WO2013183567A1 - Composition de résine thermoplastique et article moulé à base de celle-ci - Google Patents

Composition de résine thermoplastique et article moulé à base de celle-ci Download PDF

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WO2013183567A1
WO2013183567A1 PCT/JP2013/065249 JP2013065249W WO2013183567A1 WO 2013183567 A1 WO2013183567 A1 WO 2013183567A1 JP 2013065249 W JP2013065249 W JP 2013065249W WO 2013183567 A1 WO2013183567 A1 WO 2013183567A1
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thermoplastic resin
resin composition
block copolymer
composition according
acrylic block
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PCT/JP2013/065249
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English (en)
Japanese (ja)
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萌 川原
真 赤井
啓志 大島
伊藤　敏幸
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株式会社クラレ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material

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  • the present invention relates to a thermoplastic resin composition excellent in oil resistance, flexibility and fluidity, and a molded article comprising such a thermoplastic resin composition.
  • the resin composition can be formed into a molded product by various molding methods.
  • Injection molding is used as one of general molding methods.
  • Injection molding is a method of manufacturing a molded product by injecting a heated and molten resin into a cavity of a mold and solidifying the resin in the mold. It is known that a molded product produced by this method is oriented with at least a part of the resin molecular chain by shear generated in the cavity (see Non-Patent Document 1).
  • Such a markedly oriented molded article has a problem that a difference in physical properties (anisotropy) occurs between the orientation direction and a direction perpendicular thereto.
  • Patent Document 2 Patent Documents 3 and 4 do not describe any influence of anisotropy on physical properties of molded products, particularly molded products manufactured by injection molding. Further, in the resin composition described in Patent Document 4, there is a problem that the fluidity of the resin composition decreases due to crosslinking, so that the molding method and conditions are limited, and it is difficult to produce a thin molded product. . Furthermore, there has been a demand for further improvement in paintability in molded products.
  • JP 2006-225413 A International Publication No. 2008/123316 International Publication No. 2002/092696 International Publication No. 2003/068888 Japanese Patent Publication No. 7-25859 JP 11-335432 A JP-A-6-93060
  • An object of the present invention is to provide a thermoplastic resin composition excellent in oil resistance, flexibility and fluidity, and a molded article having low anisotropy and excellent paintability, comprising such a thermoplastic resin composition. .
  • the above object is [1] An acrylic block copolymer (A) having an acrylic ester polymer block (a1) and a methacrylic ester polymer block (a2), and a thermoplastic resin (B), and a differential scanning calorimeter ( DSC) was heated from 30 ° C. to 280 ° C. at a heating rate of 10 ° C./min and then cooled from 280 ° C. to 30 ° C. at a cooling rate of 10 ° C./min, and then the heating rate was 10 ° C./min.
  • thermoplastic resin composition in the acrylic block copolymer (A) and the thermoplastic resin ( B) a thermoplastic resin composition that is 15 parts by weight or more and less than 50 parts by weight with respect to a total of 100 parts by weight;
  • Tensile storage modulus (E ′ MD ) in the flow direction measured in accordance with JIS K 7244-4 and tensile storage in a direction perpendicular to the flow direction of the molded article made of the thermoplastic resin composition The thermoplastic resin composition according to [1], wherein the ratio of elastic modulus (E ′ TD ) at 30 ° C. (E ′ MD / E ′ TD ) is in the range of 0.5 to 2.0; [3] After the thermoplastic resin (B) is melted by heating from 30 ° C.
  • thermoplastic resin composition according to [1] which does not have a crystallization peak when cooled at a temperature lowering rate of 10 ° C / min; [4] The thermoplastic resin composition according to [1], wherein the thermoplastic resin (B) is an amorphous thermoplastic resin; [5] The thermoplastic resin composition according to [1], wherein the thermoplastic resin (B) is an amorphous polyester polymer; [6] The thermoplastic resin (B) is at least one selected from a copolymerized polyester in which at least a part of the polycyclohexanedimethylene terephthalate component is substituted with isophthalic acid and an ethylene terephthalate / cyclohexanedimethylene terephthalate copolymer.
