JP2010077196A - Polycarbonate resin composition for profile extrusion and shock-absorbing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition for profile extrusion, which is excellent in melt tension, is excellent in mechanical strength such as low-temperature impact resistance, tensile strength and bending strength, is excellent in heat resistance and chemical resistance and is capable of yielding a molded product that can be widely used in from low-temperature to high-temperature environments, and a shock-absorbing material. <P>SOLUTION: The polycarbonate resin composition for profile extrusion contains, against 100 pts.wt. of an aromatic polycarbonate resin (A) having a viscosity average molecular weight of ≥26,000, 20-100 pts.wt. of a crystalline polyester resin (B), 0.5-40 pts.wt. of a thermoplastic elastomer (C) and 0.5-20 pts.wt. of a polymer (D) which comprises a monomer chosen from the group consisting of a monoolefin compound and a diolefin compound and has a functional group that reacts with polycarbonate. The shock-absorbing material is made of the composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition for profile extrusion having excellent melt tension. More specifically, for profile extrusion molding that has excellent mechanical strength such as low-temperature impact resistance, tensile strength, bending strength, heat resistance, chemical resistance, and gives molded products that can be used in a wide range of environments from low to high temperatures. The present invention relates to a polycarbonate resin composition. The present invention also relates to a cushioning material formed by extruding this resin composition.

  Aromatic polycarbonate resin is a resin with excellent mechanical strength, heat resistance, electrical properties, dimensional stability, etc., including electrical, electronic and OA equipment parts, automobile parts, precision machine parts, medical equipment parts, and miscellaneous goods. Used in a wide range of fields. In particular, in the automotive parts field, considering the use in cold areas in winter and the rise in the cabin temperature during outdoor parking in summer, etc., the mechanical strength such as low-temperature impact strength, heat resistance, chemical resistance, etc. It is essential to be excellent.

  For example, a cushioning material made of aromatic polycarbonate is disposed between the bumper and the vehicle body as a bumper reinforcement, and absorbs energy at the time of collision due to its own deformation against collisions from the front and rear of the vehicle body. Protected. Further, in the passenger compartment, the shock absorber disposed between the outer periphery of the roof and the ceiling material absorbs energy at the time of collision and protects the human body.

  Such a cushioning material generally has a hollow cross section such as a square shape from the viewpoint of light weight and energy absorption efficiency, and is often manufactured by profile extrusion molding. Therefore, the polycarbonate resin composition used for the production of these buffer materials is required to have excellent mechanical properties such as low temperature impact strength, heat resistance, chemical resistance, and melting characteristics suitable for profile extrusion molding.

  By the way, a general aromatic polycarbonate resin has a linear molecular structure. Therefore, at the time of profile extrusion molding, especially at the time of molding using a sizing die that has the function of cooling while giving a desired shape to the molten resin discharged from the extruder, the draw tension tends to be insufficient, such as a large drawdown. strong.

  One method for improving the drawdown property is to use an aromatic polycarbonate resin having a large molecular weight. However, this method has a problem that the melt viscosity at the time of extrusion molding becomes too high and the productivity does not increase, and in addition, the appearance of the molded product is poor. Therefore, it is required to improve the drawdown property by other methods.

  In response to such a requirement, Patent Document 1 includes a straight-chain aromatic polycarbonate resin and a branched aromatic polycarbonate resin having a structural viscosity index N of 1.8 to 2.5. An aromatic polycarbonate resin composition having no mold and excellent moldability for extrusion molding is disclosed. However, this has insufficient chemical resistance and has limited applications.

  Patent Document 2 discloses (a) amorphous polyesters and (ii) as resin compositions that do not cause resin sag during processing and can give a modified extrusion-molded product excellent in solvent resistance and detergent resistance. There is disclosed a polyester resin composition for profile extrusion molding, characterized in that it comprises at least one of (a) crystalline polyester and (c) a crystal nucleating agent. However, this one has low heat resistance. Also, it is unclear how much impact resistance it has.

  In Patent Document 3, as a resin composition having improved impact resistance without causing a problem of pearl luster, an aromatic polycarbonate, an aromatic polyester, an α-olefin, and a glycidyl ester of an α, β-unsaturated acid are mainly used. A resin composition containing the copolymer is disclosed. However, this product still has insufficient impact resistance. Moreover, there is no description regarding low temperature impact resistance and profile extrusion formability.

