WO2013183567A1 - Thermoplastic resin composition and molded article of same - Google Patents

Abstract

[Problem] To provide: a thermoplastic resin composition which has excellent oil resistance, flexibility and fluidity; and a molded article which is formed of the thermoplastic resin composition and has excellent coating properties. [Solution] A thermoplastic resin composition which contains a specific acrylic block copolymer (A) and a thermoplastic resin (B), and which has a crystal melting enthalpy (∆H) of 25 J/g or less as determined by heating and melting the thermoplastic resin composition from 30°C to 280°C at a heating rate of 10°C/minute, then cooling the thermoplastic resin composition from 280°C to 30°C at a cooling rate of 10°C/minute, and after that heating the thermoplastic resin composition again to 280°C at a heating rate of 10°C/minute, using a differential scanning calorimeter (DSC). The content of the thermoplastic resin (B) relative to 100 parts by mass of the total of the acrylic block copolymer (A) and the thermoplastic resin (B) is 15 parts by mass or more but less than 50 parts by mass.

Description

Thermoplastic resin composition and molded article thereof

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.

Engineering plastics, especially polybutylene terephthalate (hereinafter referred to as PBT) are excellent in chemical resistance, heat resistance and mechanical properties, and are widely used as industrial resins. However, since PBT is inferior in flexibility and paintability and uses are limited, a method of adding a small amount of thermoplastic elastomer (less than 10% by mass) has been proposed as a technique for imparting flexibility (Patent Document 1). reference). However, the resin composition obtained according to Patent Document 1 does not necessarily have sufficient flexibility.

On the other hand, with respect to PBT, a specific acrylic block copolymer in which a polymer block consisting of two methacrylate units is bonded to both ends of a polymer block consisting of an acrylic ester unit is added. A resin composition having both oil resistance and oil resistance has been proposed (see Patent Document 2). In addition, as a resin composition excellent in impact resistance, flexibility and heat distortion resistance, a resin composition comprising an acrylic block copolymer and a thermoplastic resin (particularly a crystalline thermoplastic resin) (see Patent Document 3), As an automotive soft material rich in oil resistance and heat resistance, a resin composition in which an acrylic block copolymer and a thermoplastic resin are kneaded and dynamically crosslinked has been proposed (see Patent Document 4).

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.

However, 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

Injection Molding Revision 9th edition Itochu Ito, Yasuhito Sasaki and 2 others, 1990, issued by Plastic Age Co., Ltd. 32 pages Macromolecular Chemical Physics 201, 1108-1114 (2000)

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. .

According to the present invention, 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. The amount of the thermoplastic resin (B) having a heat of crystal melting (ΔH) of 25 J / g or less measured when heated again to 280 ° C. 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;
[2] 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. to 280 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), from 280 ° C. to 30 ° C. The 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. [1] 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

According to the present invention, it is possible to provide a 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.

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.

Hereinafter, the present invention will be described in detail.
(1) 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. Examples of 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. Cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-methoxyethyl acrylate, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving impact strength, fluidity, etc. of the 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. In addition, 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. Ethyl, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, methacrylic acid Cyclohexyl, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, methacrylate Such as Le acid 2-methoxy ethyl. These may be used individually by 1 type, or may use 2 or more types together. Among them, from the viewpoint of improving the impact strength, heat resistance and the like of the thermoplastic resin composition of the present invention, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, methacrylic acid 2 -An alkyl ester of methacrylic acid such as ethylhexyl, cyclohexyl methacrylate or isobornyl methacrylate is preferred, and methyl methacrylate is more preferred. In addition, within the scope of the effects of the present invention, 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).

In the range where the effects of the present invention are exhibited, 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, α-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, ε-caprolactone, valero Examples include lactones.

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. For example, {(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) and the like. From the viewpoint of improving the dispersibility of the 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. When 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. On the other hand, when it is larger than 200,000, the melt becomes highly viscous, melt fracture occurs during melt molding, and the appearance of the molded product tends to be impaired. 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 | liquidity of a thermoplastic resin composition and the softness | flexibility of the molded article obtained from it will fall. Further, the total content of the polymer block (a2) in the acrylic block copolymer (A) is preferably 15 to 60% by mass, more preferably 20 to 50% by mass, and further 25 to 45% by mass. preferable.

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. When the molecular weight distribution is in the above range, the moldability when melt-molding the thermoplastic resin composition of the present invention can be stabilized. 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.

