JP2013036019A - Resin composition and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent flowability and impact strength, and to provide a molded product made from the resin composition.SOLUTION: The resin composition contains 0.01-20 pts.mass of acrylic-based block copolymer (B) having an acrylic ester polymer block (b1) and methacrylic acid ester polymer block (b2), to 100 pts.mass of thermoplastic resin composition (A) such as a recycled polycarbonate-based resin and an acrylonitrile-butadiene-styrene copolymer (ABS resin) having ≥2,000 MPa of bend elastic constant. Also, the molded product is made from the resin composition.

Description

  The present invention relates to a resin composition excellent in fluidity and impact strength and a molded product thereof.

  Conventionally, thermoplastic resins such as engineering plastics have been used in a wide range of fields such as office equipment, electrical / electronic equipment, and automobile fields. In recent years, effective use of resources has been demanded for these thermoplastic resins from the viewpoint of environmental considerations and cost reduction. For example, thinning of molded products and material recycling of thermoplastic resins are being studied.

  In order to reduce the thickness of the molded product, high fluidity is required for the thermoplastic resin. In addition, a thin molded product is required to have high impact strength. As a technique for improving impact strength, a technique of increasing the molecular weight of a thermoplastic resin (see Patent Document 1) and a technique of adding a core-shell type modifier (see Patent Document 2) have been proposed. However, with these methods, the impact strength can be greatly improved, but the fluidity is greatly reduced, and it is difficult to achieve both improvement in fluidity and impact strength.

  The material recycling of the thermoplastic resin refers to the reuse of the thermoplastic resin collected as a waste material of office equipment as a raw material for a product such as the same office equipment or an equivalent product. Conventionally, the thermoplastic resin recovered as a waste material is significantly less deteriorated in physical properties such as mechanical strength and flexibility due to deterioration over time than a new thermoplastic resin (hereinafter referred to as virgin raw material) that has not been recycled. It was often used as a product of lower quality than raw materials (called cascade recycling). Moreover, there are many so-called thermal recyclings in which the thermoplastic resin recovered as waste material is burned to recover heat. For this reason, the amount of thermoplastic resin that can be material-recycled is small, and a method for material-recycling the thermoplastic resin more efficiently has been demanded from the viewpoint of cost and environment.

It is known that thermoplastic resins having an ester bond such as polycarbonate resin cannot avoid a decrease in molecular weight due to hydrolysis, which is one of aging deterioration, and greatly reduce mechanical properties such as impact strength and tensile strength. Yes. Polycarbonate resins are excellent in impact resistance and heat resistance, but are expensive, and therefore, material recycling techniques are actively studied.
For example, a method of adding a virgin raw material to a recycled thermoplastic resin (see Patent Document 3), core shell so that the molded product made of a recycled thermoplastic resin has the same physical properties as a molded product made of a virgin raw material A method of adding a mold modifier (see Patent Document 4) has been studied. In these methods, the amount of energy used can be reduced as compared with the case where a molded product is produced again using a virgin raw material. However, the method of adding the virgin raw material has a problem that the ratio of the added amount of the virgin raw material to the recycled resin is inevitably increased, and the usage rate of the recycled thermoplastic resin is low. In addition, the method of adding the core-shell type modifier is inferior in moldability because the fluidity of the recycled thermoplastic resin is lowered, and its use is limited, and a high molding temperature is required. There is also a problem that the deterioration of the process proceeds.

  On the other hand, as an impact modifier for thermoplastic resins having ester bonds such as polymethacrylate resins, polycarbonate resins and polyethylene terephthalate resins, block copolymers having acrylic esters and methacrylate esters as structural units Is known to be effective (see Patent Document 5 and Patent Document 6). However, Patent Document 5 and Patent Document 6 do not describe the thin-wall moldability of thermoplastic resin and material recycling.

