate resin alone is used. As a material that has both strength, heat resistance and moldability, it can be widely used in various fields including the automobile field and the electrical and electronic equipment field because it can improve the impact resistance and heat resistance compared to the case of ABS resin alone. It has been.

However, the resin composition composed of such a polycarbonate resin and an ABS resin has a problem that the impact strength of the obtained molded product in a wide temperature range is not sufficient.
Further, in recent years, the thickness and weight of molded products have been rapidly reduced, and further improvement in the performance of molded materials has been required, and among them, high hardness has also been desired. However, the polycarbonate-ABS resin composition has a drawback that it is inferior in scratch resistance due to the low surface hardness of the molded product and the surface is easily scratched. For example, the housing of home appliances and mobile terminal devices and the interior of automobiles. This is a particularly big problem in applications that require a high-class feel such as parts.

Special Publication No. 38-15225

An object (problem) of the present invention is to provide a polycarbonate-ABS resin composition and a molded product thereof, which exhibit impact resistance in a wide temperature range and high surface hardness.

As a result of diligent studies to achieve the above problems, the present inventor has added 2,2-bis (3-methyl-4-hydroxyphenyl) propane to a composition composed of a bisphenol A type polycarbonate resin and an ABS resin. That is, a polycarbonate resin derived from an aromatic dihydroxy compound having a specific structure such as bisphenol C, and a polycarbonate containing a specific amount of a graft copolymer having a vinyl polymer segment as a side chain in the main chain of the polyethylene polymer. We have found that the resin composition solves the above problems, and have completed the present invention.
The present invention relates to the following polycarbonate resin compositions and molded articles.

[1] Bisphenol A type polycarbonate resin (A), polycarbonate resin (B) having a structural unit represented by the following general formula (1), ABS resin (C), and a vinyl-based weight having a polyethylene-based polymer as a main chain. A polycarbonate resin composition containing a graft copolymer (D) having a coalesced segment as a side chain.
The content ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is 70 to 95/5 to 30 in terms of the mass ratio of (A) / (B).
The content of the ABS resin (C) is 25 to 100 parts by mass, and the content of the graft copolymer (D) is 1 to 9 parts by mass with respect to 100 parts by mass of the total of the polycarbonate resins (A) and (B). A polycarbonate resin composition characterized by being a part.
(In the general formula (1), R ¹ represents a methyl group, R ² and R ³ independently represent a hydrogen atom or a methyl group, and X represents an alkylene group or an alkylidene group.)

[2] The ABS resin (C) contains 40 to 80% by mass of the aromatic vinyl monomer component (c1), 10 to 30% by mass of the vinyl cyanide monomer component (c2), and a diene-based rubbery polymer component ( c3) The above [1], which is an ABS resin composed of 10 to 30% by mass and other monomer components (c4) to 30% by mass (however, the total of the components (c1) to (c4) is 100% by mass). The polycarbonate resin composition according to.
[3] The polycarbonate resin composition according to the above [1] or [2], which conforms to ISO 15184 and has a pencil hardness of HB or more measured under a load of 750 g.
[4] The polycarbonate resin composition according to any one of the above [1] to [3], wherein the low-temperature Charpy impact value (notched) at −30 ° C. is 20 kJ / m ² or more.
[5] A molded product of the polycarbonate resin composition according to any one of the above [1] to [4].

The polycarbonate resin composition of the present invention has high hardness and is excellent in impact resistance at room temperature and impact resistance at low temperature.
The reason why the present invention exerts such an effect has not yet been clarified, but the polycarbonate resin (B) has excellent wear resistance and high pencil due to the presence of a methyl group in R ¹ of the general formula (1). It becomes possible to provide a composition having hardness. Further, by blending the graft copolymer (D), the mutual affinity between the polycarbonate resin (A), the polycarbonate resin (B), and the ABS resin (C) is improved, and the dispersed state is improved. It is presumed that it will be possible to provide a composition having better impact resistance without lowering the hardness.
A method of producing polycarbonate or copolycarbonate having excellent surface hardness by using an aromatic dihydroxy compound having a specific structure different from that of conventional bisphenol A such as bisphenol C is known, but this is a bisphenol A type polycarbonate resin. It is difficult to achieve both the above-mentioned hardness and impact resistance in a wide range by simply blending with and ABS resin, and after further combining the above-mentioned graft copolymer (B), each component is added. For the first time, high hardness, impact resistance at room temperature, and impact resistance at low temperature can be achieved in a well-balanced manner by setting the above specific content.
The polycarbonate resin composition of the present invention having such an effect can be particularly suitably used for vehicle interior parts, electronic and electrical equipment, OA equipment, housing members of information terminal equipment, and the like.

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 shown below, and is not deviating from the gist of the present invention. It can be changed arbitrarily and implemented.

The polycarbonate resin composition of the present invention comprises a bisphenol A type polycarbonate resin (A), a polycarbonate resin (B) having a structural unit represented by the general formula (1), an ABS resin (C), and a polyethylene-based polymer. A polycarbonate resin composition containing a graft copolymer (D) having a vinyl polymer segment as a main chain and a vinyl polymer segment as a side chain.
The content ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is 70 to 95/5 to 30 in terms of the mass ratio of (A) / (B).
The content of the ABS resin (C) is 25 to 100 parts by mass, and the content of the graft copolymer (D) is 1 to 9 parts by mass with respect to 100 parts by mass of the total of the polycarbonate resins (A) and (B). It is characterized by being a part.

[Bisphenol A type polycarbonate resin (A)]
The polycarbonate resin contained in the polycarbonate resin composition of the present invention is a bisphenol A type polycarbonate resin (A).
The bisphenol A type polycarbonate resin (A) is produced from bisphenol A, that is, 2,2-bis (4-hydroxyphenyl) propane and a carbonate precursor as a raw material dihydroxy compound.

Among the monomers used as raw materials for the polycarbonate resin (A), carbonyl halide, carbonic acid diester and the like are used as an example of a carbonate precursor. As the carbonate precursor, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of the carbonyl halide include phosgene; a bischloroformate of a dihydroxy compound, and a haloformate such as a monochloroformate of a dihydroxy compound.