  • thermoplastic resin composition [7] The thermoplastic resin composition according to [1], wherein the total content of the acrylic ester polymer block (a1) is 45 to 80% by mass in the acrylic block copolymer (A); [8] A molded article comprising the thermoplastic resin composition according to any one of [1] to [7]; [9] The molded product according to [8], which is an injection molded product; [10] Grip surface layer material comprising the molded product of [8] or [9]; Is achieved by providing
  • thermoplastic resin composition having excellent oil resistance, flexibility and fluidity, and a molded article having low anisotropy and excellent paintability, comprising the thermoplastic resin composition.
  • FIG. 3 is a TEM image of a molded article made of the thermoplastic resin composition of Example 2.
  • FIG. 6 is a TEM image of a molded article made of the thermoplastic resin composition of Comparative Example 5.
  • Acrylic block copolymer (A) The acrylic block copolymer (A), which is a component constituting the thermoplastic resin composition of the present invention, is an acrylate polymer block (a1) (hereinafter sometimes simply referred to as polymer block (a1)). And a methacrylic acid ester polymer block (a2) (hereinafter sometimes simply referred to as polymer block (a2)).
  • the content of the acrylate unit in the polymer block (a1) and the content of the methacrylic ester unit in the polymer block (a2) are each preferably 60% by mass or more, and more preferably 80% by mass or more. More preferred.
  • the polymer block (a1) in the acrylic block copolymer (A) is mainly composed of acrylate units.
  • acrylic esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, and n-hexyl acrylate.
  • thermoplastic resin composition of the present invention methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, acrylic acid 2 -Preferred are alkyl acrylates such as ethylhexyl and dodecyl acrylate, and more preferred are n-butyl acrylate and 2-ethylhexyl acrylate.
  • an acrylic acid ester having a crosslinkable functional group such as 2-hydroxyethyl acrylate, glycidyl acrylate, and allyl acrylate, as long as the effects of the present invention are not impaired; a methacrylic acid ester polymer block (a2) described later; Constituent methacrylic acid ester; methacrylic acid; acrylic acid; aromatic vinyl compound; acrylonitrile; methacrylonitrile; olefin and other monomers as small amounts (10% by mass or less, preferably 5% by mass) Or less).
  • the polymer block (a2) in the acrylic block copolymer (A) is mainly composed of methacrylic acid ester units, and examples of the methacrylic acid ester for forming the polymer block include methyl methacrylate and methacrylic acid.
  • 2-hydroxyethyl methacrylate, Methacrylic acid ester having a crosslinkable functional group such as glycidyl methacrylate and allyl methacrylate; acrylic acid ester described above; methacrylic acid; acrylic acid, aromatic vinyl compound; acrylonitrile; methacrylonitrile; other monomers such as olefin May be used as a copolymerization component in a small amount (10% by mass or less, preferably 5% by mass or less).
  • the acrylic block copolymer (A) is a polymer block derived from a monomer other than the acrylic ester and methacrylic ester separately from the polymer block ( c) may be included.
  • Examples of the monomer constituting the polymer block (c) include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; styrene, ⁇ -methylstyrene, Aromatic vinyl compounds such as p-methylstyrene and m-methylstyrene; vinyl acetate, vinylpyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ⁇ -caprolactone, valero Examples include lactones.
  • olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene
  • conjugated dienes such as butadiene, isoprene and myrcene
  • the form of bonding of the respective polymer blocks constituting the acrylic block copolymer (A) is not particularly limited, and may be any of linear, branched, radial, and the like.
  • ⁇ (a1)-(a2) ⁇ n structure ⁇ (a1)-(a2) ⁇ n- (a1) structure, (a2)- ⁇ (a1)-(a2) ⁇ n structure, (a2)- ⁇ (A1)-(a2) ⁇ n- (c) structure, (c)-(a2)- ⁇ (a1)-(a2) ⁇ n- (c) structure and other linear structures
  • ⁇ (a1)- (A2) ⁇ nZ structure n is a natural number, Z represents a coupling agent residue
  • thermoplastic resin (B) in the thermoplastic resin composition of the present invention, a linear structure is preferable, and the polymer block (a2) is bonded to both ends of the polymer block (a1). It is more preferable to use a triblock copolymer.