  In Patent Document 4, two or more polycarbonate resins, polyester resins, glycidyl groups and / or isocyanate groups per molecule are used as a resin composition that improves the heat resistance, impact resistance, and profile extrusion moldability of polyester resins. A polyester resin-based resin composition for profile extrusion processing containing a reactive compound is disclosed. However, this product has low heat resistance, and there is no description regarding low temperature impact resistance and chemical resistance.

JP-A-5-295246 JP 2003-171540 A JP-A-2-202545 Japanese Patent Laid-Open No. 2005-298685

  The object of the present invention is excellent in melt tension, excellent in mechanical strength such as low-temperature impact resistance, tensile strength and bending strength, excellent in heat resistance and chemical resistance, and can be used in a wide range of environments from low temperature to high temperature. An object of the present invention is to provide a polycarbonate resin composition for profile extrusion molding that gives a molded article. Another object of the present invention is to provide a cushioning material formed by extruding this resin composition.

  As a result of extensive research, the present inventors have found that a polymer having a functional group that reacts with a polycarbonate such as a crystalline polyester resin, a thermoplastic elastomer, and an epoxy group is added to a specific high molecular weight aromatic polycarbonate resin. It was found that by blending a specific amount, a polycarbonate resin composition for profile extrusion excellent in mechanical strength, heat resistance, chemical resistance and melt tension was obtained, and the present invention was completed.

  That is, the gist of the present invention is that 20 to 100 parts by weight of the crystalline polyester resin (B) and 0.5 to 0.5 parts by weight of the thermoplastic elastomer C) per 100 parts by weight of the aromatic polycarbonate resin (A) having a viscosity average molecular weight of 26000 or more. 0.5 to 20 parts by weight of a polymer of a monomer selected from the group consisting of 40 parts by weight and a monoolefin compound and a diolefin compound and having a functional group that reacts with polycarbonate (D) The present invention resides in a polycarbonate resin composition for profile extrusion molding characterized by containing, and a buffer material formed by extrusion molding the composition.

  The polycarbonate resin composition for profile extrusion molding of the present invention is excellent in melt tension, excellent in mechanical strength such as low temperature impact resistance, tensile strength and bending strength, excellent in heat resistance and chemical resistance, from low temperature to high temperature. It can be used in fields such as electric parts, electronic parts, OA equipment parts, automobile parts, precision machine parts, medical equipment parts, miscellaneous goods, etc. Especially, it is suitable for manufacture of the shock absorbing material for motor vehicles taking advantage of the outstanding low temperature impact resistance, heat resistance, chemical resistance, and profile extrusion moldability.

The present invention will be described in detail below.
As is well known, the aromatic polycarbonate resin is produced by an interfacial polymerization method in which an aromatic dihydroxy compound is reacted with phosgene or a transesterification method in which it is reacted with a carbonic acid diester. Can be used. In the transesterification method, the terminal OH group concentration may be adjusted by reacting the terminal blocking agent, but those subjected to this treatment can also be used.

  As the aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) is mainly used, but other aromatic dihydroxy compounds such as tetramethylbisphenol A and bis (4-hydroxy) are used. Phenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, and the like can also be used. In addition, in order to impart flame retardancy to the resulting resin, a compound in which tetraalkylphosphonium sulfonate is bonded to the above aromatic dihydroxy compound, a polymer or oligomer having a siloxane structure and having a phenolic OH group at both ends are used. It can also be used together.

  In the present invention, it is preferable to use a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, but other polycarbonate resins such as 2,2-bis (4-hydroxyphenyl) propane and other A copolymer polycarbonate resin derived from an aromatic dihydroxy compound can also be used. Two or more polycarbonate resins may be used in combination.

  The aromatic polycarbonate resin (A) used in the present invention is methylene chloride as a solvent and has a viscosity average molecular weight calculated from a solution viscosity measured at a temperature of 25 ° C., which is 26,000 or more, preferably 27,000 or more. . When the viscosity average molecular weight is less than 26,000, the melt tension is insufficient and the profile extrusion moldability is lowered. The upper limit viscosity average molecular weight is 40,000, preferably 35,000. When the viscosity average molecular weight exceeds 40,000, the melt tension is too high, and the profile extrusion moldability and the appearance of the molded product are deteriorated.

