JP2015078284A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having extremely improved flowability, impact strength resistance (surface impact strength) and chemical resistance during injection molding while maintaining moldability, heat resistance or the like.SOLUTION: There is provided a polycarbonate resin composition containing 100 pts.wt. of a resin component consisting of a polycarbonate resin (A) of 95 to 40 wt.% and a rubber reinforced styrenic resin (B) of 5 to 60 wt.%, 0.1 to 5 pts.mass of alkyl ketene dimer (C) of the following formula and 3 to 30 pts.wt. of a glass fiber (D).

Description

  The present invention relates to a polycarbonate resin composition excellent in fluidity, impact strength, and chemical resistance during injection molding. More specifically, fluidity, impact strength, and chemical resistance at the time of injection molding while maintaining the moldability, heat resistance, etc., which are the characteristics of a resin composition comprising a blend of a polycarbonate resin and a rubber-reinforced styrene resin. It is related with the polycarbonate resin composition which improved significantly.

  Conventionally, a resin composition comprising a blend of a polycarbonate resin and a rubber-reinforced styrene resin is excellent in impact resistance, heat resistance, paintability, and the like, and thus has been widely used in fields such as electricity, electronics, and automobiles. However, when a molded product obtained from the resin composition is coated, defects such as cracking may occur due to chemicals and solvents such as thinner used for coating, and resistance to such defects does not occur. There is a demand for a resin composition excellent in chemicals.

  As a method for improving chemical resistance, a method of blending polyamide, which is a crystalline resin having excellent chemical resistance, has been proposed (Patent Document 1). However, when a crystalline resin is blended, the molding shrinkage ratio is increased. It is not preferable because the mold used in the resin composition cannot be used and the mechanical strength is lowered due to insufficient compatibility with the resin composition.

On the other hand, in the past, polycarbonate resin compositions are often used in applications in fields such as electricity, electronics, and automobiles. For example, the mechanical strength of a casing of a thin-walled portable information device terminal or the like is insufficient (fluidity). In order to improve the mechanical strength, heat resistance, dimensional stability, etc. of this resin composition, glass fibers may be added to improve the problem. Increasing cases. However, although mechanical strength and dimensional stability are improved by adding glass fiber, there may be a new problem that the fluidity at the time of injection molding and the impact strength of the resulting product are reduced. There is a demand for a polycarbonate resin composition having improved fluidity and impact strength so that such new problems do not occur. Also, in applications in these fields, there is a very high risk that a product using the resin composition will break or chip due to dropping, etc., so that the resin composition with high impact resistance, especially surface impact strength. There is a high demand for things.
And the method of mix | blending a polycarbonate polyorganosiloxane copolymer with a polycarbonate resin, for example until now is proposed (patent document 2). However, even in the above method, impact strength such as fluidity and drop strength of the product is not sufficiently solved.

  Thus, the present condition is that the polycarbonate resin composition which was excellent in the chemical resistance, and was excellent in the fluidity | liquidity at the time of injection molding, and the impact resistance strength (surface impact strength) until now.

Japanese Patent Publication No. 6-313091 Japanese Patent Laid-Open No. 2-173061

  An object of the present invention is that a polycarbonate resin composition excellent in fluidity, impact strength (surface impact strength) and chemical resistance at the time of injection molding has not been developed. Polycarbonate resin with significantly improved fluidity, impact strength (surface impact strength) and chemical resistance, especially during injection molding, while maintaining the molding processability, heat resistance, etc., characteristic of the resin composition comprising An object is to provide a composition.

  As a result of intensive studies in view of such problems, the present inventors have formulated a specific alkyl ketene dimer and glass fiber in a specific ratio in a resin composition comprising a blend of a polycarbonate resin and a rubber-reinforced styrene resin. As a result, it was surprisingly found that the fluidity, impact resistance (surface impact resistance), and chemical resistance during injection molding can be drastically improved, and the present invention has been completed.

