阅读说明：本技术 聚碳酸酯树脂组合物及其成型品 (Polycarbonate resin composition and molded article thereof ) 是由 鬼山祥幸 于 2020-03-27 设计创作，主要内容包括：本发明涉及聚碳酸酯树脂组合物,其中,相对于100质量份粘均分子量为18,500以上的聚碳酸酯树脂(A),含有5～30质量份的流动性改性剂(B)、3～20质量份的磷系阻燃剂(C)、0.05～2质量份的含氟聚合物(D)、以及20～45质量份的包含滑石(E)的无机填料,该无机填料中的滑石(E)以外的填料(F)的比例为20质量％以下,该聚碳酸酯树脂组合物在耐化学药品性的评价中的拉伸破坏强度的保持率为70％以上。(The present invention relates to a polycarbonate resin composition, wherein the polycarbonate resin composition comprises, relative to 100 parts by mass of a polycarbonate resin (A) having a viscosity average molecular weight of 18,500 or more, 5 to 30 parts by mass of a flowability modifier (B), 3 to 20 parts by mass of a phosphorus flame retardant (C), 0.05 to 2 parts by mass of a fluoropolymer (D), and 20 to 45 parts by mass of an inorganic filler comprising talc (E), wherein the proportion of the filler (F) other than talc (E) in the inorganic filler is 20% by mass or less, and the retention of tensile rupture strength in the evaluation of chemical resistance is 70% or more.)

1. A polycarbonate resin composition which comprises 100 parts by mass of a polycarbonate resin (A) having a viscosity average molecular weight of 18,500 or more, 5 to 30 parts by mass of a flowability modifier (B), 3 to 20 parts by mass of a phosphorus flame retardant (C), 0.05 to 2 parts by mass of a fluoropolymer (D), and 20 to 45 parts by mass of an inorganic filler comprising talc (E), wherein the proportion of the filler (F) other than talc (E) in the inorganic filler is 20% by mass or less, and wherein the polycarbonate resin composition has a tensile strength retention of 70% or more as measured by the following method (I),

process (I): an ISO multipurpose test piece having a thickness of 3mm obtained by injection molding of the polycarbonate resin composition was fixed to a jig using an injection molding machine having a mold clamping force of 75 tons under conditions of a cylinder temperature of 280 ℃, a mold temperature of 60 ℃ and a molding cycle of 48 seconds, and was bent so that the strain reached 1%, and the portion was coated with a rust inhibitor "Barrier Guard part ii", and after being placed in a hot air oven set at 55 ℃ and held for 72 hours, the test piece was removed from the jig, the tensile breaking strength was measured according to ISO527, and the value was divided by the value of the tensile breaking strength of the untreated test piece, and the obtained value was taken as the retention rate of the tensile breaking strength.

2. The polycarbonate resin composition of claim 1, wherein the flowability modifier (B) is at least one selected from the group consisting of an acrylonitrile-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, a polycarbonate oligomer, and polycaprolactone.

3. The polycarbonate resin composition according to claim 1 or 2, wherein the talc (E) has an average particle diameter of 8.5 μm or less.

4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the proportion of the phosphorus-based flame retardant (C) to the flowability modifier (B) is 20% by mass or more.

5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the phosphorus-based flame retardant (C) is a condensed phosphate-based flame retardant (C-1) and/or a phosphazene compound (C-2).

6. The polycarbonate resin composition according to any one of claims 1 to 5, further comprising 0.05 to 1 part by mass of a phosphorus compound (G) other than the phosphorus-based flame retardant (C) per 100 parts by mass of the polycarbonate resin (A).

7. The polycarbonate resin composition according to claim 6, wherein the phosphorus compound (G) is at least one selected from the group consisting of a phosphite ester, a phosphate ester and a phosphate ester metal salt.

8. The polycarbonate resin composition according to claim 7, wherein the phosphite ester is represented by the following formula (1), the phosphate ester is represented by the following formula (2), and the phosphate ester metal salt is represented by the following formula (5) or the following formula (6),

[ solution 1]

In the formula (1), R¹Is alkyl or aryl, 2R¹The same or different;

[ solution 2]

In the formula (2), R²Is alkyl or aryl, (3-n) R²The same or different; n represents an integer of 0 to 2;

[ solution 3]

In the formulae (5) and (6), R³Is alkyl or aryl; m is a metal.

9. The polycarbonate resin composition according to claim 8, wherein R in the formula (1)¹Is alkyl with 1-30 carbon atoms or aryl with 6-30 carbon atoms, R in the formula (2)²Is alkyl with 1-30 carbon atoms or aryl with 6-30 carbon atoms, R in the formulas (5) and (6)³Is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.

10. The polycarbonate resin composition according to claim 9, wherein R in the formula (1)¹Is stearyl group, nonyl group, or phenyl group having a substituent, R in the above (2)²The number of carbon atoms of the alkyl group of (2) is 13, 18 or 24, and R in the formula (5) or (6)³The number of carbon atoms of the alkyl group of (2) is 13, 18 or 24.

11. The polycarbonate resin composition of claim 10, wherein the phosphite ester is distearyl pentaerythritol diphosphite; the phosphate ester is represented by the following formula (2A) and is a mixture of distearyl acid phosphate ester in which n is 1 and monostearyl acid phosphate ester in which n is 2 in the formula (2A); the phosphate metal salt is a mixture of a zinc salt of distearyl acid phosphate represented by the following formula (5A) and a zinc salt of monostearyl acid phosphate represented by the following formula (6A),

O＝P(OH)_n(OC₁₈H₃₇)_3-n…(2A)

[ solution 4]

12. The polycarbonate resin composition according to any one of claims 6 to 11, wherein the proportion of the phosphorus compound (G) relative to the talc (E) is 0.2 to 2.0 mass%.

13. The polycarbonate resin composition of any one of claims 1-12, wherein the flame retardancy in UL94 test at a thickness of 2mm is 5 VB.

14. The polycarbonate resin composition of any of claims 1-13, wherein the unnotched charpy impact strength at 4mm thickness according to ISO179 is 35kJ/m²The above.

15. The polycarbonate resin composition of any of claims 1-14, wherein the flexural modulus according to ISO178 is 5,000MPa or greater.

16. A molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 15.

17. The molded article of claim 16 which is a chassis or an optical housing.

Technical Field

The present invention relates to a polycarbonate resin composition. More particularly, the present invention relates to a polycarbonate resin composition which is excellent in rigidity, flame retardancy, fluidity, dimensional accuracy, impact resistance and chemical resistance and is particularly suitable for chassis/frame materials of OA equipment and optical housings, and a molded article obtained by molding the polycarbonate resin composition.

Background

Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automobile materials, electrical and electronic equipment materials, housing materials, and materials for manufacturing parts in other industrial fields.

The flame-retardant polycarbonate resin composition can be suitably used as a member of information/mobile devices such as computers, notebook personal computers, tablet terminals, smart phones and cellular phones, OA devices such as printers and copiers, and the like.

Polycarbonate resin compositions having increased rigidity by compounding reinforcing materials such as glass fibers, carbon fibers, glass flakes, talc, and mica have also been widely used.

Resin materials used for chassis or frame of OA equipment such as laser beam printers, copiers, and projectors are required to have both flame retardancy and rigidity. Further, fluidity, dimensional accuracy (low anisotropy), strength (impact resistance), and chemical resistance are also required.

Patent document 1 discloses a thermoplastic resin composition containing a thermoplastic resin, an organic phosphorus compound, a plate-like filler (mica or talc), and a fibrous filler. The resin composition of patent document 1 has high rigidity because of a high content of the filler, but there is no data on impact resistance and it is not yet sufficient. Further, since a fibrous filler is blended in a large amount, anisotropy is large and dimensional accuracy is insufficient.

Patent document 2 discloses a thermoplastic resin composition containing at least one thermoplastic polymer selected from the group consisting of aromatic polycarbonate, styrenic hard polymer, and polyphenylene ether, a flame retardant composed of an organic phosphorus compound, talc, and at least one filler selected from the group consisting of mica and wollastonite. The resin composition of patent document 2 is excellent in rigidity, flame retardancy and dimensional accuracy, but is insufficient in impact resistance. Patent document 2 does not examine chemical resistance.

Patent document 3 discloses a thermoplastic resin composition containing at least one thermoplastic polymer selected from the group consisting of aromatic polycarbonate, styrenic hard polymer, and polyphenylene ether, a flame retardant composed of an organic phosphorus compound, mica, and at least one filler selected from the group consisting of talc and wollastonite. However, the resin composition of patent document 3 is excellent in rigidity, flame retardancy and dimensional accuracy, but there is no data on impact resistance and it is not yet sufficient. Patent document 3 does not examine chemical resistance.

Patent document 4 discloses an aromatic polycarbonate resin composition containing an aromatic polycarbonate, an acrylonitrile-styrene copolymer, an inorganic filler, an organic phosphorus compound-based flame retardant, and a fluorine-containing anti-dripping agent, wherein mica and at least one selected from talc and wollastonite are used as the inorganic filler. The resin composition of patent document 4 is excellent in rigidity, flame retardancy and dimensional accuracy, but is insufficient in impact resistance. Although patent document 4 has data on chemical resistance, the results are equivalent in all examples and comparative examples of the polycarbonate resin composition, and it is not sufficient to compare the chemical resistance.