  In the present invention, as the aromatic polycarbonate resin (A), not only virgin products but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins can be used. For example, optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, spectacle lenses, soundproof walls, glass windows, and building materials such as corrugated plates It is possible to use those reproduced from the above. Moreover, what was regenerated from defective products, sprues, runners, etc. at the time of molding can also be used.

  The crystalline polyester resin (B) used in the present invention is preferably a thermoplastic polyester resin obtained by subjecting an aromatic dicarboxylic acid component as a main acid component to a polycondensation reaction with an aliphatic glycol. Further, it is possible to use an aromatic dicarboxylic acid and an aliphatic glycol in combination with another reactive compound such as a hydroxy aromatic carboxylic acid. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and diphenyldicarboxylic acid.

  Examples of the aliphatic glycol include α, ω-alkylene having 2 to 10 carbon atoms such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Glycol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like, and bisphenol A polyoxyethylene glycol and polyoxytetramethylene glycol are also exemplified.

  As the crystalline polyester resin (B), those in which 70 mol% or more, particularly 90 mol% or more of all the acid components and all diol components are a single component are preferable. Specifically, for example, polybutylene terephthalate, polybutylene terephthalate copolymer using 1,4-butanediol in combination with other glycol, polybutylene naphthalate, polycyclohexanedimethanol terephthalate, polyethylene terephthalate, polyethylene naphthalate, etc. Can be mentioned. In the present invention, it is particularly preferable to use polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).

  As the polymerization catalyst for producing the polyethylene terephthalate resin, a germanium compound, an antimony compound, a tin compound, a titanium compound, or the like is used. In the present invention, it is preferable to use a polymer produced using a germanium compound as a catalyst. When using what was polymerized with another catalyst, there exists a tendency for the thermal stability and recyclability of the aromatic polycarbonate resin composition finally obtained to fall.

  Germanium compounds used as catalysts include germanium oxides such as germanium dioxide, germanium alkoxides such as germanium tetraethoxide, germanium tetraisopropoxide, germanium hydroxide and its alkali metal salts, germanium glycolate, germanium chloride, germanium acetate, etc. Is mentioned. These may be used alone or in combination of two or more. Among these, it is preferable to use germanium dioxide from the viewpoints of solvent resistance and thermal stability of the obtained polyethylene terephthalate resin.

  The germanium catalyst is preferably used so that the content in terms of germanium atoms is 15 ppm to 40 ppm in the polyethylene terephthalate resin to be produced. If it is less than 15 ppm, the polymerization reaction proceeds slowly, and if it exceeds 40 ppm, a side reaction may occur due to the germanium compound remaining in the resin. The addition timing of the germanium catalyst may be any time before the start of the polymerization reaction.

  As the polybutylene terephthalate resin, it is preferable to use a resin produced using a titanium compound as a main catalyst and a Group 1 metal compound or a Group 2 metal compound as a cocatalyst. Examples of the titanium compound include inorganic titanium compounds such as titanium oxide and titanium tetrachloride; titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate; titanium phenolates such as tetraphenyl titanate; It is done. Of these, titanium alcoholates are preferably used. Most preferred are tetraalkyl titanates, especially tetrabutyl titanate.

  The titanium compound is preferably used in the polybutylene terephthalate resin to be produced so that the content in terms of titanium atom is 20 ppm to 50 ppm, particularly 30 to 40 ppm. If the amount of the titanium compound used is too large, the color tone and hydrolysis resistance of the resulting polybutylene terephthalate resin may decrease, and the solution haze and foreign matter increase may occur due to the deactivation of the titanium catalyst. On the other hand, if the amount is too small, the polymerization reactivity of the polybutylene terephthalate resin is lowered.

  As the crystalline polyester resin (B), one having an intrinsic viscosity of 0.4 to 2.0 measured at 25 ° C. in a mixed solvent of phenol and tetrachloroethane (weight ratio = 50/50) is usually used. If the intrinsic viscosity is less than 0.4, the mechanical strength is inferior. Conversely, if it exceeds 2.0, the moldability of the finally obtained resin composition tends to be lowered. The intrinsic viscosity of the crystalline polyester resin (B) is preferably 0.6 to 1.2.