That is, the present invention relates to an alkyl ketene dimer (C) represented by the following general formula 1 per 100 parts by weight of a resin component comprising 95 to 40% by weight of a polycarbonate resin (A) and 5 to 60% by weight of a rubber-reinforced styrene resin (B). ) 0.1 to 5 parts by weight, and 3 to 30 parts by weight of glass fiber (D). A polycarbonate resin composition is provided.
General formula 1:

（一般式１において、Ｒは、同一でも異なっても良いが、炭素数６〜３３のアルキル基をあらわす。）

(In General Formula 1, R may be the same or different, but represents an alkyl group having 6 to 33 carbon atoms.)

  The polycarbonate resin composition of the present invention has fluidity and impact strength at the time of injection molding while maintaining the moldability, heat resistance, etc., which are the characteristics of a resin composition comprising a blend of a polycarbonate resin and a rubber-reinforced styrene resin. (Surface impact strength) and chemical resistance are drastically improved. When such a resin composition is used, for example, when thin-walled portable information device terminals are injection molded, insufficient filling It is possible to suppress the occurrence of such problems. In addition, the occurrence of problems such as the falling of heavy objects on the product and the occurrence of cracks when the product itself is dropped, and even if various chemicals and solvents such as thinner adhere to the molded product obtained from such a resin composition. There is a remarkable effect that the occurrence of defects such as cracks can be suppressed.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The compounding quantity of polycarbonate resin (A) is 95 to 40 weight%. If it exceeds 95% by weight, the fluidity at the time of injection molding is inferior, and if it is less than 40% by weight, the heat resistance and the like are inferior. A preferable blending amount is 90 to 50% by weight, and more preferably 80 to 60% by weight.

  The viscosity average molecular weight of the polycarbonate resin (A) is not particularly limited, but is usually in the range of 10,000 to 100,000, more preferably 14,000 to 30,000, and even more preferably 16,000 to 26,000 in terms of moldability and strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

  The rubber-reinforced styrene resin (B) used in the present invention is an acrylonitrile / butadiene / styrene copolymer (ABS resin), a high impact polystyrene resin (HIPS), or a methyl methacrylate / butadiene / styrene copolymer (MBS). Resin). Examples of a preferable rubber-reinforced styrene resin (B) include those containing a graft copolymer obtained by graft copolymerization of an aromatic vinyl monomer and a vinyl cyanide monomer component in the presence of a rubbery polymer. More preferred is an ABS resin made by bulk polymerization.

The compounding amount of the rubber-reinforced styrene resin (B) is 5 to 60% by weight (based on the total amount with the polycarbonate resin (A)). When the blending amount of the rubber-reinforced styrene resin (B) is less than 5% by weight, the fluidity and molding processability are inferior. The preferred blending amount is 10 to 50% by weight, more preferably 20 to 30% by weight.
The alkyl ketene dimer (C) used in the present invention is a compound represented by the following general formula.
General formula 1:

  In General Formula 1, R may be the same or different, but is an alkyl group having 6 to 33 carbon atoms, preferably an alkyl group having 10 to 21 carbon atoms. Most preferably, R is an alkyl group having 15 to 18 carbon atoms.

  The compounding amount of the alkyl ketene dimer (C) is 0.1 to 5 parts by weight per 100 parts by weight of the resin component consisting of 95 to 40% by weight of the polycarbonate resin (A) and 5 to 60% by weight of the rubber-reinforced styrene resin (B). It is. If the amount is less than 0.1 parts by weight, the surface (falling weight) impact strength is inferior. If the amount exceeds 5 parts by weight, pellets cannot be produced due to inferior thermal stability, such as occurrence of silver in the injection molded product, or difficulty in granulation. It is not preferable because there are cases. A preferable blending amount is 0.1 to 3 parts by weight, more preferably 1 to 3 parts by weight per 100 parts by weight of the resin component.

As the glass fiber (D) used in the present invention, any glass fiber that is usually used in thermoplastic resins can be used. The glass used for the glass fiber is preferably alkali-free glass (E glass), the diameter of the glass fiber is preferably 5 to 20 μm, and the number average fiber length of the glass fiber is preferably 1 to 8 mm.
These are produced according to any conventionally known method.