JP-A-8-127686 JP 2002-308997 A JP 2000-159900 A JP 2003-096286 A JP 2006-225413 A Japanese Patent Laid-Open No. 10-168271 Japanese Patent Publication No. 7-25859 JP-A-11-335432 JP-A-6-93060

Macromolecular Chemical Physics 201, 1108-1114 (2000)

  The objective of this invention is providing the resin composition which is excellent in fluidity | liquidity and impact strength, and the molded article consisting of this resin composition.

According to the present invention, the above object is
(1) An acrylic block copolymer having an acrylate polymer block (b1) and a methacrylic ester polymer block (b2) with respect to 100 parts by mass of the thermoplastic resin composition (A) having a flexural modulus of 2000 MPa or more. A resin composition containing 0.01 to 20 parts by mass of the polymer (B);
(2) The resin composition of (1), wherein the thermoplastic resin composition (A) contains a rubber-based reinforcing resin;
(3) The thermoplastic resin composition (A) is a recycled thermoplastic resin composition (A ′), which is a virgin raw material thermoplastic resin composition (A) and a recycled thermoplastic resin composition (A The resin composition according to (1) or (2), wherein the melt flow rate ratio (A ′ / A) at 260 ° C. and 2.16 kgf is 2.00 or less;
(4) The resin composition according to any one of (1) to (3), wherein the thermoplastic resin composition (A) contains a polycarbonate resin;
(5) The resin composition according to any one of (1) to (4), wherein the thermoplastic resin composition (A) contains a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer (ABS resin);
(6) The resin composition according to any one of (1) to (5), further comprising a core-shell elastic polymer (f);
(7) The content of the acrylic block copolymer (B) with respect to 100 parts by mass of the thermoplastic resin composition is in the range of 0.1 to 4.8 parts by mass, and any one of (1) to (6) Resin composition;
(8) A molded article comprising the resin composition according to any one of (1) to (7);
(9) The molded product of (8) which is a housing;
Is achieved by providing

  According to the present invention, a resin composition excellent in fluidity and impact strength and a molded product thereof can be provided.

3 is a TEM image of a molded article made of the resin composition of Example 2. 3 is a TEM image of a molded article made of the resin composition of Comparative Example 1.

Hereinafter, the present invention will be described in detail.
(1) Thermoplastic resin composition (A)
The thermoplastic resin composition (A) used in the present invention has a flexural modulus of 2000 MPa or more. In consideration of the balance of impact strength, elastic modulus and fluidity of the molded article containing the resin composition of the present invention, the bending elastic modulus of the thermoplastic resin composition (A) is more preferably 2300 MPa or more. If the flexural modulus is smaller than the above range, the resulting resin composition becomes too flexible and the impact strength becomes insufficient. In this specification, the flexural modulus is a flexural modulus measured at 23 ° C. in accordance with JIS K 7171 using a multi-purpose test piece B-type dumbbell-shaped test piece in accordance with JIS K 7139. .

Examples of the resin contained in the thermoplastic resin composition (A) include a resin in which a bond between monomer units is an ester bond. Specifically, a polycarbonate resin; a polyethylene terephthalate resin, a polybutylene terephthalate. Examples include, but are not limited to, aromatic polyester resins such as resins; aliphatic polyester resins such as polylactic acid. Moreover, among these resins, one kind may be used alone, or two or more kinds may be used in combination.
From the viewpoint of improving compatibility with the acrylic block copolymer (B) and improving the impact strength, heat resistance, and rigidity of the molded article made of the resin composition of the present invention, a polycarbonate resin may be used. preferable.

  The polycarbonate resin is usually produced by reacting a dihydric phenol and a carbonate precursor. As the dihydric phenol, 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 can be mentioned. Examples of the carbonate precursor include carbonyl halides such as phosgene, diaryl carbonates such as diphenyl carbonate, haloformates, dihaloformates such as dihaloformates of dihydric phenols, and the like. As the polycarbonate resin, those using bisphenol A as a raw material are preferable.