Patent document 5 discloses a polycarbonate resin composition containing a polycarbonate, a phosphate ester compound, muscovite, glass flakes, and a fibrous filler. The resin composition of patent document 5 is excellent in rigidity, flame retardancy and dimensional accuracy, but is insufficient in impact resistance.

Patent document 1: japanese patent laid-open publication No. 2003-41131

Patent document 2: japanese patent laid-open publication No. 2004-323565

Patent document 3: japanese laid-open patent publication No. 2004-315645

Patent document 4: japanese patent laid-open publication No. 2004-2737

Patent document 5: japanese patent laid-open publication No. 2005-146219

Disclosure of Invention

The present invention aims to provide a polycarbonate resin composition which is excellent in rigidity, flame retardancy, flowability, dimensional accuracy, impact resistance and chemical resistance and is particularly suitable for OA equipment chassis/frame materials and optical housings; and a molded article obtained by molding the polycarbonate resin composition.

The present inventors have found that a polycarbonate resin composition obtained by blending a polycarbonate resin having a specific molecular weight with a fluidity modifier, a condensed phosphate ester-based flame retardant, an inorganic filler mainly composed of talc, and a fluorine-containing polymer at a predetermined ratio is excellent in all of rigidity, flame retardancy, fluidity, dimensional accuracy, impact resistance, and chemical resistance.

The gist of the present invention is as follows.

[1] A polycarbonate resin composition which comprises, per 100 parts by mass of a polycarbonate resin (A) having a viscosity average molecular weight of 18,500 or more, 5 to 30 parts by mass of a flowability modifier (B), 3 to 20 parts by mass of a phosphorus flame retardant (C), 0.05 to 2 parts by mass of a fluoropolymer (D), and 20 to 45 parts by mass of an inorganic filler comprising talc (E), wherein the proportion of a filler (F) other than talc (E) in the inorganic filler is 20% by mass or less, and wherein the polycarbonate resin composition has a retention of tensile strength at break of 70% or more as measured by the following method (I).

Process (I): an ISO multipurpose test piece having a thickness of 3mm obtained by injection molding of the polycarbonate resin composition was fixed to a jig using an injection molding machine having a mold clamping force of 75 tons under conditions of a cylinder temperature of 280 ℃, a mold temperature of 60 ℃ and a molding cycle of 48 seconds, and was bent so that the strain reached 1%, and the portion was coated with a rust inhibitor "Barrier Guard part ii", and after being placed in a hot air oven set at 55 ℃ and held for 72 hours, the test piece was removed from the jig, the tensile breaking strength was measured according to ISO527, and the value was divided by the value of the tensile breaking strength of the untreated test piece, and the obtained value was taken as the retention rate of the tensile breaking strength.

[2] The polycarbonate resin composition according to [1], wherein the flowability modifier (B) is at least one selected from the group consisting of an acrylonitrile-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, a polycarbonate oligomer and polycaprolactone.

[3] The polycarbonate resin composition according to [1] or [2], wherein the talc (E) has an average particle diameter of 8.5 μm or less.

[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the proportion of the phosphorus-based flame retardant (C) to the flowability modifier (B) is 20% by mass or more.

[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the phosphorus-based flame retardant (C) is a condensed phosphate-based flame retardant (C-1) and/or a phosphazene compound (C-2).

[6] The polycarbonate resin composition according to any one of [1] to [5], further comprising 0.05 to 1 part by mass of a phosphorus compound (G) other than the phosphorus-based flame retardant (C) per 100 parts by mass of the polycarbonate resin (A).

[7] The polycarbonate resin composition according to [6], wherein the phosphorus compound (G) is at least one selected from the group consisting of a phosphite ester, a phosphate ester and a phosphate ester metal salt.

[8] The polycarbonate resin composition according to [7], wherein the phosphite is represented by the following formula (1), the phosphate is represented by the following formula (2), and the phosphate metal salt is represented by the following formula (5) or the following formula (6).

[ solution 1]

In the formula (1), R¹Is alkyl or aryl. 2R¹May be the same or different.

[ solution 2]

In the formula (2), R²Is alkyl or aryl. (3-n) R²May be the same or different. n represents an integer of 0 to 2.

[ solution 3]

In the formulae (5) and (6), R³Is alkyl or aryl. M is a metal.

[9]Such as [8]]The polycarbonate resin composition as described in (1), wherein R is represented by the formula¹Is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R in the above formula (2)²Is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R in the above formulae (5) and (6)³Is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.

[10]Such as [ 9]]The polycarbonate resin composition as described in (1), wherein R is represented by the formula¹Is a stearyl group, a nonyl group or a substituted phenyl group, R in the above-mentioned (2)²The alkyl group of (2) has 13, 18 or 24 carbon atoms, and R in the above formulae (5) and (6)³The number of carbon atoms of the alkyl group of (2) is 13, 18 or 24.

[11] The polycarbonate resin composition as described in [10], wherein the phosphite is distearyl pentaerythritol diphosphite; the phosphate is represented by the following formula (2A), and is a mixture of distearyl acid phosphate in which n is 1 and monostearyl acid phosphate in which n is 2 in the formula (2A); the phosphate metal salt is a mixture of a zinc salt of distearyl acid phosphate represented by the following formula (5A) and a zinc salt of monostearyl acid phosphate represented by the following formula (6A).

O＝P(OH)_n(OC₁₈H₃₇)_3-n…(2A)

[ solution 4]

[12] The polycarbonate resin composition according to any one of [6] to [11], wherein the proportion of the phosphorus compound (G) to the talc (E) is 0.2 to 2.0 mass%.

[13] The polycarbonate resin composition according to any one of [1] to [12], wherein the flame retardancy in UL94 test at a thickness of 2mm is 5 VB.

[14]Such as [1]]To [13]]The polycarbonate resin composition as described in any one of the above, wherein the unnotched Charpy impact strength at a thickness of 4mm according to ISO179 is 35kJ/m²The above.

[15] The polycarbonate resin composition according to any one of [1] to [14], wherein the flexural modulus according to ISO178 is 5,000MPa or more.

[16] A molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [15 ].

[17] The molded article as described in [16], which is a chassis or an optical housing.

ADVANTAGEOUS EFFECTS OF INVENTION

The polycarbonate resin composition of the present invention is excellent in rigidity, flame retardancy, flowability, dimensional accuracy, impact resistance and chemical resistance. The polycarbonate resin composition of the present invention can be suitably used for various applications, particularly, OA equipment chassis/frame materials and the like.

Detailed Description

The present invention will be described in detail below with reference to embodiments, examples, and the like. The present invention is not limited to the embodiments and examples described below, and can be implemented by being arbitrarily changed within a range not departing from the gist of the present invention.

[ polycarbonate resin composition ]

The polycarbonate resin composition of the present invention is a polycarbonate resin composition comprising: the composition comprises at least a polycarbonate resin (A), a flowability modifier (B), a phosphorus flame retardant (C), a fluoropolymer (D), and an inorganic filler mainly comprising talc (E) at a specific ratio, and has a retention of tensile rupture strength of 70% or more in the evaluation of chemical resistance described later.

The polycarbonate resin composition of the present invention may further contain other components as required.

< mechanism >

The polycarbonate resin composition of the present invention can obtain excellent flame retardancy by containing the phosphorus-based flame retardant (C) and the fluoropolymer (D) at a predetermined ratio, and further has excellent flowability and moldability.

The polycarbonate resin composition containing the phosphorus-based flame retardant (C) and the fluoropolymer (D) has excellent rigidity, dimensional accuracy, and impact resistance, and also has excellent flame retardancy, because the polycarbonate resin composition contains the inorganic filler mainly composed of talc (E) at a predetermined ratio.

Further, by including the fluidity modifier (B) at a predetermined ratio, the fluidity and moldability can be further improved without impairing the flame retardancy.

Further, by using the polycarbonate resin (a) having a viscosity average molecular weight of at least a predetermined value and appropriately selecting the fluidity modifier (B), the phosphorus flame retardant (C), and the inorganic filler, the chemical resistance can be made excellent. Therefore, the tensile rupture strength retention ratio in the evaluation of chemical resistance described later was 70% or more, and high chemical resistance was exhibited.

< polycarbonate resin (A) >

As the polycarbonate resin (a) contained in the polycarbonate resin composition of the present invention, any conventionally known polycarbonate resin can be used. Examples of the polycarbonate resin (a) include an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin. Preferably an aromatic polycarbonate resin.

The aromatic polycarbonate resin is a linear or branched aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with phosgene or a carbonic acid diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and can be carried out by a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (transesterification method). The polycarbonate resin may be produced by a melt method and the amount of the OH group of the terminal group may be adjusted.

Typical examples of the aromatic dihydroxy compound, which is one of the raw materials of the aromatic polycarbonate resin used in the present invention, include bis (4-hydroxyphenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 4-bis (4-hydroxyphenyl) heptane, 1-bis (4-hydroxyphenyl) cyclohexane, 4' -dihydroxybiphenyl, 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, and the like.

In addition, a polyhydric phenol having 3 or more hydroxyl groups in the molecule, such as 1,1, 1-tris (4-hydroxyphenyl) ethane or 1,3, 5-tris (4-hydroxyphenyl) benzene, may be used in a small amount as a branching agent.