  As the crystalline polyester resin (B), not only virgin products but also recycled materials, that is, polyester resins regenerated from used products, so-called material recycled polyester resins, can be used from an economic standpoint. Is preferably used. Recycled materials mainly include those from containers, films, sheets, fibers, etc., but recycled materials from containers such as PET bottles are preferred. It is also preferable to use recycled materials from defective products, sprues, runners and the like during molding.

  The compounding quantity of a polyester resin (B) is 20-100 weight part with respect to 100 weight part of aromatic polycarbonate resin (A). If the blending amount of the polyester resin (B) is less than 20 parts by weight, the chemical resistance of the polycarbonate resin composition tends to be lowered, and if it exceeds 100 parts by weight, the heat resistance and impact resistance may be lowered. Therefore, the compounding amount of the crystalline polyester resin (B) is preferably 20 to 80 parts by weight, more preferably 30 to 50 parts by weight, and particularly preferably 30 to 40 parts by weight.

  In the present invention, if desired, an amorphous polyester resin can be used in combination with the crystalline polyester resin (B) in order to further increase the melt tension. However, since the amorphous polyester resin tends to lower the chemical resistance, the amount used is preferably smaller than that of the crystalline polyester resin.

  What is necessary is just to use what is mix | blended with a polyester resin and a polycarbonate resin and is used in order to improve the impact resistance as a thermoplastic elastomer (C) used by this invention. For example, a rubber polymer or a rubber polymer obtained by copolymerizing a compound that reacts with the rubber polymer is used. The glass transition temperature of the thermoplastic elastomer (C) is preferably 0 ° C. or lower, particularly preferably −20 ° C. or lower.

  Specific examples of the thermoplastic elastomer (C) include polybutadiene, polyisoprene, diene copolymers (styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, acrylic / butadiene rubber, etc.), ethylene and 3 carbon atoms. Copolymers with the above α-olefins (ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / octene copolymer, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (ethylene / methacrylate) Copolymers, ethylene / butyl acrylate copolymers, etc., copolymers of ethylene and aliphatic vinyl compounds, terpolymers of ethylene, propylene and non-conjugated dienes, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl) Acrylate), butyl acrylate, 2-ethyl f Sill acrylate copolymers), silicone rubber (a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkyl (meth) IPN type composite rubber consisting of acrylate rubber), and the like. These may be used alone or in combination of two or more. In the present invention, (meth) acrylate means acrylate and methacrylate, and (meth) acrylic acid means acrylic acid and methacrylic acid.

  Another example of the thermoplastic elastomer (C) is a copolymer obtained by polymerizing a monomer component with a rubber polymer. Examples of this monomer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. In addition, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β- such as maleic acid, phthalic acid and itaconic acid Examples thereof also include unsaturated carboxylic acid compounds and anhydrides thereof (for example, maleic anhydride). These monomers can be used alone or in combination of two or more.

  The thermoplastic elastomer (C) is preferably of the core / shell type graft copolymer type from the viewpoint of improving impact resistance. Among them, a rubber polymer selected from butadiene component-containing rubber, butyl acrylate component-containing rubber, and silicone rubber is used as a core layer, and a monomer selected from an acrylate ester, a methacrylate ester, and an aromatic vinyl compound is provided around the core polymer. A core / shell type graft copolymer comprising a shell layer formed by copolymerization is particularly preferred.

  Examples of core / shell type graft copolymers include methyl methacrylate-butadiene-styrene polymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS), methyl methacrylate-butadiene polymer (MB), methyl Methacrylate-acrylic rubber polymer (MA), methyl methacrylate-acrylic rubber-styrene polymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, methyl methacrylate- (Acrylic / silicone IPN (interpenetrating polymer network) rubber) polymer and the like. These rubbery polymers may be used alone or in combination of two or more.

  The compounding quantity of a thermoplastic elastomer (C) is 0.5-40 weight part with respect to 100 weight part of aromatic polycarbonate resin (A). When the blending amount of the thermoplastic elastomer (C) is less than 0.5 parts by weight, the effect of improving the impact resistance is small, and when it exceeds 40 parts by weight, the heat resistance and rigidity may be lowered. The amount of the thermoplastic elastomer (C) is preferably 1 to 30 parts by weight, and more preferably 2 to 20 parts by weight.