  When the polycarbonate resin is produced by reacting the dihydric phenol with the carbonate precursor, the dihydric phenol may be used alone or in combination of two or more, and the catalyst and the molecular weight are adjusted as necessary. Agents, antioxidants and the like may be used. The polycarbonate resin may be, for example, a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or may be 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, the polycarbonate resin is measured at a temperature of 20 ° C. with a 0.7 g / dl methylene chloride solution. Those having a specific viscosity in the range of 0.15 to 1.5 are preferably used.

  Examples of other resins that may be contained in the thermoplastic resin composition (A) include rubber-reinforced resins. When the rubber-reinforced resin is contained, the thermoplastic resin composition (A) is preferable in that it has excellent impact strength. Examples of the rubber reinforced resin include a copolymer including an aromatic vinyl monomer component (c), a vinyl cyanide monomer component (d), and a rubbery polymer (e).

  When a copolymer containing an aromatic vinyl monomer component (c), a vinyl cyanide monomer component (d) and a rubbery polymer (e) is used as the rubber-reinforced resin, the aromatic vinyl monomer Examples of the component (c) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinylxylene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more. Of these, styrene or α-methylstyrene is preferable.

  Examples of the vinyl cyanide monomer component (d) include acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.

Examples of the rubbery polymer (e) include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, and butylenes. Diene rubbers such as isoprene copolymers and butadiene-isoprene copolymers; ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, ethylene and α-olefins Olefin-based copolymers such as copolymers with ethylene; Copolymers with ethylene-unsaturated carboxylic esters such as ethylene-methacrylic acid ester and ethylene-butyl acrylate; Acrylic acid ester-butadiene copolymers such as acrylic Acid butyl-butadiene copolymer, etc. Ethylene-propylene non-conjugated dienter such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer Polymer; chlorinated polyethylene and the like can be mentioned. These may be used alone or in combination of two or more. Of these, diene rubbers, acrylic elastic polymers, and ethylene-propylene-nonconjugated diene terpolymers are preferable, and diene rubbers such as polybutadiene and styrene-butadiene copolymers are more preferable.
The composition ratio of each component of the copolymer including the aromatic vinyl monomer component (c), the vinyl cyanide monomer component (d), and the rubbery polymer (e) is not particularly limited.

  The copolymer containing the aromatic vinyl monomer component (c), the vinyl cyanide monomer component (d), and the rubbery polymer (e) comprises the aromatic vinyl monomer component (c) and cyanide. Even if the rubber polymer (e) is mixed in the copolymer of the vinyl monomer component (d), the aromatic vinyl monomer component ( It may be a copolymer of c) and a vinyl cyanide monomer component (d), or a mixture thereof.

  In the copolymer including the aromatic vinyl monomer component (c), the vinyl cyanide monomer component (d) and the rubbery polymer (e), for example, ( (Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; acrylic acid, methacrylic acid Α, β-unsaturated carboxylic acids such as (meth) acrylic acid and maleic anhydride; maleimides such as N-phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; glycidyl groups such as glycidyl (meth) acrylate One type or two or more types of monomers may be copolymerized.

  Specific examples of the copolymer containing the aromatic vinyl monomer component (c), the vinyl cyanide monomer component (d) and the rubbery polymer (e) include an acrylonitrile-butadiene-styrene copolymer ( ABS resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer, and the like, but are not limited thereto. From the viewpoint of improving fluidity (molding processability) and impact strength, an acrylonitrile-butadiene-styrene copolymer (ABS resin) is preferable.

  The production method of the copolymer containing the aromatic vinyl monomer component (c), the vinyl cyanide monomer component (d) and the rubbery polymer (e) is not particularly limited, and bulk polymerization, solution polymerization, Known production methods such as suspension polymerization and emulsion polymerization can be used. The weight average molecular weight (Mw) of the copolymer is preferably from 30,000 to 250,000, more preferably from 60,000 to 140,000, from the viewpoint of impact strength and fluidity.