Specific examples of the carbonic acid diester include diaryl carbonates such as diphenyl carbonate and ditrill carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate of dihydroxy compound, monocarbonate of dihydroxy compound, and cyclic carbonate. Examples thereof include carbonates of dihydroxy compounds such as.

The polycarbonate resin (A) may be a copolymerized polycarbonate resin in which a dihydroxy compound other than bisphenol A is used in combination. Examples of the dihydroxy compound other than bisphenol A include the following aromatic dihydroxy compounds.
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentan, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxy) Phenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4' Examples thereof include −dihydroxybenzophenone, 4,4′-dihydroxyphenyl ether, 2,2-bis (3-methyl-4-hydroxyphenyl) propane and the like.

When the copolymerized polycarbonate resin is used, the content derived from bisphenol A is preferably 50 mol% or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly 90% by mass or more, particularly 95. It is preferably mass% or more.
Further, the polycarbonate resin (A) may be linear or branched.

Method for Producing Polycarbonate Resin The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, particularly suitable of these methods will be specifically described.

Interfacial polymerization method First, a case where the polycarbonate resin is produced by the interfacial polymerization method will be described.
In the interfacial polymerization method, the pH is usually maintained at 9 or higher in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the dihydroxy compound is reacted with a carbonate precursor (preferably phosgene), and then the polymerization catalyst is used. A polycarbonate resin is obtained by performing interfacial polymerization in the presence. If necessary, a molecular weight modifier (terminal terminator) may be present in the reaction system, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

The dihydroxy compound and carbonate precursor are as described above. It is preferable to use phosgene among the carbonate precursors, and the method using phosgene is particularly called a phosgene method.

Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene and xylene. Be done. As the organic solvent, one type may be used, or two or more types may be used in any combination and ratio.

Examples of the alkaline compound contained in the alkaline aqueous solution include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium hydrogen carbonate, and alkaline earth metal compounds. Among them, sodium hydroxide and water. Potassium oxide is preferred. As the alkaline compound, one type may be used, or two or more types may be used in any combination and ratio.

The concentration of the alkaline compound in the alkaline aqueous solution is not limited, but is usually used at 5 to 10% by mass in order to control the pH in the alkaline aqueous solution of the reaction to 10 to 12. Further, for example, when phosgene is blown, the molar ratio of the bisphenol compound to the alkaline compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Above all, it is preferably 1: 2.0 or more, and usually 1: 3.2 or less, and above all, 1: 2.5 or less.

Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine and trihexylamine; and alicyclic such as N, N'-dimethylcyclohexylamine and N, N'-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N'-dimethylaniline, N, N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. ; Ppyridine; a salt of guanidine; and the like. As the polymerization catalyst, one type may be used, or two or more types may be used in any combination and ratio.

Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; fatty alcohols such as methanol and butanol; mercaptans; phthalates, and the like, with aromatic phenols being preferable. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Substituted phenols; vinyl group-containing phenols such as isopropenylphenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; and the like. As the molecular weight adjusting agent, one kind may be used, or two or more kinds may be used in any combination and ratio.

The amount of the molecular weight modifier used is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, based on 100 mol of the dihydroxy compound. By setting the amount of the molecular weight adjusting agent used in this range, the thermal stability and hydrolysis resistance of the resin composition can be improved.

At the time of the reaction, the order in which the reaction substrate, reaction medium, catalyst, additives and the like are mixed is arbitrary as long as a desired polycarbonate resin can be obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier can be mixed at any time between the time of the reaction (phosgenation) between the dihydroxy compound and phosgene and the start of the polymerization reaction.
The reaction temperature is usually 0 to 40 ° C., and the reaction time is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

Molten transesterification method Next, a case where the polycarbonate resin is produced by the molten transesterification method will be described.
In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is carried out.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonate such as ditril carbonate. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type of carbonic acid diester may be used, and 2 or more types may be used in arbitrary combination and ratio.

The ratio of the dihydroxy compound to the carbonic acid diester is arbitrary as long as a desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, and 1.01 mol or more is particularly used. Is more preferable. The upper limit is usually 1.30 mol or less. By setting the range to such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

In polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. Therefore, the amount of terminal hydroxyl groups may be adjusted as necessary by any known method. In the transesterification reaction, usually, a polycarbonate resin having an adjusted amount of terminal hydroxyl groups can be obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound; the degree of reduced pressure during the transesterification reaction. By this operation, the molecular weight of the normally obtained polycarbonate resin can also be adjusted.

When the mixing ratio of the carbonic acid diester and the dihydroxy compound is adjusted to adjust the amount of terminal hydroxyl groups, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, a method of separately mixing a terminal terminator at the time of reaction can be mentioned. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. In addition, as the terminal terminator, one kind may be used, or two or more kinds may be used in combination in any combination and ratio.

When producing a polycarbonate resin by the transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, for example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. Alternatively, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination. As the transesterification catalyst, one type may be used, or two or more types may be used in any combination and ratio.

In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, the melt polycondensation reaction may be carried out under the above conditions while removing by-products such as aromatic hydroxy compounds.

The melt polycondensation reaction can be carried out by either a batch method or a continuous method. In the case of batch method, the order of mixing the reaction substrate, reaction medium, catalyst, additives and the like is arbitrary as long as a desired aromatic polycarbonate resin can be obtained, and an appropriate order may be arbitrarily set. However, considering the stability of the polycarbonate resin and the like, it is preferable to carry out the melt polycondensation reaction in a continuous manner.

In the molten transesterification method, a catalytic deactivator may be used if necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. As the catalyst deactivator, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. It is preferably 5 equivalents or less. Further, it is usually 1 ppm or more, and usually 100 ppm or less, preferably 20 ppm or less, with respect to the polycarbonate resin.

The viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably 15,000 to 30,000. When the viscosity average molecular weight is in this range, a molded product having good moldability and high mechanical strength is likely to be obtained, and when it is less than 15,000, the surface impact resistance is likely to be significantly lowered and exceeds 30,000. The melt viscosity increases and injection molding tends to be difficult. The lower limit of the molecular weight of the polycarbonate resin (A) is more preferably 16,000, still more preferably 17,000, and the upper limit is more preferably 28,000.

In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin is determined by using methylene chloride as a solvent and using an Ubbelohde viscometer to determine the ultimate viscosity [η] (unit: dl / g) at a temperature of 20 ° C. It is a value calculated from the following Schnell viscosity formula.
[Η] = 1.23 × 10 ^-4 Mv ^0.83

The terminal hydroxyl group concentration of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less. Thereby, the retention heat stability and the color tone of the polycarbonate resin can be further improved. Further, the lower limit thereof is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly in the case of the polycarbonate resin produced by the molten transesterification method. As a result, it is possible to suppress a decrease in molecular weight and further improve the mechanical properties of the resin composition.

The unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group expressed in ppm with respect to the mass of the polycarbonate resin. The measuring method is colorimetric quantification by the titanium tetrachloride / acetic acid method (the method described in Macromol. Chem. 88 215 (1965)).

[Polycarbonate resin (B)]
The polycarbonate resin (B) is a polycarbonate resin having a structural unit represented by the following general formula (1).
(In the general formula (1), R ¹ represents a methyl group, R ² and R ³ independently represent a hydrogen atom or a methyl group, and X represents an alkylene group or an alkylidene group.)

In the above general formula (1), R ¹ is a methyl group and R ² and R ³ are independent hydrogen atoms or methyl groups, respectively, but R ² and R ³ are particularly preferably hydrogen atoms.
Further, X is an alkylene group or an alkylidene group, and the alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, and may be linear or branched. Examples thereof include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene and the like.
As the alkylidene group, an alkylidene group having 2 to 10 carbon atoms is preferable, and examples thereof include ethylidene, 2,2-propylidene, 2,2-butylidene, and 3,3-hexylidene.
X is preferably an alkylidene group, particularly preferably a 2,2-propyridene group (ie, an isopropylidene group).

Preferred specific examples of the polycarbonate resin (B) include the following polycarbonate resins a) to b).
B) Those having 2,2-bis (3-methyl-4-hydroxyphenyl) propane structural units, that is, structural units in which R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is an isopropylidene group. Have
B) It has a 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are methyl groups, and X is an isopropylidene group. thing,
Of the above, the polycarbonate resin of the above a) is particularly preferable.

These polycarbonate resins are produced by using 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane as dihydroxy compounds. be able to.

As the polycarbonate resin (B), one type may be used, or two or more types may be used in any combination and in any ratio.

The polycarbonate resin (B) can also have a carbonate structural unit other than the structural unit represented by the general formula (1). For example, the structural unit represented by the following general formula (2), or other structural units as described later. It may have a structural unit derived from the dihydroxy compound of. At this time, the copolymerization amount of the structural unit other than the structural unit represented by the general formula (1) is usually 60 mol% or less, preferably 50 mol% or less, more preferably 40 mol% or less, and further 30. It is preferably mol% or less, particularly preferably 20 mol% or less.
(In the formula, X is synonymous with X in the general formula (1).)

A preferable specific example of the polycarbonate structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate structural unit derived from bisphenol A.
Since the polycarbonate resin (B) is different from the polycarbonate resin (A), when the polycarbonate resin (B) contains a carbonate structural unit derived from bisphenol A as a copolymerization component, the component derived from bisphenol A in the polycarbonate resin (B) Is preferably less than 50 mol%, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less, particularly 5% by mass or less.

Examples of dihydroxy compounds other than the structural unit represented by the general formula (2) are bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, and 2,2-bis (4). -Hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1 , 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) ) Cyclooctane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether and the like.

The viscosity average molecular weight (Mv) of the polycarbonate resin (B) is preferably 23,000 to 35,000. When the viscosity average molecular weight is in this range, it is easy to obtain a molded product having good moldability, high mechanical strength, and good scratch resistance. If it is less than 23,000, the pencil hardness of the resin composition becomes low. In addition, the wear resistance tends to decrease, and if it exceeds 35,000, the melt viscosity tends to increase and injection molding tends to be difficult. The lower limit of the molecular weight of the polycarbonate resin (B) is more preferably 24,000, still more preferably 25,000, particularly preferably 26,000, and the upper limit is more preferably 33,000, particularly 32,000. It is preferable to have.

The method for producing the polycarbonate resin (B) is not particularly limited, and is the same as that described in the method for producing the polycarbonate resin (A).

The content of the polycarbonate resin (B) is 70 to 95/5 to 30 in terms of the mass ratio of the polycarbonate resin (A) and the polycarbonate resin (B) (A) / (B). If the mass ratio of the polycarbonate resin (B) exceeds 30, the impact resistance at a low temperature decreases, and if it exceeds 5, the pencil hardness decreases or the abrasion resistance deteriorates. The preferable content of the polycarbonate resin (B) is 75 to 90/10 to 25, more preferably 75 to 87/13 to 25, in terms of the mass ratio of (A) / (B).

The polycarbonate resins (A) and (B) are not limited to the embodiment containing only one type of polycarbonate resin, and the polycarbonate resin alone is not limited to, for example, a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in the meaning including the aspect including.). Further, for example, a polycarbonate resin is a copolymer of an oligomer or a polymer having a siloxane structure for the purpose of further improving flame retardancy and impact resistance; a phosphorus atom for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure; a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; polystyrene or the like to improve the optical properties. Even if it is configured as a copolymer mainly composed of a polycarbonate resin, such as a copolymer with an oligomer or a polymer having an olefin structure; a copolymer with a polyester resin oligomer or a polymer for the purpose of improving chemical resistance; Good.

Further, in order to improve the appearance and fluidity of the molded product, the polycarbonate resins (A) and (B) may contain a polycarbonate oligomer. The viscosity average molecular weight (Mv) of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Further, the contained polycarbonate ligomer is preferably 30% by mass or less of the total amount of each polycarbonate resin (including the polycarbonate oligomer).