  • the weight average molecular weight of the acrylic block copolymer (A) is preferably in the range of 10,000 to 200,000, more preferably in the range of 15,000 to 150,000.
  • the weight average molecular weight of the acrylic block copolymer (A) is less than 10,000, the melt viscosity is lowered, the melt kneading property with the thermoplastic resin (B) is deteriorated, and the obtained molded product The dispersibility of the thermoplastic resin inside tends to be inferior.
  • the weight average molecular weight of the polymer block (a1) and the polymer block (a2) in the acrylic block copolymer (A) is preferably 2,000 to 100,000. More preferably, it is from 000 to 80,000.
  • the total content of the polymer block (a1) in the acrylic block copolymer (A) is preferably 40 to 85% by mass from the viewpoint of flexibility of the thermoplastic resin composition in the present invention, The content is more preferably 50 to 80% by mass, and further preferably 55 to 75% by mass. If the content of the polymer block (a1) is more than the above range, sticking may occur in the thermoplastic resin composition of the present invention, which may not be suitable as a molding material. On the other hand, when less than the said range, the fluidity
  • the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the acrylic block copolymer (A) is preferably 1.01 or more and less than 1.50, more preferably 1.01 to 1.35. 1.01 to 1.20 is more preferable.
  • the acrylic block copolymer (A) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the molecular chain terminal, if necessary.
  • a method for producing the acrylic block copolymer (A) a method of living polymerization of monomers constituting each polymer block is suitably used.
  • living polymerization include a method of living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral salt such as an alkali metal salt or an alkaline earth metal salt (see Patent Document 5), organic alkali metal Living anionic polymerization using a compound as a polymerization initiator in the presence of an organoaluminum compound (see Patent Document 6), Living polymerization using an organic rare earth metal complex as a polymerization initiator (see Patent Document 7), ⁇ -halogenation Examples include a method of living radical polymerization using an ester compound as an initiator in the presence of a copper compound (see Non-Patent Document 2).
  • the monomer which comprises each polymer block using a polyvalent radical polymerization initiator and a polyvalent radical chain transfer agent is polymerized, and the mixture containing the acrylic block copolymer (A) used by this invention
  • the acrylic block copolymer (A) is obtained with a narrow molecular weight distribution and high purity, and an oligomer or fluidity that causes the impact strength and heat resistance of the thermoplastic resin composition of the present invention to decrease.
  • a method of living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound is preferable.
  • an organic alkali metal compound conventionally used as an anionic polymerization initiator in anionic polymerization can be used without particular limitation.
  • an organolithium compound from the viewpoint of productivity.
  • the organolithium compounds that can be used in the present invention include alkyllithiums such as n-butyllithium, sec-butyllithium, and t-butyllithium; lithium salts of monoanions based on fluorenyllithium and ⁇ -methylstyrene oligomers.
  • sec-butyl lithium, t-butyl lithium, lithium ethyl isobutyrate, 1,3-bis (lithio-1,3-dimethylpentyl) benzene, 1,3-bis (lithiophenyl-3-methylpentyl) benzene Etc. are preferred.
  • organoaluminum compound examples include isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutyl bis (2,6-di-t-butylphenoxy) aluminum, isobutyl bis [2,2 ′ -Methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, n-octylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6-di-t- Butylphenoxy) aluminum, n-octylbis [2,2′-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, tris (2,6-di-t-butyl-4-methylphenoxy) aluminum, tris And (2,6-diphenylphenoxy) aluminum.
  • isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,4-di-t-butylphenoxy) aluminum, n-octylbis (2,6-di-t-) Butyl-4-methylphenoxy) aluminum or n-octylbis (2,4-di-t-butylphenoxy) aluminum is preferred.
  • the content of the acrylic block copolymer (A) in the thermoplastic resin composition of the present invention is such that the acrylic block copolymer (A) and the thermoplastic resin (from the viewpoint of flexibility, fluidity, and oil resistance ( It is more than 50 parts by mass and less than or equal to 85 parts by mass with respect to a total of 100 parts by mass of B), preferably from 55 to 80 parts by mass, and more preferably from 60 to 75 parts by mass. Preferably, it is 65 parts by mass or more and 72 parts by mass or less.