  The copolymer containing the aromatic vinyl monomer component (c), the vinyl cyanide monomer component (d) and the rubbery polymer (e) may have a narrow molecular weight distribution, and may be a block copolymer, A copolymer having high stereoregularity may be used.

  The copolymer including the aromatic vinyl monomer component (c), the vinyl cyanide monomer component (d), and the rubbery polymer (e) further contains other aromatic vinyl monomer components. It may be a mixture with a polymer or copolymer. Specific examples of the polymer or copolymer containing an aromatic vinyl monomer component include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-acrylate copolymer, and the like. The polymer or copolymer containing the aromatic vinyl monomer component may have high stereoregularity, and in the case of a copolymer, a random copolymer, a block copolymer, an alternating Any of a copolymer etc. may be sufficient. For example, acrylonitrile-butadiene-styrene copolymer is generally a mixture of acrylonitrile-styrene copolymer and acrylonitrile-butadiene-styrene copolymer, and is preferably used in the present invention in terms of improving fluidity. The

  In the acrylonitrile-butadiene-styrene copolymer, the proportion of the diene rubber component in 100% by mass of the acrylonitrile-butadiene-styrene copolymer component is preferably 8 to 50% by mass, more preferably 10 to 35% by mass. . The rubber particle size of the acrylonitrile-butadiene-styrene copolymer is preferably 0.1 to 5.0 μm, more preferably 0.3 to 1.5 μm. The structure of the rubber particles may form a single phase or may have a salami structure.

  The production of the thermoplastic resin composition (A) will be described. As a suitable example, a thermoplastic resin composition comprising a polycarbonate resin and a copolymer containing an aromatic vinyl monomer component (c), a vinyl cyanide monomer component (d) and a rubbery polymer (e) ( A) can be produced by introducing each pellet into a single-screw or twin-screw extruder with separate feeders and melt-kneading them, or by pre-blending the pellets and then melt-kneading them. The mixing ratio of the polycarbonate resin and the copolymer containing the aromatic vinyl monomer component (c), the vinyl cyanide monomer component (d) and the rubbery polymer (e) is particularly limited in a strict sense. Usually, it is preferably in the range of 20/80 to 90/10 by mass ratio.

  When the thermoplastic resin composition (A) comprises a polycarbonate resin and a copolymer containing an aromatic vinyl monomer component (c), a vinyl cyanide monomer component (d) and a rubbery polymer (e) The resin composition of the present invention obtained by using such a thermoplastic resin composition (A) and a molded product comprising the resin composition are further excellent in fluidity and impact strength.

  The thermoplastic resin composition (A) includes a polycarbonate resin and a copolymer containing an aromatic vinyl monomer component (c), a vinyl cyanide monomer component (d) and a rubbery polymer (e). When using what consists of unification, a commercial item may be used. Examples of the polycarbonate / ABS resin include “Multilon TN7500” manufactured by Teijin Chemicals Ltd. and “Cycoloy C6600” manufactured by Sabic Innovative Plastics.

  The thermoplastic resin composition (A) used in the present invention may be a recycled thermoplastic resin composition (A ′). The recycled thermoplastic resin composition (A ′) is a crushed product obtained by pulverizing and washing a molded product of thermoplastic resin used in, for example, office equipment, electrical / electronic equipment, and automobiles, or a recovered material of waste materials. Moreover, the virgin raw material of the thermoplastic resin which is the same composition as this crushed material may be included. The recycled thermoplastic resin composition (A ′) may be recycled several times. The recycled thermoplastic resin composition (A ′) is preferably composed of the same composition as that shown in the thermoplastic resin composition (A), and the polycarbonate resin and the aromatic vinyl monomer component. (C), a molded product obtained by molding a thermoplastic resin composition comprising a vinyl cyanide monomer component (d) and a copolymer containing a rubbery polymer (e) or a recovered waste material was pulverized and washed. Particularly preferred is a crushed material.