As a method for producing the acrylic block copolymer (A), a method of living polymerization of monomers constituting each polymer block is suitably used. Examples of such 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), α-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). Moreover, 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 method of manufacturing as is also mentioned. Among these, 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. From the viewpoint of suppressing the by-product of the high molecular weight compound that causes a decrease in water, 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.

As the organic alkali metal compound, an organic alkali metal compound conventionally used as an anionic polymerization initiator in anionic polymerization can be used without particular limitation. Among these, it is preferable to use an organolithium compound from the viewpoint of productivity. Examples of 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 α-methylstyrene oligomers. Aryllithium of 1,1-diphenylhexyllithium, diphenylmethyllithium, aralkyllithium such as 1,1-diphenyl-3-methylpentyllithium; trimethylsiloxylithium; lithium ethyl isobutyrate; tetra α-methylstyrene dilithium; And organic dilithium compounds such as 1,3-bis (lithio-1,3-dimethylpentyl) benzene and 1,3-bis (lithiophenyl-3-methylpentyl) benzene. These organolithium compounds may be used alone or in combination of two or more. Among them, 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.

Examples of the organoaluminum compound 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. Among them, 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. When 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. On the other hand, when 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.

(2) Thermoplastic resin (B)
The 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. . Examples of such thermoplastic resin (B) 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. For example, "Easter A150" or "Easter A004"), 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. From the standpoint that compatibility with the acrylic block copolymer (A) is enhanced and the effects of the present invention are more exhibited, the heat of crystal melting of the thermoplastic resin (B) is more preferably 10 J / g or less. preferable. In addition, from the viewpoint of the anisotropy and paintability of the molded product, after heating and melting from 30 ° C. to 280 ° C. at a temperature rising rate of 10 ° C./min, 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. Furthermore, from the viewpoint of the anisotropy and paintability of the molded product, 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.

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. Examples of 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; As the polycarbonate resin, those using bisphenol A as a raw material are preferable.

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.

When a polyester resin is used as the thermoplastic resin (B), the chemical resistance of the molded article made of the thermoplastic resin composition of the present invention is improved. The polyester resin is usually produced by condensation polymerization of dicarboxylic acid or its alkyl ester, acid halide or acid anhydride and glycol. Examples of the 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. Examples of the glycol 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. JIS K 7244 -4 tensile storage modulus of the measured flow direction in conformity with (E _'MD), and tensile storage modulus perpendicular to the flow direction (E' _TD) ratio at 30 ℃ _{E 'MD /} E' _{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.

In addition to the acrylic block copolymer (A) and the thermoplastic resin (B), the thermoplastic resin composition of the present invention is within the range that does not impair the effects of the present invention. These polymers and additives may be contained. Examples of additives include mineral oil softeners such as paraffinic oil and naphthenic oil; 炭 酸 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; Among these additives, 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. When melt-kneading, for example, 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. For the melt-kneading, various kneaders such as a kneader, a Banbury mixer, a mixing roll, and a twin-screw extruder can be used. The kneadability of the 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. Moreover, 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.

The 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. For example, 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. For example, if 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. For example, 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.

For example, 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. When heat-sealing or heat-bonding, a composite resin molded article having excellent peel strength can be obtained without particularly using an adhesive. In addition, 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.

Since 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.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. Various physical properties in Examples and Comparative Examples were measured or evaluated by the following methods.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) of acrylic block copolymer (A)
It was determined by gel permeation chromatography (hereinafter referred to as GPC) as a standard polystyrene equivalent molecular weight.
・ Equipment: Tosoh GPC equipment “HLC-8020”
Column: “TSK1 GMHXL”, “G4000HXL” and “G5000HXL” manufactured by Tosoh Corporation are connected in series. Eluent: Tetrahydrofuran Eluent flow rate: 1.0 mL / min Column temperature: 40 ° C.
・ Detection method: Differential refractive index (RI)

(2) Constitution ratio of each polymer block in each acrylic block copolymer It was determined by ¹ H-NMR measurement.
・ Equipment: JEM Nuclear Magnetic Resonance Device “JNM-LA400”
Solvent: deuterated chloroform (CDCl ₃ )

(3) Crystal heat of fusion (ΔH) and crystallization peak of thermoplastic resins (B-1) to (B-4) Using a differential scanning calorimeter (DSC) (manufactured by Mettler Toledo, TGA / DSC1 Star System) The sample melted by heating from 30 ° C. to 280 ° C. at a heating rate of 10 ° C./min was cooled from 280 ° C. to 30 ° C. at a cooling rate of 10 ° C./min, and then again 30 at a heating rate of 10 ° C./min. The heat of crystal melting (ΔH) measured when the temperature was raised from 280 ° C. to 280 ° C. was defined as the heat of crystal melting (ΔH) of the thermoplastic resins (B-1) to (B-4). In addition, when 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, When there was a crystallization peak and no crystallization peak was observed, it was regarded as no crystallization peak. As a measurement sample, 60 g of pellets of thermoplastic resins (B-1) to (B-4) were melt kneaded using a lab plast mill.