  • the content of the acrylic block copolymer (A) exceeds the above range, the oil resistance and tensile storage elastic modulus of the molded product obtained from the thermoplastic resin composition of the present invention are lowered, and sufficient physical properties are obtained. There is no tendency.
  • the content of the acrylic block copolymer (A) is less than the above range, the flexibility and fluidity of the molded product obtained from the thermoplastic resin composition of the present invention are lowered.
  • thermoplastic resin (B) used in the present invention is melted by heating from 30 ° C. to 280 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC).
  • the crystal melting heat quantity (hereinafter simply referred to as crystal melting heat quantity) measured when heated to 280 ° C. again at a temperature rising rate of 10 ° C./min after cooling at a temperature decreasing rate of 10 ° C./min is 25 J / g or less. .
  • thermoplastic resin (B) examples include polycarbonate resins such as bisphenol A-based polycarbonates; copolymer polyesters (PCT-A: Eastman Chemical) in which at least part of the acid component of polycyclohexanedimethylene terephthalate is substituted with isophthalic acid.
  • PCT-A Eastman Chemical
  • aromatic polyester resins such as ethylene terephthalate / cyclohexanedimethylene terephthalate copolymer
  • aliphatic polyester resins and the like. These may be used individually by 1 type and may use 2 or more types together.
  • the heat of crystal melting of the thermoplastic resin (B) is more preferably 10 J / g or less. preferable.
  • the temperature decreasing rate from 280 ° C. to 30 ° C. at 10 ° C./min.
  • a thermoplastic resin in which a crystallization peak is not observed in DSC when cooled is preferred.
  • the thermoplastic resin (B) is preferably an amorphous thermoplastic resin, and more preferably an amorphous polyester resin.
  • the crystal melting heat quantity is usually 0 J / g or more.
  • thermoplastic resin (B) When a polycarbonate resin is used as the thermoplastic resin (B), the heat resistance of the molded body made of the thermoplastic resin composition of the present invention is improved.
  • the polycarbonate resin is usually produced by reacting a dihydric phenol and a carbonate precursor.
  • the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A, bis (4-hydroxyphenyl) -p-isopropylbenzene.
  • Hydroquinone resorcinol, 4,4′-dihydroxyphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-Hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like.
  • Examples of the carbonate precursor include phosgene; diaryl carbonates such as diphenyl carbonate; dihaloformates such as haloformates and dihaloformates of dihydric phenols;
  • Examples of the polycarbonate resin those using bisphenol A as a raw material are preferable.
  • the polycarbonate resin In producing the polycarbonate resin, one kind of dihydric phenol may be used alone, or two or more kinds may be used in combination. Moreover, you may use a catalyst, a molecular weight modifier, antioxidant, etc. as needed.
  • the polycarbonate resin may be, for example, a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound or a mixture of two or more polycarbonate resins.
  • the molecular weight of the polycarbonate resin is not particularly limited. For example, when a polycarbonate resin is obtained using bisphenol A as a dihydric phenol and phosgene as a carbonate precursor, a ratio measured at 20 ° C. as a methylene chloride solution having a concentration of 0.7 g / dl. Those having a viscosity in the range of 0.15 to 1.5 are preferred.
  • the polyester resin is usually produced by condensation polymerization of dicarboxylic acid or its alkyl ester, acid halide or acid anhydride and glycol.
  • dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p, p′-dicarboxydiphenylsulfone, and p-carboxyl.
  • Examples include phenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid or mixtures thereof.
  • glycol examples include linear alkylene glycols having 2 to 12 carbon atoms such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; pyrocatechol, resorcinol, hydroquinone, bisphenol Aromatic glycols such as A; alicyclic glycols such as 1,4-cyclohexanedimethanol; or alkyl-substituted derivatives of these compounds.
  • Suitable polyester resins include PCT-A, ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer, and the like.
  • the thermoplastic resin composition of the present invention is a molded product obtained by injection molding under the conditions of a cylinder temperature of 240 ° C., a mold temperature of 50 ° C., an injection speed of 20 mm / second, and a cooling time of 40 seconds.
  • the TD is preferably in the range of 0.5 to 2.0, more preferably 0.8 to 1.8. When E ′ MD / E ′ TD is within the above range, the paintability of the molded article is excellent.