  The recycled thermoplastic resin composition (A ′) has a fluidity as compared with the case where the thermoplastic resin composition (A) is a virgin raw material due to hydrolysis due to deterioration over time, thermal history or ultraviolet light deterioration. Generally, it becomes higher. From the viewpoint of impact strength and fluidity, the ratio of the melt flow rate at 260 ° C. and 2.16 kg of the thermoplastic resin composition (A) of the virgin raw material and the recycled thermoplastic resin composition (A ′) (A ′ / A) is preferably 2.00 or less, and more preferably 1.60 or less. When the ratio of the melt flow rate is larger than the above range, the mechanical strength of the recycled thermoplastic resin composition (A ′) is lowered, and the impact strength of the molded product made of the obtained resin composition tends to be lowered. .

The particle size of the recycled thermoplastic resin composition (A ′) is preferably 10 mm or less, and more preferably 6 mm or less. If necessary, it may be granulated to a particle size of 10 mm or less by a method such as sheet cutting, strand cutting, hot air cutting or underwater cutting. If the particle size is larger than the above range, uniform melt kneading tends to be difficult.
In Examples to be described later, as the recycled thermoplastic resin composition (A ′), a resin in which hydrolysis was promoted by leaving the virgin raw material at 80 ° C. and 95% RH for 168 hours was used.

(2) Acrylic block copolymer (B)
The acrylic block copolymer (B), which is a component constituting the resin composition of the present invention, has an acrylate polymer block (b1) and a methacrylic ester polymer block (b2). The content of the acrylate unit or methacrylate unit in the polymer block (b1) or polymer block (b2) is preferably 60% by mass or more, more preferably 80% by mass or more. preferable.

  In the acrylic block copolymer (B), the acrylic ester polymer block (b1) is mainly composed of an acrylic ester unit, and as an acrylic ester for forming the polymer block, for example, methyl acrylate , Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate , Pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycine acrylate Le, like allyl acrylate. These may be used alone or in combination of two or more. Among them, alkyl acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate are thermoplastic resin compositions of the present invention. From the viewpoint of improving impact strength, fluidity, and the like of an object, n-butyl acrylate and 2-ethylhexyl acrylate are more preferable. Further, in the range where the effects of the present invention are exhibited, other methacrylic acid ester, methacrylic acid, acrylic acid, aromatic vinyl compound, acrylonitrile, methacrylonitrile, olefin and the like constituting the methacrylic acid ester polymer block (b2) to be described later A small amount (10 mol% or less, preferably 5 mol% or less) of a monomer may be used as a copolymerization component.

  In the acrylic block copolymer (B), the methacrylic acid ester polymer block (b2) is mainly composed of methacrylic acid ester units, and examples of the methacrylic acid ester for forming the polymer block include methacrylic acid. Methyl, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-methacrylate Hexyl, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylate Nokishiechiru, 2-hydroxyethyl methacrylate, methacrylic acid 2-methoxyethyl, glycidyl methacrylate acid and methacrylic acid allyl. These may be used alone or in combination of two or more. Among them, from the viewpoint of improving the impact strength, heat resistance and the like of the resin composition of the present invention, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate. Further, alkyl methacrylates such as cyclohexyl methacrylate and isobornyl methacrylate are preferable, and methyl methacrylate is more preferable. Further, within the range where the effects of the present invention are exhibited, a small amount (10) of other monomers such as acrylic acid ester, methacrylic acid, acrylic acid, aromatic vinyl compound, acrylonitrile, methacrylonitrile, olefin are used as a copolymerization component. (Mol% or less, preferably 5 mol% or less).