Among these aromatic dihydroxy compounds, 2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferred. These aromatic dihydroxy compounds may be used alone or in combination of two or more.

To obtain a branched aromatic polycarbonate resin, phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) -2-heptene, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 2, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) -3-heptene, 1,3, 5-tris (4-hydroxyphenyl) benzene, a polyhydroxy compound such as 1,1, 1-tris (4-hydroxyphenyl) ethane, or 3, 3-bis (4-hydroxyaryl) indolone (═ diphenol isatin), 5-chloroisatin, 5, 7-dichloroisatin, 5-bromoisatin, or the like may be used as a part of the aromatic dihydroxy compound. The amount of these compounds to be used is 0.01 to 10 mol%, preferably 0.1 to 2 mol%, based on the hydroxy compound.

In the polymerization by the transesterification method, a carbonic acid diester is used as a monomer instead of phosgene. Typical examples of the carbonic acid diester include substituted diaryl carbonates such as diphenyl carbonate and dibenzyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate. These carbonic acid diesters may be used alone or in combination of two or more. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable.

In the carbonic acid diester, the amount of 50 mol% or less, more preferably 30 mol% or less thereof may be substituted with the dicarboxylic acid or the dicarboxylic acid ester. Representative examples of dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, and the like. When a part of the carbonic diester is replaced with a dicarboxylic acid or a dicarboxylic acid ester, a polyester carbonate is obtained.

In the production of an aromatic polycarbonate resin by the transesterification method, a catalyst is generally used. The kind of the catalyst is not limited, and a basic compound such as an alkali metal compound, an alkaline earth metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound is generally used. Among them, alkali metal compounds and/or alkaline earth metal compounds are particularly preferable. The catalyst may be used alone or in combination of two or more. In the transesterification method, the polymerization catalyst is usually deactivated by p-toluenesulfonate or the like.

As the polycarbonate resin (A), an aromatic polycarbonate resin derived from 2, 2-bis (4-hydroxyphenyl) propane or an aromatic polycarbonate copolymer derived from 2, 2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compound is preferable. In order to impart flame retardancy or the like, a polymer or oligomer having a siloxane structure may be copolymerized. The polycarbonate resin (a) may be a mixture of 2 or more polymers and/or copolymers having different raw materials, or may have a branched structure of at most 0.5 mol%.

The content of terminal hydroxyl groups in a polycarbonate resin (a) such as an aromatic polycarbonate resin greatly affects thermal stability, hydrolytic stability, color tone and the like. In order to have practical physical properties, the content of terminal hydroxyl groups in the polycarbonate resin (A) is usually 30 to 2000ppm, preferably 100 to 1500ppm, and more preferably 200 to 1000 ppm. Examples of the end-capping agent for adjusting the content of the terminal hydroxyl group include p-tert-butylphenol, phenol, cumylphenol, and p-long alkyl-substituted phenol.

The residual monomer content in the polycarbonate resin (A) such as an aromatic polycarbonate resin is 150ppm or less, preferably 100ppm or less, and more preferably 50ppm or less. When the polycarbonate is synthesized by the transesterification method, the residual amount of the carbonic acid diester is further set to 300ppm or less, preferably 200ppm or less, and more preferably 150ppm or less.

The molecular weight of the polycarbonate resin (a) used in the present invention is 18,500 or more in terms of a viscosity-average molecular weight calculated from a solution viscosity measured at a temperature of 20 ℃ using methylene chloride as a solvent. When the viscosity average molecular weight of the polycarbonate resin (a) is 18,500 or more, the chemical resistance is good and there is no risk of the mechanical properties such as impact resistance being insufficient. If the viscosity average molecular weight is too large, the flowability and moldability of the polycarbonate resin composition may be impaired, and therefore, the viscosity average molecular weight of the polycarbonate resin (A) used in the present invention is preferably 18,500 to 25,000, particularly 20,000 to 25,000, particularly 20,500 to 22,500.

In the polycarbonate resin (a), 2 or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed and used. It is also possible to mix a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned suitable range and make it within the above-mentioned molecular weight range.

The polycarbonate resin (a) used in the present invention may be not only a polycarbonate resin which is an unused raw material but also a polycarbonate resin which is regenerated from a used product, that is, a so-called material-recycled polycarbonate resin. Preferable examples of the used product include an optical recording medium such as an optical disk, a light guide plate, a vehicle transparent member such as an automobile window glass, an automobile headlight lens, and a windshield, a container such as a water bottle, a spectacle lens, a sound insulating wall, a glass window, and a building member such as a wave plate. The form of the recycled polycarbonate resin is not particularly limited, and any of defective products, ground products such as injection ports and runners, and pellets obtained by melting the same can be used.

< fluidity modifier (B) >

The polycarbonate resin composition of the present invention contains a flowability modifier (B) for the purpose of improving flowability and moldability and improving the surface appearance of the molded article obtained. The fluidity modifier (B) is a component for improving the fluidity of the polycarbonate resin (A), and various low-molecular compounds or high-molecular compounds can be used.

The fluidity modifier (B) used in the present invention is preferably 1 or a combination of 2 or more selected from the group consisting of a vinyl cyanide-aromatic vinyl copolymer, a vinyl cyanide-diene-aromatic vinyl copolymer, a polycarbonate oligomer and polycaprolactone. Among them, vinyl cyanide-aromatic vinyl copolymers, vinyl cyanide-diene-aromatic vinyl copolymers, and polycarbonate oligomers are preferable, and vinyl cyanide-aromatic vinyl copolymers are particularly preferable.

The vinyl cyanide-aromatic vinyl copolymer is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. The vinyl cyanide compound includes vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. Examples of the aromatic vinyl compound include styrene and styrene derivatives such as styrene, α -methylstyrene, p-methylstyrene, vinylxylene, dimethylstyrene, p-tert-butylstyrene, bromostyrene, dibromostyrene, and the like. Among these, styrene is preferred. These compounds may be used alone, or 2 or more of them may be used in combination.

The preferable proportion of each of the structural units derived from the vinyl cyanide compound and the aromatic vinyl compound in the vinyl cyanide-aromatic vinyl copolymer is 10 to 40% by mass, more preferably 15 to 30% by mass, and the preferable proportion of the structural units derived from the vinyl cyanide compound is 90 to 60% by mass, more preferably 85 to 70% by mass, based on 100% by mass of the whole. Further, in the copolymerization, another copolymerizable vinyl compound may be mixed with these vinyl compounds and used. In this case, in the vinyl cyanide-aromatic vinyl copolymer, it is preferable that the structural unit derived from the other vinyl compound is 15% by mass or less.

The vinyl cyanide-aromatic vinyl copolymer is produced by a method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, or bulk/suspension polymerization. The vinyl cyanide-aromatic vinyl copolymer may be obtained by any method. The initiator, chain transfer agent, and the like used in the copolymerization reaction may be any known ones as necessary.

The vinyl cyanide-aromatic vinyl copolymer is particularly preferably an acrylonitrile-styrene copolymer. The melt volume flow rate (MVR) reflecting the molecular weight of the acrylonitrile-styrene copolymer is preferably 20-200 cm in terms of a measurement value at 220 ℃ under a load of 10kg³10 min, more preferably 70-150 cm³10 minutes. The acrylonitrile-styrene copolymer may be a copolymer commercially available AS an AS resin or SAN resin.

The vinyl cyanide-diene-aromatic vinyl copolymer is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound, a diene, and an aromatic vinyl compound. Examples of the diene include butadiene and isoprene. The diene rubber is preferably a diene rubber obtained by preliminary polymerization. Examples thereof include polybutadiene-based rubbers, acrylonitrile-butadiene copolymer-based rubbers, styrene-butadiene copolymer-based rubbers, and polyisoprene-based rubbers. The diene is particularly preferably a polybutadiene rubber. These may be used alone, or 2 or more of them may be mixed and used.

Examples of the vinyl cyanide compound include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Acrylonitrile is particularly preferred.

Examples of the aromatic vinyl compound include styrene and styrene derivatives such as styrene, α -methylstyrene, p-methylstyrene, vinylxylene, dimethylstyrene, p-tert-butylstyrene, bromostyrene, dibromostyrene, and the like. Among these, styrene is preferred. These compounds may be used alone, or 2 or more of them may be used in combination.

The preferable copolymerization composition ratio of the ethylene cyanide-diene-aromatic vinyl copolymer is preferably 10 to 50% by mass, more preferably 10 to 40% by mass of the structural unit derived from the diene rubber from the viewpoint of improving moldability, assuming that the total copolymer is 100% by mass. The amount of the structural unit derived from a vinyl cyanide compound is 5 to 30% by mass, more preferably 10 to 25% by mass, and the amount of the structural unit derived from an aromatic vinyl compound is 20 to 80% by mass, more preferably 40 to 70% by mass. Further, in the copolymerization, other copolymerizable vinyl compounds may be used in combination. In this case, in the ethylene cyanide-diene-aromatic vinyl copolymer, the structural unit derived from the other vinyl compound is preferably 15% by mass or less.

The vinyl cyanide-diene-aromatic vinyl copolymer is produced by a method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, or bulk/suspension polymerization. The vinyl cyanide-diene-aromatic vinyl copolymer may be obtained by any method. The initiator, chain transfer agent, and the like used in the copolymerization reaction may be any known ones as necessary.