  • thermoplastic resin composition of the present invention is within the range that does not impair the effects of the present invention.
  • additives include mineral oil softeners such as paraffinic oil and naphthenic oil; ⁇ ⁇ calcium carbonate, talc, carbon black, titanium oxide, silica, clay for the purpose of improving or increasing heat resistance, weather resistance, etc.
  • Inorganic fillers such as barium sulfate and magnesium carbonate; inorganic fibers or organic fibers such as glass fibers and carbon fibers for reinforcement; thermal stabilizers; antioxidants; light stabilizers; adhesives; Antistatic agent; foaming agent; coloring pigment; flame retardant; anti-sticking agent; crystal nucleating agent; compatibilizing agent;
  • heat stability in order to further improve heat resistance and weather resistance, it is practically preferable to add heat stability, an antioxidant, and the like.
  • the method for preparing the thermoplastic resin composition of the present invention is not particularly limited, but a melt-kneading method is preferable in order to enhance the dispersibility of each component constituting the thermoplastic resin composition.
  • a melt-kneading method is preferable in order to enhance the dispersibility of each component constituting the thermoplastic resin composition.
  • the acrylic block copolymer (A) and the thermoplastic resin (B) may be mixed simultaneously with other polymers or additives as described above, or a thermoplastic resin ( The acrylic block copolymer (A) may be mixed after mixing B) together with the other polymer or additive.
  • various kneaders such as a kneader, a Banbury mixer, a mixing roll, and a twin-screw extruder can be used.
  • thermoplastic resin (B) and the acrylic block copolymer (A) can be used. From the viewpoint of improving the compatibility, it is preferable to use a twin screw extruder.
  • the temperature at the time of melt-kneading can be appropriately adjusted according to the melting temperature of the acrylic block copolymer (A) and the thermoplastic resin (B) to be used, and is usually a temperature in the range of 180 ° C to 300 ° C.
  • the thermoplastic resin composition of this invention can be obtained with arbitrary forms, such as a pellet and powder.
  • the thermoplastic resin composition in the form of pellets, powder, etc. is suitable for use as a molding material.
  • thermoplastic resin composition of the present invention is excellent in melt fluidity, and can be molded using a molding method and molding processing apparatus generally used for thermoplastic resins.
  • a laminate that can be molded by injection molding, extrusion molding, compression molding, blow molding, calendar molding, vacuum molding, etc., and includes a mold, a pipe, a sheet, a film, a fibrous material, and a layer made of the thermoplastic resin composition
  • a molded article having an arbitrary shape such as a body can be obtained.
  • Examples of the laminate as described above include, for example, a composite resin molded body including a thermoplastic hard resin layer and a layer made of the thermoplastic resin composition of the present invention, and a metal (metal compound) layer and the thermoplastic resin of the present invention.
  • the thing containing the layer which consists of compositions is mentioned.
  • the hard resin layer or metal layer retains the rigidity of the entire laminate, the hard resin layer or metal layer forms the main body or skeleton of the laminate, and the thermoplastic resin composition layer of the present invention,
  • the laminated body which expresses the performance as a grip surface layer member and a skin member can be obtained.
  • the thing which vapor-deposited the metal to the thermoplastic resin layer may be used.
  • the thermoplastic hard resin is not particularly limited as long as it has a desired mechanical strength.
  • polycarbonate styrene resin such as acrylic resin, ABS resin and polystyrene
  • polyester resin polyamide resin
  • Vinyl resin or the like is used.
  • the metal or metal compound is not particularly limited, and is a metal such as aluminum, iron, copper, silver, gold, platinum; silicon oxide, aluminum oxide, titanium oxide, niobium oxide, tantalum oxide, yttrium oxide, indium-doped tin oxide, etc.
  • Metal nitrides such as silicon nitride and aluminum nitride; metal complex oxides such as barium titanate, strontium titanate, lead titanate, potassium niobate, lead niobate, barium tantalate, lithium tantalate; acid Examples thereof include metal oxynitrides such as silicon nitride and aluminum oxynitride; sulfides such as zinc sulfide; oxysulfides such as zinc oxysulfide and the like.