[ABS resin (C)]
The resin composition of the present invention contains an ABS resin (C). The ABS resin (C) is composed of an aromatic vinyl monomer component (c1), a vinyl cyanide monomer component (c2), a diene-based rubbery polymer component (c3), and other monomer components (c4). The total amount of the components (c1) to (c4) is 100% by mass, the aromatic vinyl monomer component (c1) is 40 to 80% by mass, and the vinyl cyanide monomer component (c2) is 10. It is preferable that the content is ~ 30% by mass, the diene-based rubbery polymer component (c3) is 10 to 30% by mass, and the other monomer component (c4) is 0 to 30% by mass.

Examples of the aromatic vinyl monomer component (c1) in the ABS resin (C) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, and p-tert-butyl. Examples thereof include styrene, vinylnaphthalene, methoxystyrene, monobromstyrene, dibromstyrene, fluorostyrene, tribromstyrene and the like, and styrene is particularly preferable.
The ratio of the aromatic vinyl monomer component (c1) in the ABS resin (C) is preferably in the range of 40 to 80% by mass, more preferably 45% by mass or more, based on 100% by mass of the ABS resin (C). It is more preferably 50% by mass or more, particularly preferably 55% by mass or more, more preferably 77% by mass or less, still more preferably 74% by mass or less, and particularly preferably 70% by mass or less.

Examples of the vinyl cyanide monomer component (c2) in the ABS resin (C) include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
The proportion of the vinyl cyanide monomer component (c2) is preferably in the range of 10 to 30% by mass, more preferably 12% by mass or more, and further, in 100% by mass of the ABS resin (C), as described above. It is preferably 14% by mass or more, particularly preferably 15% by mass or more, more preferably 28% by mass or less, still more preferably 26% by mass or less, and particularly preferably 25% by mass or less.

As the diene-based rubber polymer component (c3) of the ABS resin (C), for example, a rubber component such as polybutadiene, polyisoprene, or a styrene-butadiene copolymer is used, and the diene-based rubber polymer component (c3) is used. The proportion of the ABS resin (C) in the ABS resin (C) is preferably in the range of 10 to 30% by mass, more preferably 11% by mass or more, still more preferably 12% by mass or more, particularly in 100% by mass of the ABS resin (C). It is preferably 13% by mass or more, more preferably 25% by mass or less, and further preferably 20% by mass or less.

Further, other monomer components (c4) copolymerizable with these may be copolymerized. In this case, other monomers copolymerizable include, for example, maleimide, N-methylmaleimide, N. Maleimide-based monomers such as -cyclohexyl maleimide and N-phenylmaleimide, acrylamide-based monomers such as acrylamide and N-methylacrylamide, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, acrylic acid and methacrylic acid. And the like, unsaturated acids such as glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate and the like.
As described above, the ratio of the other monomer component (c4) in the ABS resin (C) is preferably in the range of 0 to 30% by mass in 100% by mass of the ABS resin (C), but more preferably. Is 20% by mass or less, more preferably 10% by mass or less.

Specific examples of the ABS resin (C) include acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer and the like. Illustrated.

The ABS resin is usually produced by a method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and any method can be used.

In the present invention, the ABS resin (C) is not limited to a mode containing only one type of ABS resin, and may be, for example, a mode containing a combination of a plurality of types of ABS resins having different monomer compositions and molecular weights, or ABS. The resin may be combined with other resins such as AS resin.
In the case of combining in this way, those obtained by melt-kneading in advance may be used in the production of the resin composition of the present invention, or may be collectively used in the production of the resin composition of the present invention.

The content of the ABS resin (C) is 25 to 100 parts by mass, preferably 30 parts by mass or more, and more preferably 35 parts by mass or more with respect to 100 parts by mass of the total of the polycarbonate resins (A) and (B). It is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 85 parts by mass or less, and particularly preferably 80 parts by mass or less. If it is less than 25 parts by mass, the impact resistance at low temperature is lowered, which is not preferable. On the other hand, when the content of the ABS resin (C) exceeds 100 parts by mass, the heat resistance is lowered and the surface hardness is lowered, which is not preferable.

[Graft copolymer (D)]
The polycarbonate resin composition of the present invention contains a graft copolymer (D) having a polyethylene-based polymer as a main chain and a vinyl-based polymer segment as a side chain. In this graft copolymer (D), the polyethylene-based polymer serves as the main chain of the graft copolymer, and the segment obtained by polymerizing the vinyl-based monomer serves as the side chain of the graft copolymer.

The polyethylene-based polymer constituting the main chain may be either a homopolymer of ethylene or a copolymer containing ethylene as a main component and copolymerizing with other α-olefins other than ethylene.
Other α-olefins other than ethylene are α-olefins having a carbon atom number of usually 3 to 20, preferably 3 to 12, such as propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1. -Pentene, 1-octene, 1-decene, 1-dodecene and the like are preferably mentioned.
When the polyethylene-based polymer is a copolymer, the amount of α-olefin units other than ethylene is usually 0 to 50% by mass, preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further. It is preferably 0 to 10% by mass.

The molecular weight of the polyethylene-based polymer is usually about 10,000 to 600,000 in terms of number average molecular weight (Mn). Here, the number average molecular weight means what is obtained in terms of polystyrene by gel permeation chromatography (GPC).

Examples of the polyethylene-based polymer include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (VLDPE), or high-pressure method low-density obtained by the high-pressure radical method. It may be any of ethylene (HPLD) and the like, but low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, and high-pressure low-density polyethylene are preferable, and ultra-low-density polyethylene (VLDPE) is more preferable.

The density of the low density polyethylene is usually 0.91 to 0.94 g / cm ³ , preferably 0.912 to 0.935 g / cm ³ . The linear low-density polyethylene preferably has a density of 0.91 to 0.94 g / cm ³ . Ultra-low density polyethylene is a copolymer of ethylene and α-olefin, and usually has a density in the range of 0.86 to 0.91 g / cm ³ . The high-pressure method low-density polyethylene by the high-pressure method preferably has a density of 0.91 to 0.94 g / cm ³ .