The vinyl cyanide-diene-aromatic vinyl copolymer is particularly preferably an acrylonitrile-butadiene-styrene copolymer. As the acrylonitrile-butadiene-styrene copolymer, a copolymer commercially available as an ABS resin can be used.

The polycarbonate oligomer is preferably obtained by a reaction of an aromatic diphenol compound such as 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane or 2, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane with a carbonate precursor represented by phosgene or an ester exchange reaction of an aromatic diphenol with diphenyl carbonate or the like. The aromatic diphenol compounds may be used alone or in admixture.

The average degree of polymerization of the polycarbonate oligomer is preferably 2 to 15. When the average polymerization degree of the polycarbonate oligomer is 2 or more, the polycarbonate oligomer is less likely to bleed out from a molded article during molding. When the average polymerization degree is 15 or less, the molded article has good appearance. In the interfacial polymerization method using phosgene, phenol and/or an alkyl-substituted phenol may be added to the polymerization system to adjust the degree of polymerization of the polycarbonate oligomer, and the end may be capped.

Polycaprolactone is a polymer of caprolactone, in particular epsilon-caprolactone, i.e. having [ -CH₂-CH₂-CH₂-CH₂-CH₂-CO-O-]The polycaprolactone is a polymer or copolymer containing at least 70 mass% or more, preferably 75 mass% or more, and more preferably 80 mass% or more of an epsilon-caprolactone structural unit in the polymer. When the polycaprolactone is a copolymer of e-caprolactone and another monomer, examples of the monomer copolymerizable with e-caprolactone include lactone monomers such as β -propiolactone, pivalolactone, and butyrolactone, alkylene oxides such as ethylene oxide, 1, 2-propylene oxide, 1, 3-propylene oxide, and tetrahydrofuran, unsaturated monomers such as styrene, methyl methacrylate, and butadiene, and coupling agents such as dimethyl terephthalate and diphenyl carbonate. These components may be used alone, or 2 or more of them may be mixed and used.

A part of hydrogen atoms of the methylene chain of polycaprolactone may be substituted with a halogen atom, a hydrocarbon group, and the end of polycaprolactone may be subjected to end treatment by esterification, etherification, or the like.

The number average molecular weight of polycaprolactone is preferably 4000 to 50000, more preferably 5000 to 40000, and further preferably 8000 to 30000 in terms of number average molecular weight in terms of polystyrene by Gel Permeation Chromatography (GPC).

The method for producing polycaprolactone is not particularly limited, and the following methods are used: epsilon-caprolactone is ring-opening polymerized using an appropriate initiator such as alcohol, glycol, water, etc., and a catalyst such as titanium tetrabutoxide, tin chloride, etc.

The content of the flowability modifier (B) in the polycarbonate resin composition of the present invention is 5 to 30 parts by mass, preferably 7 to 20 parts by mass, and more preferably 10 to 15 parts by mass, based on 100 parts by mass of the polycarbonate resin (A). If the content of the fluidity modifier (B) is less than the lower limit, the effect of improving moldability and the effect of improving surface appearance due to the improvement of fluidity by the addition of the fluidity modifier (B) cannot be sufficiently obtained. When the content of the fluidity modifier (B) is more than the upper limit, flame retardancy, heat resistance and impact resistance tend to be low, and appearance defects tend to occur.

< phosphorus flame retardant (C) >

The phosphorus-based flame retardant (C) used in the present invention is not particularly limited as long as it is a flame retardancy-imparting component containing phosphorus in its molecule. Preferred phosphorus flame retardants (C) include condensed phosphate flame retardants (C-1) and phosphazene compounds (C-2).

The phosphorus flame retardant (C) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(condensed phosphoric acid ester-based flame retardant (C-1))

Examples of the condensed phosphate ester-based flame retardant (C-1) include a condensed phosphate ester compound represented by the following formula (3).

[ solution 5]

The condensed phosphoric ester compound represented by the above formula (3) may be a mixture of compounds having different numbers of k. In the case of mixtures of condensed phosphoric esters differing in k, k is the average value of these mixtures. k is usually an integer of 0 to 5. In the case of a mixture of compounds having different k numbers, the average k number is preferably in the range of 0.5 to 2, more preferably 0.6 to 1.5, still more preferably 0.8 to 1.2, and particularly preferably 0.95 to 1.15.

X¹Represents a divalent arylene group. X¹For example from resorcinol, hydroquinone, bisphenol A, 2 '-dihydroxybiphenyl, 2, 3'Divalent groups of dihydroxy compounds such as dihydroxybiphenyl, 2,4 '-dihydroxybiphenyl, 3' -dihydroxybiphenyl, 3,4 '-dihydroxybiphenyl, 4' -dihydroxybiphenyl, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, and 2, 7-dihydroxynaphthalene. Among these, divalent groups derived from resorcinol, bisphenol a, and 3, 3' -dihydroxybiphenyl are particularly preferable.

P, q, r and s in formula (3) each represent 0 or 1, and 1 is preferred.

R in the formula (3)¹¹、R¹²、R¹³And R¹⁴Each represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, an isopropylphenyl group, a butylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, and a p-cumylphenyl group. As the aryl group, phenyl, tolyl, xylyl are more preferable.

Specific examples of the condensed phosphate ester compound represented by the formula (3) include aromatic phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyldiphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- (tert-butylphenyl) phenyl phosphate, tri- (tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, and tri- (isopropylphenyl) phosphate; condensed phosphates such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylyl phosphate (RDX), bisphenol a bis-diphenyl phosphate (BDP), and biphenyl bis-diphenyl phosphate; and so on.

The acid value of the condensed phosphoric ester compound represented by the formula (3) is preferably 0.2mgKOH/g or less, more preferably 0.15mgKOH/g or less, still more preferably 0.1mgKOH or less, and particularly preferably 0.05mgKOH/g or less. The lower limit of the acid value may be substantially 0. The content of the half fat of the condensed phosphoric ester compound represented by the formula (3) is preferably 1% by mass or less, more preferably 0.5% by mass or less. When the acid value is 0.2mgKOH/g or less and the half fat content is 1 mass% or less, the polycarbonate resin composition of the present invention is excellent in thermal stability and hydrolysis resistance.

The phosphate ester compound includes, in addition to the above components, a polyester resin, a polycarbonate resin, or an epoxy resin containing a phosphate ester moiety.

The condensed phosphate flame retardant (C-1) may be used in a single amount of 1 kind, or may be used in combination of 2 or more kinds.

(phosphazene Compound (C-2))

The phosphazene compound (C-2) is an organic compound having-P ═ N-bonds in the molecule. The phosphazene compound (C-2) is preferably a cyclic phosphazene compound represented by the following formula (4A), a chain phosphazene compound represented by the following formula (4B), or a crosslinked phosphazene compound obtained by crosslinking at least one phosphazene compound selected from the group consisting of the following formula (4A) and the following formula (4B) with a crosslinking group. The cross-linked phosphazene compound is preferably a component cross-linked by a cross-linking group represented by the following formula (4C) from the viewpoint of flame retardancy.

[ solution 6]

In the formula (4A), a is an integer of 3 to 25. R⁵Which may be the same or different, represent an aryl or alkylaryl group.

[ solution 7]

In the formula (4B), B is an integer of 3 to 10,000. Z represents-N ═ P (OR)⁵)₃OR-N ═ P (O) OR⁵And (4) a base. Y represents-P (OR)⁵)₄OR-P (O) (OR)⁵)₂And (4) a base. R⁵Which may be the same or different, represent an aryl or alkylaryl group.

[ solution 8]

In the formula (4C), A is-C (CH)₃)₂-、-SO₂-, -S-or-O-. l is 0 or 1.

Examples of the cyclic and/or chain phenoxyphosphazene compounds represented by the formulae (4A) and (4B) include, for example, phenoxyphosphazenes, (poly) tolyloxyphosphazenes (e.g., o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, etc.), cyclic and/or chain C (poly) xyloxyphosphazenes such as (poly) xyloxyphosphazene_1-6Alkyl radical C_6-20Aryloxyphosphazene, (poly) phenoxytolyloxyphosphazene (e.g., phenoxyo-tolyloxyphosphazene, phenoxym-tolyloxyphosphazene, phenoxyp-tolyloxyphosphazene, phenoxyo-, p-tolyloxyphosphazene, phenoxym-, p-tolyloxyphosphazene, phenoxyo-, m-, p-tolyloxyphosphazene, etc.), (poly) phenoxyxylmethoxyphenoxyphosphazene, (poly) phenoxytolyloxyphosphazene, etc., (cyclic and/or chain C_6-20Aryl radical C_1-10Alkyl radical C_6-20Aryloxyphosphazenes, etc., preferably cyclic and/or chain phenoxyphosphazenes, cyclic and/or chain C_1-3Alkyl radical C_6-20Aryloxy phosphazene, C_6-20Aryloxy radical C_1-3Alkyl radical C_6-20Aryloxyphosphazenes (e.g., cyclic and/or chain tolyloxyphosphazenes, cyclic and/or chain phenoxytolylphenoxyphosphazenes, etc.). Here, "C" is_1-6The expression "is" C1-6 ", and" C "is_6-20”、“C_1-10The same applies to "and the like. The statement of "(poly) phenoxy" refers to either or both of "phenoxy" and "poly-phenoxy".