  • the composite resin molded body is obtained by extruding two materials of the hard resin and the thermoplastic resin composition of the present invention separately by using two extruders, and joining them into one die so that the two-piece material is heat-melted.
  • Co-extrusion molding method to form a two-layer molded body by wearing, or two-layer molded body by heat-sealing two materials in one mold using an injection molding machine equipped with two injection cylinders A two-layer molded body obtained by injection-injecting the thermoplastic resin composition of the present invention into a mold in which the hard resin molded body molded by an injection molding machine is inserted and thermally fused. It is manufactured by the insert injection molding method.
  • the laminate of the metal layer and the layer made of the thermoplastic resin is formed by a method in which each layer is molded and thermally fused, a method of insert injection molding in the same manner as described above, a layer formed by the thermoplastic resin composition, It can be manufactured by a method of forming a metal layer by vacuum deposition or the like.
  • the molded article comprising the thermoplastic resin composition of the present invention as described above has both paintability and oil resistance and is excellent in flexibility, for example, daily goods such as grip materials; stationery supplies; household appliances; sports Products: Molded parts for automobile interior and exterior such as door handles, side garnishes, instrument panels, console boxes, door trims, and bumpers; electrical and electronic equipment parts such as connectors and switch covers; housings; containers and containers.
  • thermoplastic resins (B-1) to (B-4) were defined as the heat of crystal melting ( ⁇ H) of the thermoplastic resins (B-1) to (B-4).
  • ⁇ H heat of crystal melting
  • a sample was heated and melted from 30 ° C. to 280 ° C. at a heating rate of 10 ° C./min, and a peak was observed when the sample was cooled from 280 ° C. to 30 ° C. at a cooling rate of 10 ° C./min.
  • a crystallization peak and no crystallization peak was observed it was regarded as no crystallization peak.
  • 60 g of pellets of thermoplastic resins (B-1) to (B-4) were melt kneaded using a lab plast mill.
  • melt flow rate (MFR) of the thermoplastic resin compositions or thermoplastic resins obtained in Examples 1 to 14 and Comparative Examples 1 to 5 conforms to JIS K 7210. It was measured under the conditions of 230 ° C., load 2.16 kg and 10 minutes, and used as an index of melt fluidity.
  • an injection molding machine (SE18DU, manufactured by Sumitomo Heavy Industries, Ltd.) is used for measuring the tensile storage elastic modulus and molding processability of the molded product, and the cylinder temperature is 240 ° C. and the mold temperature is 50.
  • An injection-molded article having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm molded under the conditions of ° C, injection speed of 20 mm / second and cooling time of 40 seconds was used.
  • the test piece was cut out 10 mm so that the center of the short side of the test piece was in the center in the TD direction of the injection molded product 25 mm in the MD direction from the end on the gate side.
  • the position of 10 mm in the MD direction from the gate of the injection molded product is 10 mm so that the center of the short side of the test piece is located, and the width of the injection molded product is the long side (25 mm). Cut out.
  • the viscoelasticity spectrometer (the SII nanotechnology company make, SII EXSTAR6000 series DMS6100) was used for the measurement of the tensile storage elastic modulus.
  • thermoplastic resin compositions obtained in Examples 1 to 14 or Comparative Examples 1 to 5 were injection molded under the above conditions, and the sprue breakage was recorded when 10 molded products were continuously molded. And used as an index of moldability.
  • ⁇ No sprue breakage occurred in 1 out of 10 pieces, indicating good moldability.
  • X One or more sprue breaks out of ten pieces occurred.
  • Paintability color development and adhesion
  • a paint (Planet PX-1, Origin Electric) was applied with a sponge roll to injection molded products obtained by molding the thermoplastic resin compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 5 under the above-mentioned predetermined conditions.
  • the appearance was visually evaluated from the vertical direction and the oblique direction with respect to the coated surface, and used as an index of color development.
  • ⁇ There is no uneven coloring and the appearance is good.
  • ⁇ Color unevenness was observed when observed from an oblique direction.
  • X Color unevenness was observed when observed from the vertical and oblique directions.