  If the diameter of the crow fiber is less than 5 μm, it is difficult to obtain it because it is inferior in productivity in mass production. When the number average fiber length is 1 mm or less, the mechanical strength is not sufficiently improved. When the number average fiber length exceeds 8 mm, the glass fiber drops from the resin because the dispersibility of the glass fiber in the polycarbonate resin is inferior when the polycarbonate resin is produced. Etc., productivity is likely to decrease. The diameter of the glass fiber is preferably 8 to 15 μm, and the number average length is preferably 2 to 6 mm.

  The glass fiber (D) can be surface-treated with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion to the polycarbonate resin. Further, when glass fiber is handled, it can be focused by a bundling material such as urethane or epoxy for the purpose of improving the handleability.

  The compounding amount of the glass fiber (D) is 3 to 30 parts by weight per 100 parts by weight of the resin component consisting of 95 to 40% by weight of the polycarbonate resin (A) and 5 to 60% by weight of the rubber-reinforced styrene resin (B). . If it is less than 3 parts by weight, the flexural modulus is inferior, and if it exceeds 30 parts by weight, the surface impact strength is inferior. A preferable blending amount is 5 to 20 parts by weight, more preferably 5 to 15 parts by weight.

  There are no particular limitations on the method of blending the various blending components (A), (B), (C) and (D) of the present invention, and these may be mixed using any mixer such as a tumbler, ribbon blender, high-speed mixer or the like. It can be melt-kneaded with a normal single-screw or twin-screw extruder or the like. Moreover, there is no restriction | limiting in particular also about the mixing | blending order of these compounding components, collective mixing, and division | segmentation mixing.

  When mixing, other known additives such as mold release agents, ultraviolet absorbers, antistatic agents, antioxidants, thermal stabilizers, dyes and pigments, epoxy soy oil, liquid paraffin as necessary Etc.) and reinforcing materials other than glass fibers (carbon fiber, talc, mica, etc.), and other resins can be blended.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified.

The compounding components used are as follows.
Polycarbonate resin (A):
Polycarbonate resin synthesized from bisphenol A and phosgene (Caliber 200-20 manufactured by Sumika Stylon Polycarbonate Co., Ltd.)
Viscosity average molecular weight: 19000, hereinafter abbreviated as PC)
Rubber reinforced styrene resin (B):
Bulk polymerization method ABS resin (Santac AT05, manufactured by Nippon A & L Co., Ltd., rubber amount: 20%,
Hereinafter abbreviated as ABS)
Alkyl ketene dimer (C):
AKD1840 (hereinafter abbreviated as AKD) manufactured by Eiheng Chemical Company
The ingredients are as follows:

上記式でＲは炭素数が１５〜１８のアルキル基であるアルキルケテンダイマー
ガラス繊維（Ｄ）：
無アルカリガラス繊維
（オーウェンスコーニングジャパン（株） ＣＳ０３ＭＡＦＴ７３７）
繊維直径１３μｍ、数平均繊維長３ｍｍ（以下、ＧＦと略記）

In the above formula, R is an alkyl ketene dimer glass fiber (D), which is an alkyl group having 15 to 18 carbon atoms:
Alkali-free glass fiber (Owens Corning Japan Co., Ltd. CS03MAFT737)
Fiber diameter 13 μm, number average fiber length 3 mm (hereinafter abbreviated as GF)

  The above-mentioned various blending components are collectively put into a tumbler at the blending ratio shown in Table 1, and after dry mixing for 10 minutes, using a single screw extruder (Tanabe Plastic VS40-3) at a melting temperature of 260 ° C. It knead | mixed and the pellet of the polycarbonate resin composition was obtained.

Hereinafter, each evaluation item and measurement method in the present invention will be described.
(Evaluation of surface impact strength)
The pellets of the resin compositions obtained above were each dried at 95 ° C. for 4 hours, and then set using an injection molding machine (Japan Steel Works J-100E-C5) at a set temperature of 250 ° C. and an injection pressure of 1600 kg / cm ^2. A test piece (60 × 60 × 2 mm) was prepared.
Using the obtained test piece, the 50% fracture energy was determined according to JIS K-7221 and defined as the surface impact strength. A surface impact strength of 70 kg / cm or more was considered good.