As the cyclic phosphazene compound represented by the formula (4A), R is particularly preferable⁵A cyclic phenoxyphosphazene which is a phenyl group. The cyclic phenoxyphosphazene compound is produced by, for example, allowing ammonium chloride and phosphorus pentachloride to react at 120 to 130 DEG CReacting and taking out cyclic chlorophosphazenes such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene and decachlorocyclopentapzene from the obtained mixture of cyclic and linear chlorophosphazenes, and then substituting with phenoxy group to obtain compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene and decaphenoxycyclopentapzene.

The cyclic phenoxyphosphazene compound is preferably a compound in which a in formula (4A) is an integer of 3 to 8, and may be a mixture of compounds having different a. Among them, a mixture of 50 mass% or more of the compounds having a-3, 10 to 40 mass% of the compounds having a-4, and 30 mass% or less of the compounds having a-5 or more in total is preferable.

As the chain phosphazene compound represented by the formula (4B), R is particularly preferable⁵A chain phenoxyphosphazene which is a phenyl group. Examples of such chain phenoxyphosphazene compounds include compounds obtained by ring-opening polymerization of hexachlorocyclotriphosphazene obtained by the above method at a temperature of 220 to 250 ℃ and substitution of the obtained linear dichlorophosphazene having a polymerization degree of 3 to 10,000 with a phenoxy group. In the linear phenoxyphosphazene compound, B in the formula (4B) is preferably 3 to 1,000, more preferably 3 to 100, and further preferably 3 to 25.

Examples of the crosslinked phenoxyphosphazene compound include compounds having a crosslinked structure of 4,4 '-biphenylene (bisphenol S residue), compounds having a crosslinked structure of 2,2- (4, 4' -biphenylene) isopropylidene, compounds having a crosslinked structure of 4,4 '-oxabiphenylene, compounds having a crosslinked structure of 4, 4' -thiabiphenylene, and the like.

As the cross-linked phosphazene compound, R in the above formula (4A) is preferable from the viewpoint of flame retardancy⁵A crosslinked phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound which is a phenyl group is crosslinked by a crosslinking group represented by the formula (4C), or R in the formula (4B)⁵A crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound which is a phenyl group with a crosslinking group represented by the formula (4C). More preferably a cyclic benzeneAnd a crosslinked phenoxyphosphazene compound obtained by crosslinking the oxyphosphazene compound with a crosslinking group represented by the formula (4C).

The content of phenylene in the crosslinked phenoxyphosphazene compound is usually 50 to 99.9%, preferably 70 to 90%, based on the total number of phenyl groups and phenylene groups in the cyclic phosphazene compound represented by formula (4A) and/or the chain phenoxyphosphazene compound represented by formula (4B). The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule thereof.

The phosphazene compound (C-2) is preferably at least one selected from the group consisting of a cyclic phenoxyphosphazene compound represented by the formula (4A) and a crosslinked phenoxyphosphazene compound in which the cyclic phenoxyphosphazene compound represented by the formula (4A) is crosslinked by a crosslinking group, from the viewpoint of flame retardancy and mechanical properties.

Examples of commercially available products of the phosphazene compound (C-2) include phenoxyphosphazene such as "Rabbit FP-110T" manufactured by Kokuku K.K. and "SPS 100" manufactured by Otsuka chemical Co.

The phosphazene compound (C-2) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The polycarbonate resin composition of the present invention contains the phosphorus-based flame retardant (C) in an amount of 3 to 20 parts by mass, preferably 3 to 15 parts by mass, and more preferably 3 to 10 parts by mass, based on 100 parts by mass of the polycarbonate resin (A). When the content of the phosphorus-based flame retardant (C) is less than 3 parts by mass, the flame retardancy is insufficient. When the content of the phosphorus-based flame retardant (C) exceeds 20 parts by mass, the heat resistance and mechanical properties are deteriorated.

The phosphorus-based flame retardant (C) is preferably contained so that the weight ratio of the content of the phosphorus-based flame retardant (C) to the content of the flowability modifier (B) (hereinafter sometimes referred to as "(C)/(B) ratio") is 20 mass% or more, particularly 35 mass% or more, particularly 50 mass% or more, and particularly 60 mass% or more. (C) When the ratio of (B) is 20% by mass or more, the flame retardancy-improving effect by the phosphorus-based flame retardant (C) can be more effectively obtained. (C) If the ratio of (C)/(B) is too large, the appropriate contents of the fluidity modifier (B) and the phosphorus-based flame retardant (C) may not be satisfied, and therefore the ratio of (C)/(B) is preferably 100 mass% or less, particularly preferably 80 mass% or less.

< fluoropolymer (D) >

The fluoropolymer (D) is a polymer or copolymer generally comprising a polyvinyl fluoride structure. Specific examples of the fluoropolymer (D) include a vinylidene fluoride polymer, a tetrafluoroethylene polymer, and a tetrafluoroethylene/hexafluoropropylene copolymer. Among them, tetrafluoroethylene polymer is preferable.

The fluoropolymer (D) is preferably a component having fibril-forming ability, and specifically, a fluoropolymer resin having fibril-forming ability may be mentioned. By providing the fluoropolymer (D) with fibril-forming ability, the dripping resistance during combustion tends to be significantly improved.

As the fluorine-containing polymer (D), an organic polymer-coated fluoroolefin resin can also be suitably used. By coating the fluoroolefin resin with an organic polymer, the dispersibility is improved, the surface appearance of the molded article is improved, and foreign matter on the surface can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by a known method. For example, the following methods can be mentioned.

(1) A method for producing the polyvinyl fluoride powder, which comprises mixing an aqueous dispersion of polyvinyl fluoride particles with an aqueous dispersion of organic polymer particles, and powdering the mixture by coagulation or spray drying.

(2) A method for producing the polyvinyl fluoride particles by polymerizing monomers constituting the organic polymer in the presence of an aqueous dispersion of polyvinyl fluoride particles, and then powdering the resultant polymer by coagulation or spray drying.

(3) A method for producing a dispersion in which an aqueous dispersion of polyvinyl fluoride particles and an aqueous dispersion of organic polymer particles are mixed, which comprises emulsion-polymerizing a monomer having an ethylenically unsaturated bond and then powdering the resulting mixture by coagulation or spray-drying.

As the monomer for producing the organic polymer for coating the fluorine-containing polymer, a monomer having high affinity with the polycarbonate resin (a) is preferable, and an aromatic vinyl monomer, (meth) acrylate monomer, and vinyl cyanide monomer are more preferable, from the viewpoint of dispersibility when blended in the polycarbonate resin (a).

The fluoropolymer (D) preferably has an apparent density of 0.4g/ml or more. The anti-dripping property during combustion is further improved by setting the apparent density of the fluoropolymer (D) to 0.4g/ml or more. The fluoropolymer has an apparent density of more preferably 0.45g/ml or more, and from the viewpoint of handling properties, preferably 2.0g/ml or less, more preferably 1.5g/ml or less, and still more preferably 1.0g/ml or less.

The apparent density of the fluoropolymer (D) was measured in accordance with JIS K6820 using an apparent density measuring apparatus.

The fluoropolymer (D) may be used alone or in combination of 2 or more.

The content of the fluoropolymer (D) in the polycarbonate resin composition of the present invention is 0.05 to 2 parts by mass per 100 parts by mass of the polycarbonate resin (A). When the content of the fluoropolymer (D) is less than 0.05 part by mass, the effect of improving flame retardancy tends to be insufficient. When the content of the fluoropolymer (D) exceeds 2 parts by mass, molded articles obtained by molding the resin composition tend to have poor appearance or reduced mechanical strength. The content of the fluoropolymer (D) is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and preferably 1.5 parts by mass or less, and particularly preferably 1.2 parts by mass or less.

< inorganic Filler >

The inorganic filler used in the present invention mainly contains talc (E) and the talc (E) is contained in the inorganic filler in an amount of 80 mass% or more. If the proportion of talc (E) in the inorganic filler is less than 80% by mass, the objective high impact resistance cannot be obtained by the present invention. The content of talc (E) in the inorganic filler is more preferably 85 mass% or more, and still more preferably 90 mass% or more, from the viewpoint of impact resistance. It is particularly preferable that 100% by mass of the inorganic filler is talc (E).

The average particle diameter of talc (E) is preferably 8.5 μm or less. When the average particle diameter of talc (E) is 8.5 μm or less, the mechanical strength such as bending characteristics is further excellent. From this viewpoint, the average particle diameter of talc (E) is more preferably 8 μm or less.

In order to effectively obtain the effect of improving rigidity, dimensional accuracy and the like by compounding talc (E), the average particle diameter of talc (E) is preferably 2 μm or more, more preferably 4 μm or more.

The particle diameter of talc (E) means the length of the portion of the parallel plates having the largest distance when talc (E) is sandwiched between 2 parallel plates, and corresponds to the major diameter of the plate surface of the plate-like talc (E). The cross section of the obtained molded article was observed by SEM (scanning electron microscope), and the number average of arbitrarily selected 50 measured values was determined as the average particle diameter of talc (E). Alternatively, the average particle diameter of talc (E) may be measured by Microtrac laser diffraction method. In the case of talc (E) to be supplied as a product, the average particle diameter of the product may be used.