  In the range where the effects of the present invention are exhibited, the acrylic block copolymer (B) is a polymer block derived from a monomer other than the acrylic ester and methacrylic ester separately from the above-described polymer block ( s). The form of the bond between the polymer block (s), the acrylate polymer block (b1), and the methacrylic ester polymer block (b2) is not particularly limited. For example, (b2)-{(b1) -(B2)} n- (s) structure (n represents a natural number) and (s)-(b2)-{(b1)-(b2)} n- (s) structure. Examples of the monomer constituting the polymer block (s) include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; styrene, α- Aromatic vinyl compounds such as methylstyrene, p-methylstyrene, m-methylstyrene; vinyl acetate, vinylpyridine, acrylonitrile, methacrylonitrile, vinyl ketone monomers, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide , Ε-caprolactone, valerolactone and the like.

  The acrylic block copolymer (B) is composed of an acrylic ester polymer block (b1) and a methacrylic ester polymer block (b2), and the molecular chain form is not particularly limited. , Branched or radial. Among these, it is preferable to use a triblock copolymer in which the polymer block (b2) is bonded to both ends of the polymer block (b1) from the viewpoint of improving the impact strength, heat resistance and the like of the resin composition of the present invention.

  The weight average molecular weight of the acrylic block copolymer (B) is preferably in the range of 10,000 to 200,000, from 15,000, from the viewpoint of improving impact strength, fluidity, etc. of the resin composition of the present invention. A range of 150,000 is more preferred. If the weight average molecular weight of the acrylic block copolymer (B) is smaller than the above range, the melt viscosity is lowered, the melt kneadability with the thermoplastic resin composition (A) is deteriorated, and the resulting molding The mechanical strength of the product 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 acrylic ester polymer block (b1) in the acrylic block copolymer (B) is preferably 2,000 to 100,000, and is 5,000 to 80,000. Is more preferable. Further, the weight average molecular weight of the methacrylic acid ester polymer block (b2) is preferably 2,000 to 100,000, and more preferably 5,000 to 80,000.

  The content in the acrylic block copolymer (B) of the acrylic ester polymer block (b1) constituting the acrylic block copolymer (B) is a viewpoint of improving the impact strength of the resin composition of the present invention. Therefore, it is preferably 30 to 90% by mass, more preferably 50 to 85% by mass, and further preferably 65 to 80% by mass. If the content of the acrylate polymer block (b1) is more than the above range, the resin composition of the present invention may cause sticking and may not be suitable as a molding material. On the other hand, when less than the said range, the softness | flexibility and fluidity | liquidity of an acryl-type block copolymer (B) will fall, and it will become the tendency for the fluidity | liquidity and impact strength of a resin composition and a molded article obtained from it to deteriorate.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the acrylic block copolymer (B) is preferably 1.01 or more and less than 1.50, more preferably 1.01 to 1.35. . When the molecular weight distribution is in the above range, molding processability when melt-molding the resin composition of the present invention can be stabilized.

  The acrylic block copolymer (B) 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 end, if necessary.

As a method for producing the acrylic block copolymer (B), a method of living polymerization of monomers constituting each 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 or alkaline earth metal salt (see Patent Document 7), organic alkali metal, and the like. Living anion polymerization using a compound as a polymerization initiator in the presence of an organoaluminum compound (see Patent Document 8), Living polymerization using an organic rare earth metal complex as a polymerization initiator (see Patent Document 9), 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 1). Moreover, the monomer which comprises each polymer block is polymerized using a polyvalent radical polymerization initiator and a polyvalent radical chain transfer agent, and the acrylic block copolymer (B) used by this invention is contained. The method of manufacturing as a mixture is also mentioned. Among these, the acrylic block copolymer (B) is obtained with a narrow molecular weight distribution and high purity, that is, an oligomer that causes a decrease in impact strength and heat resistance of the resin composition of the present invention, and fluidity. A method of living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound is preferable because by-product formation of a high molecular weight substance that causes a reduction can be suppressed.
Examples of the organoaluminum compound include isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutyl bis (2,6-di-t-butylphenoxy) aluminum, and 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-tert-butylphenoxy)] aluminum, tris (2,6-di-tert-butyl-4-methylphenoxy) aluminum, tris Examples include (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 particularly preferred from the viewpoint of polymerization activity, block efficiency and the like.