(4) Melt fluidity of thermoplastic resin compositions The 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.

In the following, 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.

(5) Measurement of Tensile Storage Modulus of Molded Product From the molded product obtained by injection molding of the thermoplastic resin compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 5 under the above conditions, a short side of 10 mm and a long side cut 25mm of the test piece, the tensile storage elastic modulus in the flow direction (MD direction) (E _'MD) and tensile storage modulus perpendicular to the flow direction (TD direction) (E' the _TD), JIS K 7244 -4, respectively, and the ratio of the tensile storage modulus at 30 ° C. E ′ _MD / E ′ _TD was determined. It shows that the anisotropy of a molded article is so small that this figure is near 1.0. For the measurement of E ′ _MD , 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. Regarding the measurement of E ′ _TD , 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. In addition, the viscoelasticity spectrometer (the SII nanotechnology company make, SII EXSTAR6000 series DMS6100) was used for the measurement of the tensile storage elastic modulus.

(6) Molding workability The 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.

(7) 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.
Δ: Color unevenness was observed when observed from an oblique direction.
X: Color unevenness was observed when observed from the vertical and oblique directions.
Moreover, the crosscut test was done based on JISK5400 using the said sample, and it was set as the parameter | index of the adhesiveness of a coating material. Ten points indicate good adhesion and zero points indicate low adhesion.

The symbols described in Tables 1 to 4 indicate the following components. (Hereinafter described with the following symbols.)
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 DSC measurement is performed under the condition (5).

[Reference Example 1] [Organic Aluminum Compound: Preparation of Isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum]
After drying with sodium, 25 ml of dry toluene obtained by distillation under an argon atmosphere and 11 g of 2,6-di-t-butyl-4-methylphenol were added to a 200 ml flask whose inside was replaced with argon. And dissolved with stirring at room temperature. 6.8 ml of triisobutylaluminum was added to the obtained solution and stirred at 80 ° C. for about 1 hour, so that isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum was added at 0.7 mmol / A toluene solution containing a concentration of g was prepared.

[Reference Example 2] [Synthesis of acrylic block copolymer (A-1)]
After the inside of the 2 liter three-necked flask was purged with nitrogen, 1040 g of toluene and 100 g of 1,2-dimethoxyethane were added at room temperature, and then isobutyl bis (2,6-di-t-butyl) obtained by the method of Reference Example 1 was added. 66 g of a toluene solution containing 46 mmol of (-4-methylphenoxy) aluminum was added, and further a sec-butyllithium solution was added so that sec-butyllithium was 10 mmol. Subsequently, 68 g of methyl methacrylate was added to the mixed solution and reacted at room temperature for 1 hour, and then 0.1 g of the reaction solution was collected (sampling sample 1). Subsequently, the reaction mixture was cooled to −25 ° C., and 249 g of n-butyl acrylate was added dropwise over 2 hours. After completion of the addition, the mixture was stirred for 5 minutes, and 0.1 g of the reaction solution was collected (sampling sample 2). Subsequently, 68 g of methyl methacrylate was added to the reaction mixture, the reaction mixture was returned to room temperature and stirred for 8 hours, and then 4 g of methanol was added to terminate the polymerization. The reaction mixture after termination of polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 3). When ¹ H-NMR measurement and GPC measurement were performed using the sampling samples 1 to 3, 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%).