An inorganic filler other than talc (E) (hereinafter sometimes referred to as "other inorganic filler (F)") as the inorganic filler may be used in combination with talc (E) in a range in which the proportion of the other inorganic filler (F) in the inorganic filler (hereinafter sometimes referred to as "the proportion of (F) in the inorganic filler") is 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.

The other inorganic filler (F) is not particularly limited. Examples of the other inorganic filler (F) include glass fillers such as glass fibers (chopped fibers), milled glass fibers (glass short fibers), glass flakes, and glass beads; carbon fillers such as carbon fibers, short carbon fibers, carbon nanotubes, and graphite; whiskers such as potassium titanate and aluminum borate; silicate compounds such as wollastonite, mica, kaolinite, xonotlite, sepiolite, attapulgite clay, montmorillonite, bentonite, and montmorillonite; silica, alumina, calcium carbonate, and the like. Glass fiber, glass flake, mica, and the like are preferred. Among them, glass flakes and mica are preferable from the viewpoint of dimensional accuracy. The other inorganic fillers (F) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

In order to improve the adhesiveness with the polycarbonate resin (a), the inorganic filler such as talc may be surface-treated with various surface-treating agents such as silane-treating agents. The surface treatment agent is not particularly limited, and conventionally known surface treatment agents can be used. The surface-treating agent is preferably a hydrogen siloxane compound such as methylhydrogensiloxane, an epoxy group-containing silane coupling agent such as epoxysilane, or an amino group-containing silane coupling agent such as aminosilane, because these compounds hardly deteriorate the physical properties of the polycarbonate resin (A). Furthermore, polyoxyethylene silane and the like can also be used.

The method for treating the inorganic filler with the surface treatment agent is not particularly limited, and can be carried out by a usual method. For example, the surface treatment agent may be added to talc, and the mixture may be stirred or mixed in the solution or while heating.

The content of the inorganic filler in the polycarbonate resin composition of the present invention is 20 to 45 parts by mass per 100 parts by mass of the polycarbonate resin (A). If the content of the inorganic filler is less than 20 parts by mass, the effect of improving rigidity and dimensional stability is insufficient. If the content of the inorganic filler exceeds 45 parts by mass, problems such as embrittlement (reduction in impact strength) and deterioration in appearance may occur. From these viewpoints, the content of the inorganic filler is preferably 25 to 40 parts by mass, particularly 25 to 35 parts by mass, based on 100 parts by mass of the polycarbonate resin (a).

< phosphorus Compound (G) >

In the polycarbonate resin composition of the present invention, it is preferable to contain a phosphorus compound (G) other than the phosphorus flame retardant (C) in order to improve thermal stability and chemical resistance. The phosphorus compound (G) preferably includes a phosphite ester represented by the following formula (1), a phosphate ester represented by the following formula (2), and a phosphate ester metal salt represented by the following formula (5) or (6).

These phosphorus compounds will be described below.

[ solution 9]

In the formula (1), R¹Is alkyl or aryl. 2R¹May be the same or different.

[ solution 10]

In the formula (2), R²Is alkyl or aryl. (3-n) R²May be the same or different. n represents an integer of 0 to 2.

[ solution 11]

In the formulae (5) and (6), R³Is alkyl or aryl. M is a metal.

(phosphite ester)

In the formula (1), R¹When the alkyl group is used, the alkyl group has 1 to 30 carbon atoms is preferable, and a stearyl group and a nonyl group are particularly preferable. R¹In the case of an aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group having an alkyl group as a substituent is particularly preferable.

Specific examples of the phosphite ester include distearylpentaerythritol diphosphite, dinonylpentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-isopropylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and the like.

Among the above, the preferred phosphite ester is distearylpentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and distearylpentaerythritol diphosphite is particularly preferred.

(phosphoric acid ester)

In the formula (2), R²Preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, more preferablyAlkyl group having 2 to 25 carbon atoms, phenyl group, nonylphenyl group, stearylphenyl group, 2, 4-di-t-butylphenyl group, 2, 4-di-t-butyl-methylphenyl group, and tolyl group, and particularly preferably alkyl group having 2 to 25 carbon atoms. Examples of the alkyl group include octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, and octadecyl.

n is preferably 1 or 2.

(phosphate Metal salt)

In the formulae (5) and (6), R³Preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, more preferably an alkyl group having 2 to 25 carbon atoms, a phenyl group, a nonylphenyl group, a stearylphenyl group, a 2, 4-di-t-butylphenyl group, a 2, 4-di-t-butyl-methylphenyl group or a tolyl group, and particularly preferably an alkyl group having 2 to 25 carbon atoms. As the alkyl group, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl and the like are mentioned.

M may be a metal such as an alkali metal, an alkaline earth metal, zinc, or aluminum.

In particular, the phosphorus compound (G) is preferably the above-mentioned phosphite ester, phosphate ester or phosphate ester metal salt having an alkyl group having 10 or more carbon atoms, and particularly preferably a phosphite ester, phosphate ester or phosphate ester metal salt having a stearyl group as the alkyl group, from the viewpoint of chemical resistance.

As phosphite, distearyl pentaerythritol diphosphite is preferred.

As the phosphoric ester, R is more preferable²The alkyl group of (2) has 13, 18 or 24 carbon atoms, and a mixture of distearyl acid phosphate represented by the following formula (2A) wherein n is 1 and monostearyl acid phosphate wherein n is 2 in the formula (2A) is particularly preferred.

O＝P(OH)_n(OC₁₈H₃₇)_3-n…(2A)

As the metal phosphate, R is preferred³The alkyl group of (2) has 13, 18 or 24 carbon atoms, and M is zincParticularly preferred is a mixture of a zinc salt of distearyl acid phosphate represented by the following formulae (5A) and (6A) and represented by the following formula (5A) and a zinc salt of monostearyl acid phosphate represented by the following formula (6A).

[ solution 12]

These phosphorus compounds (G) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the polycarbonate resin composition of the present invention contains the phosphorus compound (G), the content of the phosphorus compound (G) in the polycarbonate resin composition is preferably 0.05 to 1 part by mass, more preferably 0.1 to 0.7 part by mass, and still more preferably 0.2 to 0.5 part by mass, based on 100 parts by mass of the polycarbonate resin (a). When the content of the phosphorus compound (G) is not less than the lower limit, the effects of thermal stability, chemical resistance, and the like due to the phosphorus compound (G) can be sufficiently obtained. Even if the content of the phosphorus compound (G) is too large, the effect corresponding to the content may not be obtained, and problems such as deterioration of hydrolysis resistance and mold deposit may be caused, so that the content of the phosphorus compound (G) is preferably not more than the upper limit.

When the polycarbonate resin composition of the present invention contains the phosphorus compound (G), the content of the phosphorus compound (G) in the polycarbonate resin composition is preferably 0.2 to 2.0% by mass, more preferably 0.5 to 1.8% by mass, and further preferably 0.8 to 1.5% by mass, based on the talc (E). When the content ratio of the phosphorus compound (G) to talc (E) (hereinafter sometimes referred to as "(G)/(E) ratio") is not less than the lower limit, the effects of the phosphorus compound (G) such as thermal stability and chemical resistance can be sufficiently obtained. Even if the ratio (G)/(E) is too large, the effect corresponding to this may not be obtained, and problems such as reduction in hydrolysis resistance and mold deposit may occur, so the ratio (G)/(E) is preferably not more than the upper limit.

< other thermoplastic resins >

The polycarbonate resin composition of the present invention may contain a thermoplastic resin other than the polycarbonate resin (a) within a range not impairing the effects of the present invention. The kind and amount of the other thermoplastic resin may be appropriately selected for the purpose of improving the moldability, chemical resistance, and other properties. Examples of the thermoplastic resin other than the polycarbonate resin (a) include thermoplastic polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and copolyester, polyolefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene and High Impact Polystyrene (HIPS), acrylic resins such as polyacrylate and polymethacrylate, polyamide resins, polyimide resins, polyamideimide resins, polyetherimide resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, and polyphenylene sulfide resins. The thermoplastic resin other than the polycarbonate resin (A) may contain 1 kind, or may contain 2 or more kinds in any combination and ratio.

When a thermoplastic resin other than the polycarbonate resin (a) is contained in the polycarbonate resin composition of the present invention, the compounding amount thereof is preferably less than 50% by mass, more preferably 30% by mass or less, and most preferably 20% by mass or less of the total amount of the polycarbonate resin (a) and the thermoplastic resin other than the polycarbonate resin (a).

< additives >

In order to obtain desired physical properties, the polycarbonate resin composition of the present invention may be blended, as necessary, with various additives, for example, an impact resistance modifier, an ultraviolet absorber, an antioxidant, a stabilizer such as a heat stabilizer other than the phosphorus compound (G), a pigment, a dye, a lubricant, a flame retardant other than the phosphorus flame retardant (C), a mold release agent, a sliding property improver, and the like.

(impact modifier)

The impact resistance modifier may be a core/shell type graft copolymer. As the impact resistance modifier, a core/shell type graft copolymer is preferred which has a rubber component as a core layer and contains a shell layer around the rubber component, the shell layer being formed by copolymerizing at least one monomer component selected from the group consisting of (meth) acrylate compounds, (meth) acrylic acid compounds, aromatic vinyl compounds, unsaturated nitrile compounds, and the like.