  • the crosscut test was done based on JISK5400 using the said sample, and it was set as the parameter
  • B-1 Polyethylene terephthalate / polycyclohexanedimethylene terephthalate copolymer (Eastman GN007, manufactured by Eastman)
  • B-2 Polyethylene terephthalate / polycyclohexanedimethylene terephthalate copolymer (Eastman's “Eastar DN011”)
  • B-3 Polycyclohexanedimethylene terephthalate substituted with isophthalic acid (Eastman CHEMICAL) “Eastar AN004”)
  • B-4 Polycarbonate resin ("Iupilon S2000" manufactured by Mitsubishi Engineering Plastics)
  • PBT resin "Novaduran 5010L” manufactured by Mitsubishi Engineering Plastics
  • PET resin: “KS710B8S” manufactured by Kuraray Table 1 shows the heat of crystal fusion of B-1 to B-4, PBT and PET, and the presence or absence of a crystallization peak when D
  • the obtained acrylic block copolymer (A-1) was polymethyl methacrylate (PMMA) block (a2) -poly A triblock copolymer comprising an n-butyl acrylate (PnBA) block (a1) -polymethyl methacrylate (PMMA) block (a2), and the PMMA block (a2) has an Mw of 9,700, Mw / Mn is 1.07, and Mw of the acrylic block copolymer (A-1) as a whole is 65,000 and Mw / Mn is 1.11.
  • the ratio of each polymer block is PMMA (15 Mass%)-PnBA (70 mass%)-PMMA (15 mass%).
  • the reaction mixture after termination of polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 6).
  • the obtained acrylic block copolymer (A-2) was obtained as PMMA block (a2) -PnBA block (a1) -PMMA.
  • a triblock copolymer (PMMA-b-PnBA-b-PMMA) comprising the block (a2), wherein the first PMMA block (a2) has an Mw of 9,800 and Mw / Mn of 1.07.
  • the Mw of the acrylic block copolymer (A-2) as a whole is 70,000 and Mw / Mn is 1.13, and the ratio of each polymer block is PMMA (14% by mass) -PnBA (50 % By mass) -PMMA (36% by mass).
  • the reaction mixture after termination of the polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 9).
  • the obtained acrylic block copolymer (A-3) was PMMA block (a2) -PnBA block (a1) -PMMA.
  • the block (a2) is a triblock copolymer, and the PMMA block (a2) has an Mw of 8,900 and an Mw / Mn of 1.05.
  • the acrylic block copolymer (A- 3) The total Mw was 76,000, Mw / Mn was 1.08, and the ratio of each polymer block was PMMA (12 mass%)-PnBA (76 mass%)-PMMA (12 mass%). .
  • Weight average molecular weight Mw, molecular weight distribution Mw / Mn of the acrylic block copolymers (A-1) to (A-3), content of the polymer block (a1) in the acrylic block copolymer (A) Is shown in Table 2.
  • thermoplastic resin composition [Examples 1 to 14, Comparative Examples 1 to 7]
  • the acrylic block copolymers (A-1) to (A-3) obtained in the above reference examples and the thermoplastic resins (B-1) to (B-4), PBT and PET are shown in Table 3 below.
  • the pellets of the thermoplastic resin composition were produced by melting and kneading at 240 ° C. with a twin screw extruder at the blending ratio shown in Table 4 and then extruding and cutting.
  • the obtained thermoplastic resin composition pellets were injection molded by the predetermined method to obtain a molded product.
  • Tables 3 and 4 show the evaluation results of these thermoplastic resin compositions and molded articles.
  • the molded products obtained from the thermoplastic resin compositions of Examples 1 to 14 are different from the molded products obtained from the thermoplastic resin compositions of Comparative Examples 1 to 6. It can be seen that the directivity is low and the moldability is higher. Among them, when comparing Example 4, Example 8 and Example 11, Example 2, Example 6, Example 9, Example 12, and Comparative Example 5, or Example 5, Example 13 and Comparative Example 6, respectively. It can be seen that when the heat of crystal melting of the thermoplastic resin composition (B) is low, the molded product obtained has low anisotropy and a good molded product can be obtained. In Comparative Example 7, the acrylic block copolymer (A-1) and PET could not be uniformly melt-kneaded, and a molded product could not be obtained. Moreover, when the anisotropy of a molded article is low, it turns out that coloring is favorable and the adhesiveness of a coating material is also favorable.
