JP5258078B2 - Polycarbonate resin composition having high fluidity - Google Patents

Description

  The present invention relates to a polycarbonate resin composition having high fluidity. More specifically, the present invention relates to a polycarbonate resin composition having extremely excellent fluidity by blending a specific amount of a non-rubber reinforced styrene resin and a specific organic acid and an amide compound with a polycarbonate resin, and a molded article comprising the same.

Polycarbonate resins are excellent in transparency, impact resistance and heat resistance, and are widely used in many products in fields such as electricity, electronics and IT. In these fields in recent years, high fluidity of materials has been demanded as products become thinner. Therefore, in this field, there is a demand in the market for materials that have a good balance of fluidity without impairing impact resistance and flame retardancy.

  At the time of increasing the fluidity of the polycarbonate resin, the applicant has already filed an application regarding a polycarbonate resin composition having high fluidity by blending an organic acid and an amide compound in the polycarbonate resin (Patent Document 1).

JP 2006-37032 A

However, in fields such as electricity, electronics, and IT, even higher fluidity may be required, and improvements have been sought to provide even higher fluidity.

  As a result of intensive studies in view of such problems, the present inventors have formulated a specific amount of a non-rubber reinforced styrene resin and a specific organic acid and amide compound in a polycarbonate resin, thereby improving the heat resistance of the composition. The present invention has been achieved by successfully improving the fluidity without impairing the impact resistance.

That is, the present invention relates to an organic acid (C) of 0.01 to 0.00 per 100 parts by weight of a resin component consisting of 85 to 95% by weight of a polycarbonate resin (A) and 5 to 15% by weight of a non-rubber reinforced styrene resin (B). The present invention provides a polycarbonate resin composition having a high fluidity comprising 6 parts by weight and amide compound (D) 0.4 to 1.0 part by weight, and a molded product formed by using the polycarbonate resin composition.

  The thermoplastic resin composition of the present invention has significantly improved fluidity without greatly impairing heat resistance, impact resistance, etc., so that it is light and thin in various fields such as electricity, electronics, IT, and design. It can be suitably used for products that require a high degree of industrial utility value.

  The present invention is described in detail below.

  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.

  Although there is no restriction | limiting in particular in the viscosity average molecular weight of polycarbonate resin (A), Usually, it is 10,000-100000, More preferably, it is 15000-30000, More preferably, it is 17000-26000 from the surface of moldability and intensity | strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

  Examples of the non-rubber reinforced styrene resin (B) used in the present invention include a polymer composed of an aromatic vinyl monomer component (a) or a copolymer composed of a monomer copolymerizable therewith.

  Examples of the aromatic vinyl monomer component (a) include styrene, α-methylstyrene, o-, m-, p-methylstyrene, vinylxylene, ethylstyrene, vinylnaphthalene, and the like. More than seeds can be used. Styrene is preferably used.

  Examples of the monomer copolymerizable with the aromatic vinyl monomer component (a) include a vinyl cyanide monomer (b).

  Examples of the vinyl cyanide monomer component (b) include acrylonitrile, methacrylonitrile and the like, and these can be used alone or in combination. Preferably, acrylonitrile is used.

  Examples of the non-rubber reinforced styrene resin (B) include polystyrene and styrene-acrylonitrile (SAN) resin, and a SAN resin is preferably used.

  In the SAN resin, the composition ratio of the components (a) and (b) is not particularly limited and can be adjusted according to the use. Preferably, the component (a) is 95 to 50% by weight, (B) A component is 5 to 50 weight%, More preferably, (a) is 90 to 65 weight%, (b) is 10 to 35 weight%. In addition to the above components (a) and (b), a monomer copolymerizable with these components can be used in the SAN resin as long as the object of the present invention is not impaired.

Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; And imide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, and the like. Can be used alone or in combination of two or more.

  The blending ratio of the non-rubber reinforced styrene resin (B) is in the range of 5 to 15% by weight based on the polycarbonate resins (A) and (B). If the blending ratio is less than 5% by weight, the fluidity is inferior, and if it exceeds 15% by weight, the impact strength is inferior. More preferably, it is in the range of 5 to 10% by weight.

As the organic acid (C) used in the present invention, various types can be used. For example, a C6-C30 fatty acid is mentioned, A caprylic acid, capric acid, lauric acid, a palmitic acid, a stearic acid, an arachidic acid etc. are illustrated as a typical compound. In particular, capric acid is preferably used.

  The compounding amount of the organic acid (C) is 0.01 to 0.6 parts by weight per 100 parts by weight of the resin component comprising the polycarbonate resin (A) and the non-rubber reinforced styrene resin (B). If the blending amount is less than 0.01 parts by weight, the fluidity is inferior, and if it exceeds 0.6 parts by weight, the impact strength decreases, which is not preferable. A more preferable blending amount is in the range of 0.05 to 0.2 parts by weight.

The amide compound (D) is a compound represented by the following general formula (1).
General formula (1)
_{R1-CONH- (CH 2) n} -NHCO-R2
However, R1 and R2 are linear or branched alkyl groups having 6 to 30 carbon atoms, and n is an integer of 2 to 6. Specific examples include ethylene bisstearyl amide and ethylene bis oleyl amide, and ethylene bisstearyl amide is particularly preferably used.