(Evaluation of flexural modulus)
The pellets of the resin compositions obtained above were each dried at 95 ° C. for 4 hours, and then set using an injection molding machine (Japan Steel Works J-100E-C5) at a set temperature of 250 ° C. and an injection pressure of 1600 kg / cm ^2. A test piece according to the ISO test method was prepared, and the bending elastic modulus was measured according to ISO 178 using the obtained test piece, and the bending elastic modulus was determined to be 2800 MPa or more.

(Evaluation of liquidity)
The pellets of the various resin compositions obtained above were dried at 95 ° C. for 4 hours, respectively, and then a spiral flow mold (1 mm thickness) at a set temperature of 250 ° C. and an injection pressure of 160 MPa using an injection molding machine (S2000i100B manufactured by FАNUC). ) Was used to measure the flow length, and 80 mm or more was considered good.

(Evaluation of chemical resistance)
The pellets of the resin compositions obtained above were each dried at 95 ° C. for 4 hours, and then set using an injection molding machine (Japan Steel Works J-100E-C5) at a set temperature of 250 ° C. and an injection pressure of 1600 kg / cm ^2. A test piece (127 × 13 × 3.2 mm) was prepared.
The obtained test piece was subjected to 0.3% strain using a cantilever chemical resistance test jig (see the following formula), and the following chemicals were respectively applied to the center of the test piece.
Drug for evaluation No5700 thinner manufactured by Ohashi Chemical Industry Co., Ltd. (hereinafter abbreviated as thinner)
The test piece after application of the above-mentioned drug was allowed to stand in an atmosphere at 23 ° C. for 72 hours, and then the test piece was bent by hand to evaluate whether the test piece was not broken (◯) / cracked (×). It was considered good that it was not broken (◯).

(formula)

表中「判定」は ○： 良好 、×：不良 を表す。

In the table, “judgment” indicates ○: good, ×: bad.

表中「判定」は ○： 良好 、×：不良 を表す。

In the table, “judgment” indicates ○: good, ×: bad.

  When the polycarbonate resin composition satisfies the constituent requirements of the present invention (Examples 1 to 4), good results were obtained over all of the surface impact strength, the spiral flow length, the flexural modulus, and the chemical resistance. showed that.

On the other hand, in the case where the polycarbonate resin composition does not satisfy the constituent requirements of the present invention, each case has some drawbacks.
Comparative Example 1 was a case where the rubber-reinforced styrene resin (ABS) was less than the range defined by the present invention and was inferior in fluidity.
In Comparative Example 2, the alkyl ketene dimer (AKD) was less than the range defined by the present invention, and the chemical resistance was poor.
In Comparative Example 3, the glass fiber was less than the range defined by the present invention, and the bending elastic modulus was inferior.
The comparative example 4 is a case where there are more alkyl ketene dimers (AKD) than the range which this invention specifies, and the pellet was not able to be created by granulation difficulty.
The comparative example 5 is a case where there are more glass fibers than the range which this invention defines, and it was inferior to the surface impact strength.

Claims (5)

The alkyl ketene dimer (C) 0.1-5 shown in the following general formula 1 per 100 parts by weight of the resin component consisting of 95-40% by weight of the polycarbonate resin (A) and 5-60% by weight of the rubber-reinforced styrene resin (B) A polycarbonate resin composition comprising 3 parts by weight and 3 to 30 parts by weight of glass fiber (D).
General formula 1:

(In General Formula 1, R may be the same or different, but represents an alkyl group having 6 to 33 carbon atoms.)   The polycarbonate resin composition according to claim 1, wherein the rubber-reinforced styrene resin (B) is an ABS resin.   The polycarbonate resin composition according to claim 1, wherein the compounding amount of the alkyl ketene dimer (C) is 1 to 3 parts by weight per 100 parts by weight of the resin component.   The polycarbonate resin composition according to claim 1, wherein the alkyl ketene dimer (C) is an alkyl group having 15 to 18 carbon atoms represented by R in the general formula 1.   2. The polycarbonate resin composition according to claim 1, wherein an amount of the glass fiber (D) is 5 to 15 parts by weight per 100 parts by weight of the resin component.