[Reference Example 3] [Synthesis of acrylic block copolymer (A-2)]
After the inside of the 2 liter three-necked flask was purged with nitrogen, 1040 g of toluene and 100 g of 1,2-dimethoxyethane were added at room temperature, and then isobutyl bis (2,6-di-t-butyl) obtained by the method of Reference Example 1 was added. 66 g of a toluene solution containing 46 mmol of (-4-methylphenoxy) aluminum was added, and further a sec-butyllithium solution was added so that sec-butyllithium was 10 mmol. Subsequently, 69 g of methyl methacrylate was added to the mixed solution and reacted at room temperature for 1 hour, and then 0.1 g of the reaction solution was collected (sampling sample 4). Subsequently, the reaction mixture was cooled to −25 ° C., and 194 g of n-butyl acrylate was added dropwise over 2 hours. After completion of dropping, the mixture was stirred for 5 minutes, and 0.1 g of the reaction mixture was collected (sampling sample 5). Subsequently, 173 g of methyl methacrylate was added, the reaction mixture was returned to room temperature and stirred for 8 hours, and then 4 g of methanol was added to the reaction mixture to terminate the polymerization. The reaction mixture after termination of polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 6). When ¹ H-NMR measurement and GPC measurement were performed using sampling samples 4 to 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. Further, 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).

[Reference Example 4] [Synthesis of acrylic block copolymer (A-3)]
After the inside of the 2 liter three-necked flask was purged with nitrogen, 1040 g of toluene and 100 g of 1,2-dimethoxyethane were added at room temperature, and then isobutyl bis (2,6-di-t-butyl) obtained by the method of Reference Example 1 was added. 30 g of a toluene solution containing 21 mmol of (-4-methylphenoxy) aluminum was added, and a sec-butyllithium solution was further added so that sec-butyllithium was 8.0 mmol. Subsequently, 52 g of methyl methacrylate was added to the reaction mixture and reacted at room temperature for 1 hour, and then 0.1 g of the reaction mixture was collected (sampling sample 7). Subsequently, the reaction mixture was cooled to −25 ° C., and 347 g of n-butyl acrylate was added dropwise over 2 hours. After completion of dropping, 0.1 g of the reaction solution was collected (sampling solution 8). Subsequently, 52 g of methyl methacrylate was added, the reaction solution was returned to room temperature and stirred for 8 hours, and then 4 g of methanol was added to the reaction mixture to terminate the polymerization. The reaction mixture after termination of the polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 9). When ¹ H-NMR measurement and GPC measurement were performed using sampling samples 7 to 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.

[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.

From Tables 3 and 4, 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.

From Examples 1 and 2 and Comparative Examples 1 and 2, the content of the acrylic block copolymer (A) is 100 masses in total of the acrylic block copolymer (A) and the thermoplastic resin (B). When 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. From these figures, in Example 2, 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. On the other hand, in 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.

Claims (10)

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) The sample was melted by heating from 30 ° C. to 280 ° C. at a heating rate of 10 ° C./min, cooled from 280 ° C. to 30 ° C. at a cooling rate of 10 ° C./min, and then again at 280 ° C. at a heating rate of 10 ° C./min. The amount of heat of crystal melting (ΔH) measured when heated to 0 ° C. is 25 J / g or less. The content of the thermoplastic resin (B) is that of the acrylic block copolymer (A) and the thermoplastic resin (B). The thermoplastic resin composition which is 15 mass parts or more and less than 50 mass parts with respect to a total of 100 mass parts. The molded article made of the thermoplastic resin composition has a tensile storage elastic modulus (E ′ _MD ) in a flow direction measured according to JIS K 7244-4, and a tensile storage elastic modulus in a direction perpendicular to the flow direction (E ′ _MD ). 2. The thermoplastic resin composition according to claim 1, wherein the ratio (E ′ _MD / E ′ _TD ) of E ′ _TD ) at 30 ° C. is in the range of 0.5 to 2.0. The thermoplastic resin (B) is melted by heating from 30 ° C. to 280 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), and then the cooling rate of 10 from 280 ° C. to 30 ° C. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition does not have a crystallization peak when cooled at a temperature of ° C / minute. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (B) is an amorphous thermoplastic resin. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (B) is an amorphous polyester polymer. The thermoplastic resin (B) is at least one selected from a copolymerized polyester in which at least a part of a component of polycyclohexanedimethylene terephthalate is substituted with isophthalic acid and an ethylene terephthalate / cyclohexanedimethylene terephthalate copolymer. 2. The thermoplastic resin composition according to 1. The thermoplastic resin composition according to claim 1, wherein the total content of the acrylic ester polymer block (a1) is 45 to 80% by mass in the acrylic block copolymer (A). A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 7. The molded product according to claim 8, which is an injection molded product. A grip surface layer material comprising the molded product according to claim 8 or 9.

Images