Specific examples of the rubber component include polyalkyl acrylate rubbers such as polybutadiene rubber, polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate) and butyl acrylate-2-ethylhexyl acrylate copolymer, silicone rubbers such as polyorganosiloxane rubbers, butadiene-acrylic acid composite rubbers, silicone-acrylate composite rubbers, styrene-butadiene rubbers, ethylene-propylene rubbers, ethylene-butene rubbers, ethylene-octene rubbers and other ethylene- α -olefin rubbers, ethylene-acrylate rubbers, fluororubbers and the like. These components may be used alone, or 2 or more of them may be mixed and used.

As the core/shell type graft copolymer, a graft copolymer having a silicone-acrylate composite rubber as a core is preferable. Particularly preferred is a core/shell type graft copolymer having an acrylic polymer or copolymer component as a shell layer around a core of the silicone-acrylate composite rubber.

The silicone-acrylate composite rubber constituting the core layer is preferably composed of a polyorganosiloxane (e.g., a polymer containing a dimethylsiloxane unit as a constituent unit) and an acrylic component such as a (meth) acrylate compound or an unsaturated nitrile compound such as acrylonitrile.

The shell of the acrylic component is obtained by polymerizing a (meth) acrylate compound, a (meth) acrylic acid compound, and the like.

Examples of the (meth) acrylate compound include alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and hexyl methacrylate; aryl (meth) acrylates such as phenyl methacrylate and naphthyl methacrylate; glycidyl group-containing (meth) acrylates such as glycidyl acrylate and glycidyl methacrylate; and so on. Among them, alkyl methacrylate is preferable, and methyl methacrylate is more preferable.

The (meth) acrylate compound may be used in 1 kind or 2 or more kinds.

Other vinyl monomers may be contained in addition to the (meth) acrylate compound. Examples of the other vinyl monomer include: aromatic vinyl groups such as styrene and α -methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; 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, or anhydrides thereof (e.g., maleic anhydride); and so on.

In addition, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene; unsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, 1, 3-butanediol diacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, etc.; unsaturated carboxylic acid allyl esters such as allyl acrylate and allyl methacrylate; and crosslinkable monomers such as diallyl phthalate, diallyl sebacate, and triallyl triazine, and diallyl and triallyl compounds.

When the polycarbonate resin composition of the present invention contains an impact modifier, the content thereof is 1 to 10 parts by mass, preferably 3 to 8 parts by mass, based on 100 parts by mass of the polycarbonate resin (a). When the content of the impact resistance modifier is 1 part by mass or more, the impact resistance-improving effect can be sufficiently obtained. When the content of the impact resistance modifier is 10 parts by mass or less, the deterioration of heat resistance and flame retardancy can be suppressed.

(antioxidant)

Examples of the antioxidant include hindered phenol antioxidants. Specific examples thereof include pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 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 ] phosphate, 3,3 ', 3', 5,5 '-hexa-tert-butyl-a, a' - (trimethylbenzene-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. More than 2 of them may be used in combination.

Among the above, pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate are preferred. These 2 phenolic antioxidants are commercially available under the names "IRGANOX 1010" and "IRGANOX 1076" from Ciba Specialty Chemicals.

When the polycarbonate resin composition of the present invention contains an antioxidant, the amount thereof is usually 0.001 to 1 part by mass, preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the polycarbonate resin (a) in the polycarbonate resin composition of the present invention. When the amount of the antioxidant is 0.001 parts by mass or more, the effect as an antioxidant is sufficient. When the compounding amount of the antioxidant exceeds 1 part by mass, the effect is not further improved. When the compounding amount of the antioxidant is 1 part by mass or less, problems such as mold deposit are not caused.

(mold releasing agent)

The release agent includes at least one compound selected from the group consisting of 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 15000, and a silicone-based silicone oil.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic 1-, 2-or 3-membered carboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. The aliphatic carboxylic acid is preferably a 1-or 2-membered carboxylic acid having 6 to 36 carbon atoms, and more preferably an aliphatic saturated 1-membered carboxylic acid having 6 to 36 carbon atoms. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetradecanoic acid, montanic acid, adipic acid, and azelaic acid.

As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same aliphatic carboxylic acids as described above can be used. Examples of the alcohol include saturated or unsaturated 1-or polyhydric alcohols. The alcohol may have a substituent such as a fluorine atom or an aryl group. The alcohol is preferably a 1-membered or polyhydric saturated alcohol having not more than 30 carbon atoms, and more preferably an aliphatic saturated 1-membered or polyhydric alcohol having not more than 30 carbon atoms. Aliphatic also includes alicyclic compounds. Specific examples of the alcohol include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like.

The ester compound may contain an aliphatic carboxylic acid and/or an alcohol as impurities, or may be a mixture of 2 or more compounds.

Specific examples of the ester of an aliphatic carboxylic acid and an alcohol include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl 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 15000 include liquid paraffin, solid paraffin, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and an α -olefin oligomer having 3 to 12 carbon atoms. As the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. These hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight of the aliphatic hydrocarbon is preferably 200 to 5000. The aliphatic hydrocarbon may be a single substance or a mixture of different components and different molecular weights as long as the main component is within the above range.

Examples of the silicone-based silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluoroalkyl silicone oil.

When a release agent is contained in the polycarbonate resin composition of the present invention, the compounding amount thereof is usually 0.001 to 2 parts by mass, preferably 0.01 to 1 part by mass, based on 100 parts by mass of the polycarbonate resin (a) in the polycarbonate resin composition of the present invention. When the compounding amount of the release agent is 0.001 parts by mass or more, the effect of releasability is sufficient. When the compounding amount of the release agent is 2 parts by mass or less, problems such as deterioration of hydrolysis resistance and mold deposit do not occur.

(ultraviolet absorber)

Specific examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds and triazine compounds. Among these, organic ultraviolet absorbers are preferred. Particularly preferred is at least one selected from the group consisting of benzotriazole compounds, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- (octyloxy) phenol, 2' - (1, 4-phenylene) bis [4H-3, 1-benzoxazin-4-one ], [ (4-methoxyphenyl) -methylene ] -malonic acid dimethyl ester.

Specific examples of the benzotriazole compound include a condensate of methyl-3- [ 3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] propionate-polyethylene glycol. Specific examples of the other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ', 5 ' -di-tert-butyl-2 ' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [ 2-hydroxy-3, 5-bis (. alpha., α -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2' -methylene-bis [4- (1,1,3, 3-tetramethylbutyl) -6- (2N-benzotriazole 2-yl) phenol ] [ methyl-3- [ 3-tert-butyl-5- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] propionate-polyethylene glycol ] condensate, and the like. These substances may be used in combination of 2 or more.

Among the above, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol are preferable, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- (octyloxy) phenol, 2' -methylene-bis [4- (1,1,3, 3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol ].

When the polycarbonate resin composition of the present invention contains an ultraviolet absorber, the amount thereof is usually 0.01 to 3 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the polycarbonate resin (a) in the polycarbonate resin composition of the present invention. When the amount of the ultraviolet absorber is 0.01 parts by mass or less, the effect of improving weather resistance is sufficient; when the blending amount of the ultraviolet absorber is 3 parts by mass or less, problems such as mold deposit can be suppressed.

(dye/pigment)

Examples of the dye/pigment include inorganic pigments, organic pigments, and organic dyes.

Examples of the inorganic pigment include: sulfide-based pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; oxide-based pigments such as zinc white, red iron oxide, chromium oxide, titanium oxide, iron black, titanium yellow, zinc-iron-based brown, titanium-cobalt-based green, cobalt blue, copper-chromium-based black, and copper-iron-based black; chromic acid-based pigments such as chrome yellow and molybdate orange; and ferrocyanide pigments such as prussian blue.

Examples of the organic pigment and the organic dye include phthalocyanine-based dyes/pigments such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes/pigments such as nickel-complex azo yellow; fused polycyclic dyes/pigments such as thioindigo-based, perinone-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, quinophthalone-based, and the like; anthraquinone-based, heterocyclic-system, methyl-based dyes/pigments, and the like.

These components may be used in combination of 2 or more.

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

When the dye/pigment is contained in the polycarbonate resin composition of the present invention, the compounding amount thereof is usually 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 12 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (a) in the polycarbonate resin composition of the present invention. When the amount of the dye/pigment mixture is 20 parts by mass or less, the impact resistance is not impaired.

< method for producing polycarbonate resin composition >

The polycarbonate resin composition of the present invention can be produced by mixing the respective components by a conventionally known method and melt-kneading the mixture. Specific mixing methods include the following: predetermined amounts of the thermoplastic resin (a), the flowability modifier (B), the phosphorus-based flame retardant (C), the fluoropolymer (D), the inorganic filler containing talc (E), and the phosphorus compound (G) and other additive components blended as needed are weighed, mixed by various mixers such as a tumbler mixer and a henschel mixer, and then melt-kneaded by a banbury mixer, a roll, a brabender extruder, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, and the like.

< suitable physical Properties of polycarbonate resin composition >

The polycarbonate resin composition of the present invention preferably has excellent flame retardancy such that the flame retardancy at a thickness of 2mm in the UL94 test described in the following example section satisfies 5 VB.