  In the present invention, the aromatic polycarbonate resin (A) is a polymer of a monomer selected from the group consisting of a monoolefin compound and a diolefin compound and has a functional group that reacts with the polycarbonate (D). Containing. Examples of the functional group include an epoxy group, a hydroxyl group, a carboxyl group, and an acid anhydride group. These functional groups are considered to react with the terminal carboxyl group or terminal hydroxyl group of the polycarbonate resin or polyester resin to produce a so-called crosslinking effect and improve the melt tension of the resin composition.

  Examples of the polymer of the monoolefin compound include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutene, poly-4-methyl-pentene-1, propylene-ethylene block copolymer, propylene-ethylene random copolymer. And a copolymer of ethylene and another copolymerizable monomer (ethylene-α-olefin copolymer, ethylene-acrylic acid copolymer, etc.).

  Examples of polymers of diolefin compounds include polyisoprene, polybutadiene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, and butadiene-isoprene copolymers. Diene rubbers such as polymers, acrylic ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, ethylene-propylene non-conjugated dienes such as ethylene-propylene-hexadiene copolymers 3 Examples thereof include an original copolymer.

  One preferable as the polymer (D) is a polymer of an aromatic vinyl compound. Examples include polystyrene, syndiotactic polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, maleimide-modified acrylonitrile-butadiene-styrene copolymer. Examples thereof include acrylonitrile-butyl acrylate-styrene copolymer, acrylonitrile-ethylene / propylene-styrene copolymer, and methyl methacrylate-styrene copolymer.

  The functional group of the polymer (D) is preferably an epoxy group in terms of high reactivity. The epoxy group content is preferably 100 to 600 g / eq as an epoxy equivalent. When the epoxy equivalent exceeds 600 g / eq, the melt tension of the polycarbonate resin composition may become too high, or the appearance of the molded product may be deteriorated due to the occurrence of blisters. Moreover, if it is less than 100 g / eq, the effect which makes melt tension high will not express so much.

  The compounding quantity of a polymer (D) is 0.5-20 weight part with respect to 100 weight part of aromatic polycarbonate resin (A), Preferably it is 1-15 weight part. When the compounding amount of the compound (D) is less than 0.5 parts by weight, the effect of improving the melt tension is small, and when it exceeds 20 parts by weight, the moldability of the resin composition and the heat resistance of the molded product may be lowered. The preferred blending amount of the polymer (D) varies depending on its structure. In the case of a polymer of an aliphatic monoolefin compound having an epoxy group, such as glycidyl methacrylate-containing polyethylene, 3 to 13 parts by weight is preferred. In the case of a styrene polymer containing an epoxy group such as methacrylate-containing polystyrene, the amount is preferably 0.5 to 5 parts by weight.

  In addition to the above components (A) to (D), the polycarbonate resin composition of the present invention includes, if necessary, phosphate esters, condensed phosphate esters, other flame retardants, UV absorbers, heat resistance and residence heat stability. Phosphorus compounds, hindered phenolic antioxidants, pigments, dyes, lubricants, mold release agents, plasticizers, antistatic agents, slidability improvers, compatibilizers, etc. can be added it can.

  Also, a fluororesin that has a drip-preventing action during combustion of difluoroethylene polymer, tetrafluoroethylene polymer, tetrafluoroethylene-hexafluoropropylene copolymer, copolymer of tetrafluoroethylene and ethylene monomer not containing fluorine, etc. Further, reinforcing materials such as glass fibers, glass flakes, carbon fibers, and metal fibers, or inorganic fillers such as whiskers such as potassium titanate, aluminum borate, and calcium silicate, mica, talc, and clay can be blended.

  The polycarbonate resin composition of the present invention can be produced according to a conventional method for producing a thermoplastic resin composition. For example, a method of melting and kneading the above components with a uniaxial or multiaxial kneader, Banbury mixer, roll, Brabender plastogram, etc., and then cooling and solidifying can be used. Add the above components to a suitable solvent such as hydrocarbons such as hexane, heptane, benzene, toluene, xylene and their derivatives, mix in solution or in suspension containing insoluble components, and then remove the solvent The method can also be used. Industrially, it is preferable to melt and knead using a single screw or twin screw extruder.