Examples of the vinyl-based monomer for forming the vinyl-based polymer segment include a styrene-based monomer, α, β-unsaturated carboxylic acid, α, β-unsaturated carboxylic acid ester, and an unsaturated nitrile-based single amount. The body and the like are preferably mentioned.

Examples of the styrene-based monomer include styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene and the like, and styrene is particularly preferable.
Examples of α, β-unsaturated carboxylic acids include (meth) acrylic acid esters such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate, acrylic acid, and methacrylic acid. , Fumaric acid, maleic anhydride, itaconic acid and the like are preferable.
Examples of α, β-unsaturated carboxylic acid esters include methyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and n methacrylate. -Butyl, isobutyl methacrylate and the like are preferable.
As the unsaturated nitrile-based monomer, acrylonitrile is preferably mentioned.

Among these vinyl-based monomers, styrene-based monomers, particularly styrene, are preferable because they have high compatibility with the polycarbonate resin (A) and are excellent in scratch resistance, and styrene alone or with styrene. It is preferable to copolymerize with OH group-containing (meth) acrylate such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, or acrylonitrile.

The molecular weight of the vinyl-based polymer segment is preferably 5,000 to 500,000 in terms of mass average molecular weight. Here, the mass average molecular weight means what is obtained in terms of polystyrene by gel permeation chromatography (GPC).

It is also preferable that the graft copolymer (D) further contains polyorganosiloxane. When it contains polyorganosiloxane, it may be present as the main chain or side chain of the graft copolymer (D), and is one of the graft copolymers that forms a multi-layer structure such as a core / shell type. It may be contained as a part.

The polyorganosiloxane is not particularly limited, and examples thereof include polydimethylsiloxane and polymethylphenylsiloxane, and examples thereof include polydimethyldiphenylsiloxane copolymer, polydimethylphenylmethylsiloxane copolymer, and polymethylphenyldiphenylsiloxane copolymer. Of these, a polymer containing a dialkylsiloxane unit, particularly a dimethylsiloxane unit as a constituent unit is preferable.
Further, as the polyorganosiloxane, those containing a siloxane containing a vinyl group as a constituent component are preferable. A siloxane containing a vinyl group is well known, and is a siloxane containing a vinyl group to which an organosiloxane is bonded via a siloxane bond.

The proportion of the polyethylene-based polymer segment in the graft copolymer (D) composed of the main chain of the polyethylene-based polymer and the side chain of the vinyl-based polymer segment is preferably 50 to 95% by mass. It is more preferably 60 to 90% by mass, and even more preferably 65 to 85% by mass. The proportion of the vinyl-based polymer segment is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 20 to 35% by mass.
Further, when the polyorganosiloxane segment is further contained, the content is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 2 to 10% by mass. .. However, when the polyorganosiloxane segment is contained, the total amount of the polyethylene-based polymer segment, the vinyl-based polymer segment, and the polyorganosiloxane segment is 100% by mass.

The graft copolymer (D) preferably has an endothermic peak of 100 ° C. or lower as measured by a differential scanning calorimetry (DSC) in accordance with JIS K7121. When the endothermic peak temperature is 100 ° C. or lower, the scratch resistance on the nail when blended with the polycarbonate resin and the slight scratch resistance at low hardness in the pencil hardness test are good, which is preferable. The reason for this is that when the heat absorption peak temperature is 100 ° C. or lower, the polyethylene-based polymer main chain having a low affinity with the polycarbonate resin easily enters between the polycarbonate resin molecules, and the affinity with the polycarbonate resin is improved. It is presumed that this is because the dispersion of the graft copolymer (C) phase in the polycarbonate resin phase is improved.
The graft copolymer (D) may have a plurality of endothermic peaks, and even if there are a plurality of endothermic peaks, it is preferable to have an endothermic peak at 100 ° C. or lower. The endothermic peak temperature is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and the lower limit thereof is usually 60 ° C. or higher.

In the present invention, the endothermic peak of the graft copolymer (D) is measured according to JIS K7121 using a differential scanning calorimeter DSC7020 manufactured by Seiko Instruments Inc. of the graft copolymer (D). This is done by observing 10 mg of the sample by heating from 30 ° C. to 300 ° C. at 10 ° C./min. The graft copolymer (D) has a plurality of endothermic peaks, and the temperature of the endothermic peak on the lowest temperature side is measured.

Any of various known graft copolymerization methods may be used for producing the graft copolymer (D), and examples thereof include the methods shown below.

That is, the polyethylene-based polymer is suspended in water, and the vinyl-based monomer, a radically polymerizable organic peroxide (for example, t-butylpeoxymethacryloyloxyethyl carbonate, etc.) and a polymerization initiator (for example, t-butylpeoxymethacryloxyethyl carbonate) are suspended therein. For example, a mixed solution in which 3,5,5-trimethylhexanoyl peroxide or the like is dissolved is added, and then the mixture is heated and copolymerized to produce a graft copolymer.

Further, the graft copolymer (D) is commercially available and can also be used. For example, it is sold as "NOFALOY (registered trademark) KA series" by NOF CORPORATION, for example, "NOFALOY KA147". Etc. can be used.

The content of the graft copolymer (D) is 1 to 9 parts by mass, preferably 1.5 parts by mass, based on 100 parts by mass of the total of the polycarbonate resins (A) and (B). By mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, and preferably 8.5 parts by mass or less, more preferably 8.0 parts by mass or less. is there. If it is less than 1 part by mass, the improvement effect of scratch resistance becomes small, and if it exceeds 9 parts by mass, the scratch resistance is deteriorated or the mechanical strength is lowered.

[Elastomer (E)]
The polycarbonate resin composition of the present invention preferably contains an elastomer (E). As the elastomer (E), a graft copolymer obtained by graft-copolymerizing a rubber component with a copolymerizable monomer component is preferable. However, the graft copolymer here is defined as being different from the ABS resin (C) described above.
The method for producing the graft copolymer may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, and the copolymerization method may be a one-step graft or a multi-step graft.