The polycarbonate resin composition of the present invention has an unnotched Charpy impact strength of 35kJ/m at a thickness of 4mm according to ISO179 described in the examples section below²Above, in particular 40kJ/m²The above high impact resistance.

The polycarbonate resin composition of the present invention has high rigidity such that the flexural modulus according to ISO178 described in the examples section below is 5,000MPa or more.

The polycarbonate resin composition of the present invention has excellent chemical resistance such that the retention of tensile rupture strength is 70% or more in the evaluation of chemical resistance described in the following examples. The tensile strength at break is preferably 80% or more, more preferably 90% or more.

[ molded article ]

The molded article of the present invention is obtained by molding the polycarbonate resin composition of the present invention.

As a molding method for producing the molded article of the present invention, a conventionally known method of molding a molded article from a thermoplastic resin material can be used without limitation. Specifically, there may be mentioned a common injection molding method, an ultrahigh-speed injection molding method, an injection extrusion molding method, a two-color molding method, a hollow molding method such as a gas assist molding method, a molding method using a heat insulating mold, a molding method using a rapid-heating mold, a foam molding (including a supercritical fluid), an insert molding, an in-mold coating (IMC) molding method, an extrusion molding method, a sheet molding method, a thermoforming method, a rotational molding method, a lamination molding method, a press molding method and the like.

[ use ]

The molded article of the present invention is excellent in rigidity, flame retardancy, fluidity, dimensional accuracy, impact resistance and chemical resistance, and can be suitably used for various applications. In particular, the molded article of the present invention can be suitably used for chassis, frame material, optical housing, and the like of OA equipment.

Examples

The present invention will be described more specifically with reference to the following examples. The present invention is not limited to the following examples, and can be implemented by being arbitrarily changed within a range not departing from the gist of the present invention.

[ materials used ]

The raw materials used in the following examples and comparative examples are shown in tables 1 and 2 below.

[ Table 1]

[ Table 2]

[ evaluation method ]

The evaluation methods of various properties and physical properties in the following examples and comparative examples are as follows.

< flowability >

The pellets obtained in examples and comparative examples were dried at 100 ℃ for 6 hours, and then subjected to injection molding using NEX80III (mold clamping force 80 tons) manufactured by Nichisu resin industries, under conditions of a cylinder temperature of 280 ℃, a mold temperature of 60 ℃, an injection pressure of 100MPa, and a molding cycle of 40 seconds, to obtain a rod flow molding having a width of 20mm and a thickness of 2mm, and the flow length (unit: mm) thereof was evaluated.

The value is preferably about 200 to 350 mm.

< anisotropy of mold shrinkage >

The pellets obtained in examples and comparative examples were dried at 100 ℃ for 6 hours, and then injection-molded into test pieces 80mm long, 40mm wide and 3.2mm thick using NEX80III (mold clamping force 80 tons) manufactured by Nichisu resin industries, under conditions of a cylinder temperature of 280 ℃, a mold temperature of 80 ℃, an injection pressure of 90MPa and a molding cycle of 45 seconds. The dimensions of the resin in the flow direction (MD) and The Direction (TD) perpendicular to the flow of the obtained test piece were measured, the shrinkage was calculated from the dimensions of the mold, the MD value was divided by the TD value, and the anisotropy of the molding shrinkage was evaluated from the obtained value.

As the value calculated by this method approaches 1, the smaller the anisotropy of the shrinkage ratio, and the more excellent the dimensional accuracy and low warpage.

< bending characteristics >

The flexural modulus and flexural strength were measured in accordance with ISO178 using ISO multipurpose test pieces having a thickness of 4mm obtained in examples and comparative examples, and evaluated. The flexural modulus is preferably 5000MPa or more. The bending strength is preferably 110MPa or more.

< impact resistance >

Using the ISO multipurpose test pieces 4mm thick obtained in examples and comparative examples, unnotched Charpy impact strength was measured in accordance with ISO179 and evaluated. This value was 35kJ/m²The higher the content, the more preferable the content.

< Heat resistance >

Using the ISO multipurpose test pieces 4mm thick obtained in examples and comparative examples, the load deflection temperature of 1.8MPa was measured in accordance with ISO75 and evaluated. The higher the deformation temperature under load, the more excellent the heat resistance.

< evaluation of flame retardancy >

The test pieces for UL test obtained in examples and comparative examples were conditioned in a thermostatic chamber at a temperature of 23 ℃ and a humidity of 50% for 48 hours, and subjected to a 5V strip specimen burning test in accordance with the UL94 test (plastic material burning test for parts of equipment) specified by the Underwriters Laboratories (UL). The 5V bar sample burn test was the following method: with respect to a test piece of a predetermined size kept vertical, the flame was contacted at a predetermined position of the test piece for 5 seconds at a predetermined flame size and at a burner angle, and kept for 5 seconds, and this operation was repeated 4 times, and further the flame was contacted for 5 seconds (5 th time), and thereafter, the flame retardancy was evaluated based on the follow-up time and the dripping property. The test was carried out using a total of 5 test pieces. In order to have flame retardancy of 5VB, all of 5 test pieces should satisfy the criteria shown in Table 3 below.

[ Table 3]

Afterflame time after 5 th flame contact	Less than 60 seconds
		Caused by dripping from the test stripCotton ignition	Is free of

The follow-on time herein is the sum of the time during which the test piece continues to burn with a flame after the ignition source is removed and the time during which the test piece continues to emit light (in the presence of a fire). Ignition of cotton due to dripping can be determined by whether or not cotton for marking located at a position below about 300mm from the lower end of the test piece is ignited by dripping (dripping) from the test piece.

In tables 4 to 14, the expression "NR" means not satisfying 5 VB.

The average of the afterflame times of 5 test pieces in the 5V strip combustion was calculated separately from the 5VB determination. The smaller the value, the higher the self-extinguishing property and the higher the flame retardancy.

< chemical resistance >

The ISO multipurpose test pieces having a thickness of 3mm obtained in examples and comparative examples were fixed to a jig, bent at a strain of 1%, coated with a rust preventive agent "Barrier Guard PartII" (colorless, manufactured by Shanghai chemical industries, Ltd.), and kept in a hot air oven set at 55 ℃ for 72 hours. Thereafter, the test piece was removed from the jig, the tensile strength at break was measured in accordance with ISO527, and the value was divided by the value of the tensile strength at break of the untreated test piece, and the obtained value was evaluated as the retention rate of the tensile strength at break. This value is 70% or more, preferably 80% or more, and more preferably 90% or more, and the higher the value is, the more preferable the higher the value is.

Examples 1 to 37 and comparative examples 1 to 20

< production of resin pellets >

The raw materials shown in tables 4 to 14 were used, and the components other than the phosphorus flame retardant (C) were mixed in the proportions shown in tables 4 to 14, and the mixture was mixed for 20 minutes in a tumble mixer. The mixture was fed from an upstream feeder to a twin-screw extruder "TEX 30 alpha" manufactured by Nippon Steel works having 1 vent, and the phosphorus-based flame retardant (C) was kneaded under conditions of a rotation speed of 200rpm, a discharge rate of 30kg/h, and a barrel temperature of 270 ℃ while being fed from the middle of the barrel by an infusion pump. The molten resin extruded into strands was cooled in a water tank and pelletized using a pelletizer to obtain pellets of the polycarbonate resin composition.

< preparation of test piece >

The obtained pellets were dried at 100 ℃ for 6 hours, and then injection-molded using an injection molding machine "Si-80-6" (mold clamping force 80 ton) manufactured by Toyo Mechanical Co., Ltd under conditions of a cylinder temperature of 280 ℃, a mold temperature of 60 ℃ and a molding cycle of 50 seconds to obtain ISO multipurpose test pieces having a thickness of 4 mm.

Similarly, the obtained pellets were dried at 100 ℃ for 6 hours, and then injection-molded using an injection molding machine "EC 75 SX" (mold clamping force of 75 tons) manufactured by Toshiba mechanical Co., Ltd under conditions of a cylinder temperature of 280 ℃, a mold temperature of 60 ℃ and a molding cycle of 48 seconds, to obtain ISO multipurpose test pieces having a thickness of 3 mm.

Similarly, the obtained pellets were dried at 100 ℃ for 6 hours, and then injection-molded using an injection molding machine "SE 100D" (clamping force 100 ton) manufactured by Sumitomo heavy machinery industries under conditions of a cylinder temperature of 280 ℃, a mold temperature of 60 ℃ and a molding cycle of 30 seconds, to obtain a UL test piece having a length of 125mm, a width of 13mm and a thickness of 2 mm.

The pellets and test pieces thus obtained were used to conduct the above evaluations, and the results are shown in tables 4 to 14.

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

[ Table 12]

[ Table 13]

[ Table 14]

As is clear from tables 4 to 14, the polycarbonate resin compositions of the present invention are all excellent in rigidity, flame retardancy, flowability, dimensional accuracy, impact resistance and chemical resistance.

On the other hand, in comparative examples 1 to 20 which did not satisfy the conditions of the present invention, any of rigidity, flame retardancy, fluidity, dimensional accuracy, impact resistance and chemical resistance was poor.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes can be made therein without departing from the spirit and scope thereof.

The present application is based on japanese patent application 2019-.