  The compounding amount of the amide compound (D) is 0.4 to 1.0 part by weight per 100 parts by weight of the resin component composed of the polycarbonate resin (A) and the non-rubber reinforced styrene resin (B). If the blending amount is less than 0.4 parts by weight, the fluidity is inferior, and if it exceeds 1.0 parts by weight, the impact strength decreases, which is not preferable. A more preferable blending amount is in the range of 0.5 to 0.8 parts by weight.

  The mixing method of various components of the polycarbonate resin composition having high fluidity of the present invention is not particularly limited, and is mixed with an arbitrary mixer such as a tumbler, ribbon blender, high-speed mixer, etc., and is usually uniaxial or biaxial. It can be easily melt-kneaded with an extruder or the like.

  In addition, other known additives such as mold release agents, ultraviolet absorbers, fillers, impact modifiers, antistatic agents, antioxidants, heat stabilizers, other flame retardants, other difficult additives may be added at the time of mixing. Combustion aids (organic metal salts, etc.), dyes and pigments, spreading agents (epoxy soybean oil, liquid paraffin, etc.) can be blended.

  Examples of the filler include glass fiber, glass bead, glass flake, carbon fiber, talc, clay, mica, potassium titanate whisker, aluminum borate whisker, wollastonite, silica and the like.

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

The details of the used blending components are as follows.
・ Polycarbonate resin (hereinafter abbreviated as PC)
Caliber 200-20 (molecular weight: 18600) manufactured by Sumitomo Dow
-SAN resin MD-1 made by Japan A & L (hereinafter abbreviated as SAN)
・ Organic acid Capric acid (NAA-102 manufactured by NOF Corporation)
Amide compound Ethylene bisstearyl amide (Alfro H-50TF manufactured by NOF Corporation)

  Various blending components are collectively put into a tumbler at the blending ratios shown in Tables 1 and 2, and after 10 minutes of dry mixing, using a twin screw extruder (KTX37 manufactured by Kobe Steel) to a melting temperature of 240 ° C. And kneaded to obtain pellets of the thermoplastic resin composition. The following evaluation was performed from the obtained pellets. A J100E-C5 injection molding machine manufactured by Nippon Steel Co., Ltd. was used for the pellet injection molding process.

(1) Archimedes spiral flow fluidity The flow length at a channel thickness of 1 mm was measured using an Archimedes spiral flow mold under the conditions of a melting temperature of 250 ° C. and an injection pressure of 1600 kg / cm ² . A flow length of 170 mm or more was regarded as acceptable.

(2) Izod impact test
A specimen for an Izod impact test was processed under the condition of a melting temperature of 280 ° C., and the Izod impact strength was measured in accordance with ASTM D256. The measurement temperature is 23 ° C., and the thickness of the test piece is 3.2 mm. An impact value of 10 kg / cm / cm or more was regarded as acceptable.

  As shown in Table 1, when the polycarbonate resin composition satisfied the configuration of the present invention (Examples 1 to 6), the standard was satisfied over all evaluation items.

As shown in Table 2, when the polycarbonate resin composition did not satisfy the constitution of the present invention, each had the following drawbacks.
Comparative Example 1 was a case where SAN was not blended, and resulted in poor fluidity.
Comparative Example 2 was a case where SAN was blended in excess of the specified amount, resulting in poor impact resistance.
Comparative Example 3 was a case where no organic acid and amide compound were blended, resulting in poor fluidity.
Comparative Example 4 was a case where the amide compound was blended in excess of the specified amount, resulting in poor impact resistance.
Comparative Example 5 was a case where the organic acid was blended in excess of the specified amount, resulting in poor impact resistance.

Claims (6)

Organic acid (C) 0.01-0.6 parts by weight and amide per 100 parts by weight of resin component consisting of 85-95% by weight of polycarbonate resin (A) and 5-15% by weight of non-rubber reinforced styrene resin (B) Compound (D) A resin composition comprising 0.4 to 1.0 part by weight , wherein the non-rubber reinforced styrene resin (B) is a styrene-acrylonitrile copolymer (SAN resin), and the organic acid A polycarbonate resin composition having high fluidity, wherein (C) is a fatty acid having 6 to 30 carbon atoms . Claim amount of organic acid (C) is 0.05 to 0.2 parts by weight, and the amount of the amide compound (D) is characterized in that 0.5 to 0.8 parts by weight 1 A polycarbonate resin composition having high fluidity as described in 1. The high fluidity according to claim 1 , wherein the organic acid ( C ) is one or more fatty acids selected from caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, and arachidic acid. Polycarbonate resin composition. The polycarbonate resin composition having high fluidity according to claim 1 , wherein the amide compound ( D ) is a compound represented by the following general formula (1).
General formula (1)
R1-CONH- (CH2) n-NHCO-R2
Here, R1 and R2 are linear or branched alkyl groups having 6 to 30 carbon atoms, and n is an integer of 2 to 6. 2. The polycarbonate resin composition having high fluidity according to claim 1 , wherein the organic acid ( C ) is capric acid and the amide compound ( D ) is ethylenebisstearylamide. A molded product formed by using the polycarbonate resin composition having high fluidity according to any one of claims 1 to 5 .