As the rubber component, the glass transition temperature is usually 0 ° C. or lower, particularly preferably −20 ° C. or lower, and further preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate and 2-ethylhexyl acrylate copolymer, and polyorganosiloxane rubber. IPN (Interpentrating Polymer Network) type composite rubber composed of silicone rubber, butadiene-acrylic composite rubber, polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. Examples thereof include ethylene-α-olefin rubber, ethylene-acrylic rubber, and fluororubber. These may be used alone or in combination of two or more. Among these, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, and styrene-butadiene rubber are preferable from the viewpoint of mechanical properties and surface appearance. ..

Specific examples of the rubber component and the monomer component that can be graft-copolymerized include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and glycidyl (meth) acrylate. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides. Examples include compounds (eg, maleic anhydride, etc.). One of these monomer components may be used alone, or two or more thereof may be used in combination. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable, and (meth) acrylic acid ester is more preferable, from the viewpoint of mechanical properties and surface appearance. It is a compound. Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate. be able to.

The graft copolymer obtained by copolymerizing the rubber component is preferably a core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from an IPN type composite rubber composed of polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, polyorganosiloxane rubber and polyalkylacrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer composed of a shell layer formed by copolymerizing a (meth) acrylic acid ester is particularly preferable. Among the core / shell type graft copolymers, those containing 40% by mass or more of the rubber component are preferable, and those containing 60% by mass or more are more preferable. Further, the (meth) acrylic acid preferably contains 10% by mass or more. Here, the core / shell type does not necessarily mean that the core layer and the shell layer can be clearly distinguished, and the purpose is to broadly include a compound obtained by graft-polymerizing a rubber component around the core portion. is there.

Preferred specific examples of these core / shell type graft copolymers are methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-butadiene copolymer (MB), and methyl methacrylate-acrylic rubber copolymer (MA). ), Methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymer, methyl methacrylate- (acrylic silicone IPN rubber) Examples thereof include copolymers. Such a rubbery polymer may be used alone or in combination of two or more.

Examples of such an elastomer (E) include "Paraloid (registered trademark, the same applies hereinafter) EXL2602", "Paraloid EXL2603", "Paraloid EXL2655", and "Paraloid EXL2311" manufactured by Rohm & Hearth Japan Co., Ltd. "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", "Paraloid KCZ201", "Metabren (registered trademark, same below) C-223A", "Metabren E-901" manufactured by Mitsubishi Rayon Corporation , "Metabren S-2001", "Metabren SRK-200", "Kaneace (registered trademark, same below) M-511", "Kaneace M-600", "Kaneace M-400", "Kaneace M-400" manufactured by Kaneka Co., Ltd. Examples thereof include "Kane Ace M-580", "Kane Ace M-711", "Kane Ace MR-01", and "UBESTA XPA" manufactured by Ube Industries, Ltd.

When the resin composition of the present invention contains the elastomer (E), the content of the elastomer (E) is preferably 1 to 12 parts by mass with respect to 100 parts by mass in total of the polycarbonate resins (A) and (B). 2 to 11 parts by mass is more preferable, and 3 to 10 parts by mass is further preferable. Only one type of elastomer may be contained, or two or more types may be contained. When two or more types are included, the total amount is preferably in the above range.

[Stabilizer (F)]
The polycarbonate resin composition of the present invention preferably contains a stabilizer (F). Examples of the stabilizer (F) in the present invention include antioxidants and heat stabilizers. In the present invention, the antioxidant or the heat stabilizer may be used alone, but it is preferable to use both the antioxidant and the heat stabilizer in combination.

[Antioxidant]
Examples of the antioxidant applicable to the polycarbonate resin composition of the present invention include hindered phenolic antioxidants. 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-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) ] Methyl] Phosphoate, 3,3', 3 ", 5,5', 5" -hex-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], 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-triazine-2-ylamino ) Phenol and the like. These may be contained in only one kind, or two or more kinds may be contained in any combination and ratio.

Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from BASF Japan Ltd. under the names "Irganox (registered trademark, the same applies hereinafter) 1010" and "Irganox 1076".

The content of the antioxidant is usually 0.001 to 1 part by mass, preferably 0.01 to 0.5, based on 100 parts by mass of the total of the polycarbonate resin (A), (B) and ABS resin (C). It is a mass part. If the content of the antioxidant is less than 0.001 part by mass, the effect as an antioxidant is insufficient, and if it exceeds 1 part by mass, the effect reaches a plateau and is not economical.

[Heat stabilizer]
Examples of the heat stabilizer applicable to the polycarbonate resin composition of the present invention include phosphorus compounds. Any known phosphorus compound can be used as the phosphorus compound. Specific examples include phosphoric acid, phosphonic acid, phosphite, phosphinic acid, polyphosphoric acid and other phosphorus oxo acids; acidic sodium pyrophosphate, potassium pyrophosphate, acidic calcium pyrophosphate and other acidic pyrophosphate metal salts; phosphoric acid. Phosphates of Group 1 or Group 2B metals such as potassium, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc., but organic phosphite compounds Especially preferable.

Examples of the organic phosphite compound include triphenylphosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl-phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and monooctyl. Diphenylphosphite, dioctylmonophenylphosphite, monodecyldiphenylphosphite, didecylmonophenylphosphite, tridecylphosphite, trilaurylphosphite, tristearylphosphite, 2,2-methylenebis (4,6-di-) tert-Butylphenyl) octylphosphite and the like can be mentioned.
Specific examples of such an organic phosphite compound include "Adecastab (registered trademark, the same applies hereinafter) 1178", "Adecastab 2112", "Adecastab HP-10" manufactured by ADEKA Ltd., and Johoku Chemical Industry Co., Ltd. Examples thereof include "JP-351", "JP-360", "JP-3CP" manufactured by the company, and "Irgafos (registered trademark) 168" manufactured by BASF Japan Ltd.
The heat stabilizer may be contained in only one type, or two or more types may be contained in any combination and ratio.