  The profile extrusion of the polycarbonate resin composition of the present invention can be performed according to a conventional method. Usually, an extruder having a die (shaped die) for forming a desired shape at the tip is used, and the resin composition plasticized in the extruder is continuously passed through the die with a constant cross section. By extruding in a shape and cooling and solidifying the extruded molten resin, even a molded product having a complicated cross-sectional shape can be easily produced. By changing the shape of the mold, a profile extrusion-molded product having a desired cross-sectional shape can be produced.

  Applications of the profile extrusion-molded product obtained using the polycarbonate resin composition of the present invention include window frames, outer wall materials, desk drawers, edge materials, OA equipment panels, automotive parts, and the like. In particular, the profile extrusion molded product comprising the polycarbonate resin composition of the present invention is excellent in mechanical strength such as low temperature impact resistance, tensile strength and bending strength, excellent in heat resistance and chemical resistance, and from low to high temperatures. Since it can be used in a wide range of environments, it can be suitably used as a cushioning material for automobiles, that is, a cushioning material disposed between the bumper and the vehicle body, a cushioning material between the outer periphery of the roof and the ceiling material, and the like. The cross-sectional shape of the profile extrusion-molded product used as such a cushioning material is a cylindrical shape, an elliptical cylindrical shape, a rectangular cylindrical shape, a rhombus shape, or a U-shape in terms of light weight and energy absorption efficiency. It is preferable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The raw materials used in Examples and Comparative Examples are as follows.

Aromatic polycarbonate resin (1): Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (Novalex (registered trademark) 7030PJ, viscosity average molecular weight 30000 manufactured by Mitsubishi Engineering Plastics)

Aromatic polycarbonate resin (2): Bisphenol A type aromatic polycarbonate produced by the interfacial polymerization method (Novalex (registered trademark) 7022PJ, viscosity average molecular weight 22000, manufactured by Mitsubishi Engineering Plastics)

Aromatic polycarbonate resin (3): Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (Iupilon (registered trademark) E-2000FN manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 28000)

Polyethylene terephthalate resin (1): “Novapex (registered trademark) GG900” manufactured by Mitsubishi Chemical Corporation (germanium atom content 28 ppm, intrinsic viscosity 1.10 dl / g)

Polyethylene terephthalate resin (2): “Novapex (registered trademark) GG500” manufactured by Mitsubishi Chemical Corporation (germanium atom content 28 ppm, intrinsic viscosity 0.76 dl / g)

Polyethylene terephthalate resin (3): “Novapex (registered trademark) GS385” manufactured by Mitsubishi Chemical Corporation (antimony atom content: 230 ppm, intrinsic viscosity: 0.66 dl / g)

Polybutylene terephthalate resin (1): NOVADURAN (registered trademark) 5020 manufactured by Mitsubishi Engineering Plastics, intrinsic viscosity 1.20 dl / g, titanium atom content 40 ppm

Polybutylene terephthalate resin (2): NOVADURAN (registered trademark) 5008 manufactured by Mitsubishi Engineering Plastics, intrinsic viscosity 0.85 dl / g, titanium atom content 40 ppm

Recycled polyethylene terephthalate resin: A flaky recycled polyethylene terephthalate resin obtained from used PET bottles for beverages and the like through separation, pulverization, washing and drying. Intrinsic viscosity 0.72 dl / g. (Intrinsic viscosity is a value measured at a temperature of 30 ° C. by dissolving in an equal weight mixture of phenol and tetrachloroethane at a concentration of 1% by weight)

Amorphous polyester resin: Byron RF-100-01C (trade name) manufactured by Toyobo Co., Ltd., which is a modifier for abnormal extrusion of polyester and has high melt viscosity and shear dependency.

Thermoplastic elastomer: Core / shell type graft copolymer consisting of polybutadiene / polystyrene copolymer (core) / alkyl acrylate / alkyl methacrylate copolymer (shell) (Rohm and Hearth Japan) Paraloid KCZ201N (trade name))

Epoxy group-containing polymer (1): ethylene-glycidyl methacrylate (GMA) polymer (Bond First E (trade name) manufactured by Sumitomo Chemical Co., Ltd.), GMA content 6% by weight, glass transition temperature Tg <−25 ° C., epoxy equivalent 350 g / eq

Epoxy group-containing polymer (2): Glycidyl methacrylate-containing polystyrene masterbatch (Cela-Extend 1588 (table name) manufactured by Clariant, glass transition temperature 55 ° C., epoxy equivalent of about 285 g / eq

Phosphorus compound (1): Tris (2,4-di-t-butylphenyl) phosphite, ADK STAB AS2112 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.)