  • the content of the acrylic block copolymer (A) is 100 masses in total of the acrylic block copolymer (A) and the thermoplastic resin (B).
  • the amount is more than 50 parts by mass with respect to the part, the anisotropy of the molded product is low, and it can be seen that a good molded product can be obtained.
  • FIGS. 1 and 2 are cross-sectional TEM images of molded articles of the thermoplastic resin composition in Example 2 and Comparative Example 5, respectively.
  • the observation position is the central portion in the thickness direction at a position 10 mm from the gate.
  • the thermoplastic resin composition (B) is dispersed in a spherical form of submicron order in the acrylic block copolymer (A), and dispersion in the dispersion diameter is small. I understand that.
  • Comparative Example 5 PBT is dispersed in the acrylic block copolymer (A) in a submicron spherical shape or a single micron cylindrical shape, and both the dispersion diameter and the dispersion state vary greatly. Recognize. In Comparative Example 5, it is presumed that the anisotropy of the molded product was particularly increased because the PBT was partially cylindrical.
  • the molded article comprising the thermoplastic resin composition of the present invention has both paintability and oil resistance, and is excellent in flexibility. Therefore, daily goods such as grip materials; stationery supplies; household appliances and sports goods; door handles, side garnishes It is useful in various applications such as molded parts for automobile interior and exterior such as instrument panels, console boxes, door trims, and bumpers; electrical and electronic equipment parts such as connectors and switch covers; housings and containers. Moreover, since the molded article obtained from the thermoplastic resin composition of the present invention is excellent in paintability, it can be subjected to surface treatments such as printing, painting, plating, vapor deposition, and sputtering according to the purpose.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a pour but de proposer : une composition de résine thermoplastique qui a une excellente résistance aux huiles, une excellente flexibilité et une excellente fluidité ; et un article moulé qui est formé de la composition de résine thermoplastique et a d'excellentes propriétés de revêtement. A cet effet, l'invention concerne une composition de résine thermoplastique qui contient un copolymère à blocs acrylique spécifique (A) et une résine thermoplastique (B), et qui a une enthalpie de fusion cristalline (ΔH) de 25 J/g ou moins telle que déterminée par chauffage et fusion de la composition de résine thermoplastique de 30°C à 280°C à une allure de chauffage de 10°C/minute, puis refroidissement de la composition de résine thermoplastique de 280°C à 30°C à une allure de refroidissement de 10°C/minute, et après cela chauffage de la composition de résine thermoplastique à nouveau jusqu'à 280°C à une allure de chauffage de 10°C/minute, à l'aide d'un calorimètre différentiel à balayage (DSC). La teneur de la résine thermoplastique (B) par rapport à 100 parties en masse du total du copolymère à blocs acrylique (A) et de la résine thermoplastique (B) est 15 parties en masse ou plus mais inférieure à 50 parties en masse.
PCT/JP2013/065249 2012-06-08 2013-05-31 Composition de résine thermoplastique et article moulé à base de celle-ci WO2013183567A1 (fr)

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US20220221681A1 (en) * 2019-07-23 2022-07-14 Sumitomo Electric Fine Polymer, Inc. Optical element holder and optical component

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JP2004231940A (ja) * 2002-09-30 2004-08-19 Kanegafuchi Chem Ind Co Ltd 熱可塑性エラストマー組成物
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WO2020075655A1 (fr) * 2018-10-10 2020-04-16 株式会社クラレ Pastilles contenant un copolymère séquencé et article moulé obtenu à partir de ces pastilles
CN112805331A (zh) * 2018-10-10 2021-05-14 株式会社可乐丽 包含嵌段共聚物的粒料和由该粒料得到的成型体
JPWO2020075655A1 (ja) * 2018-10-10 2021-09-16 株式会社クラレ ブロック共重合体を含むペレット及び該ペレットから得られる成形体
CN112805331B (zh) * 2018-10-10 2023-06-09 株式会社可乐丽 包含嵌段共聚物的粒料和由该粒料得到的成型体
JP7312190B2 (ja) 2018-10-10 2023-07-20 株式会社クラレ ブロック共重合体を含むペレット及び該ペレットから得られる成形体

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