The content of the heat stabilizer is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, based on 100 parts by mass of the total of the polycarbonate resin (A), (B) and ABS resin (C). It is preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass or less, and more preferably 0.3 part by mass or less. If the content of the heat stabilizer is less than the lower limit of the above range, the heat stabilization effect may be insufficient, and if the content of the heat stabilizer exceeds the upper limit of the above range, the effect peaks out. It may become uneconomical.

[Release agent (G)]
The polycarbonate resin composition of the present invention also preferably contains a mold release agent (G). Examples of the release agent (G) include an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil. ..

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, bechenic acid, lignoceric acid, cerotic acid, melissic acid, tetraliacontanic acid, montanic acid, and adipine. Examples include acid and azelaic acid.

As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same one as the above-mentioned aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monohydric or polyhydric saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, the aliphatic term also contains an alicyclic compound.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Can be mentioned.

The above ester may contain an aliphatic carboxylic acid and / or an alcohol as an impurity. Further, the above ester may be a pure substance or a mixture of a plurality of compounds. Further, as the aliphatic carboxylic acid and the alcohol which are combined to form one ester, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acid and alcohol include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer. Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, fisher-tropus wax, α-olefin oligomer having 3 to 12 carbon atoms, and the like. Here, the aliphatic hydrocarbon also includes an alicyclic hydrocarbon. Moreover, these hydrocarbons may be partially oxidized. The number average molecular weight is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, or a mixture of various constituents and molecular weights can be used as long as the main component is within the above range.

Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, paraffin wax and polyethylene wax are more preferable, and polyethylene wax is particularly preferable.

The release agent (G) may contain one type or two or more types in any combination and ratio.
The content of the release agent (G) is usually 0.001 part by mass or more, preferably 0.01 part by mass, based on 100 parts by mass of the total of the polycarbonate resin (A), (B) and ABS resin (C). It is usually 2 parts by mass or less, preferably 1 part by mass or less. If the content of the release agent is less than the lower limit of the above range, the effect of the release property may not be sufficient, and if the content of the release agent exceeds the upper limit of the above range, the hydrolysis resistance There is a possibility that the mold will be reduced and the mold will be contaminated during injection molding.

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other components other than the above, if necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins and elastomers other than the above-mentioned resins, and various resin additives other than the above. In addition, 1 type may be contained in the other component, and 2 or more types may be contained in arbitrary combinations and ratios.

Other resin additives include, for example, dye pigments, colorants, UV absorbers, flame retardants, dripping inhibitors, antistatic agents, antifogging agents, lubricants, antiblocking agents, plasticizers, dispersants, antibacterial agents, etc. Can be mentioned. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.

[Manufacturing method of polycarbonate resin composition]
The method for producing the polycarbonate resin composition of the present invention is not limited, and a known method for producing the polycarbonate resin composition can be widely adopted, and the polycarbonate resin (A), (B) and ABS resin (C), and if necessary, can be used. The other components to be blended are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then mixed with a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, and the like. A method of melting and kneading with a machine can be mentioned.
The temperature of melt-kneading is not particularly limited, but is preferably in the range of 240 to 320 ° C, particularly preferably 240 to 300 ° C.

[Molding]
The above-mentioned polycarbonate resin composition (pellet) is molded by various molding methods to obtain a molded product.
The shape of the molded product is not particularly limited and may be appropriately selected depending on the intended use and purpose of the molded product. For example, plate-shaped, plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, etc. Examples thereof include a circular shape, an elliptical shape, a polygonal shape, a deformed product, a hollow product, a frame shape, a box shape, and a panel shape.

The method for molding the molded product is not particularly limited, and a conventionally known molding method can be adopted. For example, an injection molding method, an injection compression molding method, an extrusion molding method, a deformed extrusion method, a transfer molding method, a hollow molding method, etc. Gas assist hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotary molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method , Pressurization molding method and the like.
Above all, molding is preferably performed by an injection molding method, and for example, injection molding is performed using a known injection molding machine such as an injection molding machine, an ultra-high speed injection molding machine, or an injection compression molding machine. The cylinder temperature of the injection molding machine at the time of injection molding is preferably 240 to 320 ° C, more preferably 250 to 300 ° C, still more preferably 260 to 280 ° C. The injection speed during injection molding is preferably 10 to 1,000 mm / sec, more preferably 10 to 500 mm / sec.

[Room temperature impact resistance]
The room temperature impact resistance of the molded product made of the polycarbonate resin composition of the present invention can be determined by a Charpy impact test at + 23 ° C. The room temperature impact resistance is preferably 40 kJ / m ² or more, more preferably 50 kJ / m ² or more, and further preferably 60 kJ / m ² .
If the room temperature impact resistance is less than 40 kJ / m ² , the low temperature impact resistance tends to be low, which is not preferable. This value is achieved by adjusting the blending ratio of the polycarbonate resin (A), the polycarbonate resin (B), and the ABS resin (C), and adding the elastomer (E) as necessary.

[Low temperature impact resistance]
The low temperature impact resistance of the molded product made of the polycarbonate resin composition of the present invention can be determined by a Charpy impact test at −30 ° C. The low temperature impact resistance is preferably 20 kJ / m ² or more, more preferably 25 kJ / m ² or more, further preferably 30 kJ / m ² or more, and particularly preferably 35 kJ / m ² or more. If it is less than 20 kJ / m ^2, it is not preferable because when it is made into a molded product, it tends to cause brittle fracture due to impact under low temperature conditions. For this value, the blending ratio of the polycarbonate resin (A), the polycarbonate resin (B), and the ABS resin (C) is adjusted so that the room temperature impact resistance is at least a predetermined value, and if necessary, the elastomer ( It is necessary to add E), but more preferably, the graft copolymer (D) needs to be adjusted so as to obtain the desired low-temperature impact resistance within a range that does not lose the effect of scratch resistance.

[Pencil hardness]
The pencil hardness of the molded product made of the polycarbonate resin of the present invention is preferably HB or higher, more preferably F or higher, and even more preferably H or higher. If the pencil hardness is less than HB, the surface of the resin molded product tends to be easily scratched. In the present invention, the pencil hardness of HB or higher is adjusted by adjusting the blending ratio of the polycarbonate resin (A), the polycarbonate resin (B), and the ABS resin (C) at a specific ratio, and if necessary, the graft copolymer (D). It can be achieved by adjusting the amount of addition of.
In the present invention, the pencil hardness is measured under a load of 750 g in accordance with ISO 15184.