Phosphorus compound (2): Chemical formula O = P (OH) _{n ′} (OC ₁₈ H ₃₇ ) _{3-n ′} (mixture of n ′ = 1 and 2) (Adeka Stab AX-71 manufactured by Asahi Denka Kogyo Co., Ltd.) (Product name))

Talc: PKP-53 (trade name) manufactured by Fuji Talc, average particle diameter of 18.5 μm by laser analysis

Carbon black: Oil furnace carbon black (Mitsubishi Chemical # 1000 (trade name))

Examples 1-13 and Comparative Examples 1-6:
After blending each component in the ratio shown in Table 1 and uniformly mixing with a tumbler mixer, using a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12), cylinder temperature The pellet of the resin composition was produced by feeding to the extruder from the barrel 1 at 280 degreeC and screw rotation speed 250rpm, and melt-kneading.

Measurement of melt tension:
The pellets obtained above were dried at 120 ° C. for 4 hours or longer, using a “Capillograph 1C” manufactured by Toyo Seiki, cylinder temperature 260 ° C., orifice diameter φ1.0 mm, length 10 mm, piston descending speed 10 mm / min, strand take-up The melt tension was measured at a speed of 3.8 m / min. The results are shown in Table 1. In addition, the measurement lower limit of the melt tension in the said measuring apparatus is 15 mN, and generally the practical melt tension of the resin composition used for extrusion molding is 20 mN or more.

Measurement of impact resistance (Charpy impact strength with notch):
After drying the pellets obtained above at 120 ° C for 4 hours or more, using a FANUC "α100iA type" injection molding machine, under conditions of a cylinder temperature of 280 ° C, a mold temperature of 80 ° C, and a molding cycle of 40 seconds, An ISO tensile test piece (thickness 4.0 mm) was injection molded. In accordance with ISO 179, a notched test piece having a thickness of 4.0 mm was prepared from this test piece, and the notched Charpy impact strength (unit: KJ / m ² ) was measured at 23 ° C. and −30 ° C. It was measured. The results are shown in Table 1.

Chemical resistance (visual):
An ISO tensile test piece (thickness 4 mm) was prepared by the same method as described above, and a test chemical was applied in a state in which a deflection of 0.59% was applied thereto, and kept at room temperature for 72 hours. About this thing, the crack generation degree was investigated using visual observation and a microscope, and chemical resistance was evaluated. Commercially available regular gasoline was used as the test chemical. In addition, the crack generation degree was evaluated by the ratio of the number of cracks generated among the five test pieces. The results are shown in Table 1.

  The resin compositions described in Examples 1 to 13 have an excellent balance of melt tension characteristics, impact resistance, and chemical resistance. On the other hand, the resin compositions of Comparative Examples 1 to 6, which are outside the range defined in the present invention, are inferior in the balance of melt tension characteristics, impact resistance, and chemical resistance as compared with the resin compositions described in the examples. Is obvious.

Claims (18)