The molded product of the polycarbonate resin composition of the present invention can be used in a wide range of fields, such as electronic and electrical equipment and its parts, OA equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building materials, and various types. It is useful for various applications such as containers, leisure goods / miscellaneous goods, and lighting equipment, and is expected to be particularly applied to housing members of electronic and electrical equipment, OA equipment, information terminal equipment, and vehicle interior parts.

Housing components for electronic and electrical equipment, OA equipment, and information terminal equipment include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks, PDAs, cameras, video cameras, mobile phones, and various other types. Examples include housing members such as mobile terminals, recording medium drives and readers.
Vehicle interior parts include inner door handles, center panels, instrumental panels, console boxes, luggage floorboards, door pockets, display housings for car navigation, and the like.

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.
The raw material components used in the following examples and comparative examples are as shown in Table 1 below.

In Table 1 above, the polycarbonate resin B used as the polycarbonate resin (B) was produced according to the following Production Example 1.

<Manufacturing Example 1: Production of Polycarbonate Resin B>
26.14 mol (6.75 kg) of 2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as "BPC") and 26.79 mol (5.74 kg) of diphenyl carbonate were added. It was placed in a SUS reactor (internal volume 10 liters) equipped with a stirrer and a distillate condensing device, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor was stirred, and cesium carbonate (Cs ₂ CO ₃ ) as a transesterification reaction catalyst was added to the reaction solution in the molten state so as to be 1.5 × ^10-6 mol with respect to 1 mol of BPC. In addition, the reaction solution was stirred and cultivated at 220 ° C. for 30 minutes in a nitrogen gas atmosphere. Next, at the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further carried out for 100 minutes to distill out phenol.

Next, the temperature inside the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr to distill off phenol corresponding to almost the entire theoretical amount of distillation. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was continued for another 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, the reaction liquid temperature immediately before the end of the reaction was 289 ° C., and the stirring power was 1.00 kW.
Next, the reaction solution in the molten state is fed into the twin-screw extruder, and a 4-fold molar amount of butyl p-toluenesulfonate with respect to cesium carbonate is supplied from the first supply port of the twin-screw extruder. It was kneaded with the reaction solution, and then the reaction solution was extruded into a strand shape through a die of a twin-screw extruder and cut with a cutter to obtain polycarbonate resin pellets.

The physical properties of the obtained polycarbonate resin (B) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 26,000

(Examples 1 and 2 and Comparative Examples 1 to 6)
Each component listed in Table 1 above is blended in the proportion shown in Table 2 below (all indicated by parts by mass), mixed uniformly with a tumbler mixer, and then a twin-screw extruder (Japan Steel Works, Ltd.). TEX30α) was fed to the extruder from the barrel at the upstream part of the extruder at a cylinder temperature of 260 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 25 kg / hr, and melt-kneaded to obtain pellets of a polycarbonate resin composition. ..

[Impact resistance at room temperature and low temperature (Charpy impact strength with notch)]
After the pellets obtained by the above manufacturing method are dried at 100 ° C. for 5 hours, a cylinder temperature of 260 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds are used using a NEX80III type injection molding machine manufactured by Nissei Resin Industry Co., Ltd. An ISO multipurpose test piece (4 mm thick) was prepared by injection molding under the conditions of. The obtained test piece is cut into a predetermined shape by cutting according to the ISO 179-1 standard, and the Charpy impact test is performed under the conditions of room temperature (23 ° C) and low temperature (-30 ° C) based on the ISO 179-2 standard. (With notch) was performed, and the impact resistance value (unit: kJ / m ² ) was determined.

[Measurement of pencil hardness]
An ISO multipurpose test piece (4 mm thick) was prepared in the same manner as above. For this molded product, the pencil hardness measured under a load of 750 g was determined using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with ISO 15184.
The above evaluation results are shown in Table 2 below.

Since the polycarbonate resin composition of the present invention is a polycarbonate resin material having high hardness and excellent impact resistance at room temperature and impact resistance at low temperature, housing members for electronic and electrical equipment, OA equipment, and information terminal equipment in particular. , Can be suitably used for parts such as application to vehicle interior parts, and has very high industrial utility.

Claims (5)

A vinyl polymer segment containing a bisphenol A type polycarbonate resin (A), a polycarbonate resin (B) having a structural unit represented by the following general formula (1), an ABS resin (C), and a polyethylene polymer as a main chain. A polycarbonate resin composition containing a graft copolymer (D) as a side chain.
The content ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is 70 to 95/5 to 30 in terms of the mass ratio of (A) / (B).
The content of the ABS resin (C) is 25 to 100 parts by mass, and the content of the graft copolymer (D) is 1 to 9 parts by mass with respect to 100 parts by mass of the total of the polycarbonate resins (A) and (B). part der is,
Graft copolymer polycarbonate resin composition vinyl polymer segment vinyl monomer for forming is characterized in styrene monomer der Rukoto of (D).
(In the general formula (1), R ¹ represents a methyl group, R ² and R ³ independently represent a hydrogen atom or a methyl group, and X represents an alkylene group or an alkylidene group.) The ABS resin (C) contains 40 to 80% by mass of the aromatic vinyl monomer component (c1), 10 to 30% by mass of the vinyl cyanide monomer component (c2), and the diene-based rubbery polymer component (c3) 10. The polycarbonate according to claim 1, which is an ABS resin composed of ~ 30% by mass and other monomer components (c4) 0 to 30% by mass (however, the total of the components (c1) to (c4) is 100% by mass). Resin composition. The polycarbonate resin composition according to claim 1 or 2, wherein the pencil hardness measured under a load of 750 g is HB or more according to ISO 15184. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the low-temperature Charpy impact value (notched) at −30 ° C. is 20 kJ / m ² or more. A molded product of the polycarbonate resin composition according to any one of claims 1 to 4.