20 to 100 parts by weight of crystalline polyester resin (B), 0.5 to 40 parts by weight of thermoplastic elastomer (C), and monoolefin with respect to 100 parts by weight of aromatic polycarbonate resin (A) having a viscosity average molecular weight of 26000 or more It is a polymer of a monomer selected from the group consisting of a series compound and a diolefin type compound, and contains 0.5 to 20 parts by weight of a polymer (D) having a functional group that reacts with a polycarbonate. Polycarbonate resin composition for profile extrusion molding. The polycarbonate resin composition for profile extrusion molding according to claim 1, wherein the polymer (D) has an epoxy group as a functional group that reacts with the polycarbonate. The polycarbonate resin composition for profile extrusion molding according to claim 1 or 2, wherein the crystalline polyester resin (B) is selected from the group consisting of a polyethylene terephthalate resin and a polybutylene terephthalate resin. The crystalline polyester resin (B) has an intrinsic viscosity of 0.4 to 2.0 dl / g measured at 25 ° C. using an equal weight mixed solvent of phenol and tetrachloroethane. 3. The polycarbonate resin composition for profile extrusion molding according to 3. The crystalline polyester resin (B) has a specific viscosity of 0.6 to 1.2 dl / g measured at 25 ° C. using a mixed solvent of 50% by weight of phenol and 50% by weight of tetrachloroethane. The polycarbonate resin composition according to claim 3. The polycarbonate resin composition for profile extrusion molding according to any one of claims 1 to 5, wherein the content of the crystalline polyester resin (B) is 25 to 50 parts by weight. The polycarbonate resin composition for profile extrusion molding according to any one of claims 1 to 6, wherein the thermoplastic elastomer (C) is a core / shell type graft copolymer. The polycarbonate resin composition for profile extrusion molding according to any one of claims 1 to 7, wherein the content of the thermoplastic elastomer (C) is 2 to 20 parts by weight. The variant according to any one of claims 1 to 8, wherein the polymer (D) has an epoxy group as a functional group that reacts with the polycarbonate, and an epoxy equivalent thereof is 100 to 600 g / eq. Polycarbonate resin composition for extrusion molding. The polymer (D) is produced using ethylene and glycidyl (meth) acrylate as monomers, and the content thereof is 3 to 13 parts by weight. The polycarbonate resin composition for profile extrusion molding described in 1. The polymer (D) is produced using styrene and glycidyl (meth) acrylate as monomers, and the content thereof is 0.5 to 5 parts by weight. The polycarbonate resin composition for profile extrusion molding according to any one of the above. It was selected from the group consisting of polyethylene terephthalate and polybutylene terephthalate with respect to 100 parts by weight of aromatic polycarbonate resin (A) having a viscosity average molecular weight of 26000 or more, and measured at 25 ° C. using a mixed solvent of equal weight of phenol and tetrachloroethane. 25 to 50 parts by weight of a crystalline polyester resin (B) having an intrinsic viscosity of 0.6 to 1.2 dl / g, 2 to 20 parts by weight of a thermoplastic elastomer (C) that is a core / shell type graft copolymer, and It is manufactured using ethylene and glycidyl (meth) acrylate as a monomer, and contains 3 to 13 parts by weight of a polymer (D) containing an epoxy group at 100 to 600 g / eq. Polycarbonate resin composition. It was selected from the group consisting of polyethylene terephthalate and polybutylene terephthalate with respect to 100 parts by weight of aromatic polycarbonate resin (A) having a viscosity average molecular weight of 26000 or more, and measured at 25 ° C. using a mixed solvent of equal weight of phenol and tetrachloroethane. 25 to 50 parts by weight of a crystalline polyester resin (B) having an intrinsic viscosity of 0.6 to 1.2 dl / g, 2 to 20 parts by weight of a thermoplastic elastomer (C) that is a core / shell type graft copolymer, and a monomer A profile extrusion molding characterized by containing 0.5 to 5 parts by weight of a polymer (D) produced using styrene and glycidyl (meth) acrylate as an epoxy group and containing 100 to 600 g / eq of epoxy groups Polycarbonate resin composition. The crystalline polyester resin (B) is a polyethylene terephthalate resin produced by using a germanium compound as a catalyst, and contains 15 to 40 ppm of germanium as germanium atoms. A polycarbonate resin composition for profile extrusion according to claim 1. The crystalline polyester resin (B) is a polybutylene terephthalate resin produced using a titanium compound as a catalyst, and contains 20 to 50 ppm of titanium as a titanium atom. The polycarbonate resin composition for profile extrusion according to any one of the above. The profile extrusion according to any one of claims 1 to 15, wherein the aromatic polycarbonate resin (A) is a mixture of an aromatic polycarbonate resin having a viscosity average molecular weight of 24,000 or less and an aromatic polycarbonate resin having a viscosity average of 28000 or more. Polycarbonate resin composition for molding. The polycarbonate resin composition for profile extrusion molding according to any one of claims 1 to 16, wherein the aromatic polycarbonate resin (A) has a viscosity average molecular weight of 40,000 or less. A cushioning material comprising an extrusion molding of the polycarbonate resin composition according to any one of claims 1 to 17, and having a cross-sectional shape of a cylindrical shape, an elliptical cylindrical shape, a rectangular cylindrical shape, or a U-shape.