  The content of the acrylic block copolymer (B) in the resin composition of the present invention is 0.01 to 20 masses per 100 mass parts of the thermoplastic resin composition (A) from the viewpoint of impact strength and fluidity. Parts, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 4.8 parts by mass or less. Moreover, it is preferable that it is 0.1 mass part or more, It is more preferable that it is 0.5 mass part or more, It is further more preferable that it is 1 mass part or more. When the content of the acrylic block copolymer (B) exceeds the above range, the elastic modulus of the molded product obtained from the resin composition of the present invention is lowered, and sufficient impact strength tends not to be obtained.

  The impact strength improving effect of the acrylic block copolymer (B) appears more conspicuously when the thermoplastic resin composition (A) contains a rubber-reinforced resin. In particular, the rubber-reinforced resin is a copolymer containing an aromatic vinyl monomer component (c), a vinyl cyanide monomer component (d), and a rubbery polymer (e), and examples described later and As is apparent from the TEM photographs in the comparative examples, the polymer component (c) of the aromatic vinyl monomer, the polymer component (d) of the vinyl cyanide monomer, and the rubber polymer (e) The polymer component (c) of the aromatic vinyl monomer and the weight of the vinyl cyanide monomer are more uniformly dispersed in the resin (eg, polycarbonate resin) which is the main component of the plastic resin composition (A). It is presumed that the impact strength is improved by preventing interlaminar peeling between the coalesced component (d) and the rubbery polymer (e) and the thermoplastic resin composition (A).

  The resin composition of the present invention is within the range where the effects of the present invention are exhibited, in addition to the above-described thermoplastic resin composition (A) and acrylic block copolymer (B), if necessary, other polymers and An additive may be contained. Examples of other polymers include core-shell elastic polymer (f), and examples of additives include paraffinic oil and naphthenic oil for improving fluidity during molding. Mineral oil softener; inorganic filler such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate for the purpose of improving or increasing heat resistance, weather resistance, etc .; for reinforcement Inorganic or organic fibers such as glass fiber and carbon fiber; heat stabilizer; antioxidant; light stabilizer; adhesive agent; tackifier; plasticizer; antistatic agent; foaming agent; Agents and the like. Among these additives, in order to further improve heat resistance and weather resistance, it is practically preferable to add a heat stabilizer, an antioxidant and the like.

  When the resin composition of the present invention contains the core-shell elastic polymer (f), the impact strength may be further improved while maintaining excellent fluidity. Here, the core-shell elastic polymer (f) is a core-shell structure polymer or resin composition having a rubber component (f1) as a core and a polymer component (f2) as a shell.

  Examples of the rubber component (f1) include those mentioned as the rubber polymer (e); acrylic rubber; silicone rubber; silicone-acrylic composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate; polybutene Rubber: Polyisobutylene rubber or a mixture thereof is used. From the viewpoint of improving weather resistance and low-temperature impact strength, among them, diene rubbers such as polybutadiene and styrene-butadiene copolymers; acrylic elastic polymers; silicone rubbers; acrylic rubbers; silicone-acrylic composite rubbers are preferable. Acrylic rubber, silicone rubber, and silicone-acrylic composite rubber are more preferable, and silicone-acrylic composite rubber is more preferable.

  The rubber component (f1) preferably has an average particle size of 0.03 to 5.0 μm. Within this range, the impact strength of the resin composition of the present invention can be improved.

  The core-shell elastic polymer (f) can be obtained by graft copolymerizing a vinyl monomer with the rubber component (f1). The polymer component of the vinyl monomer is a polymer component (f2) that becomes a shell. Examples of the vinyl monomer constituting the polymer component (f2) include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methyl (meth) acrylate, ethyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as 2-ethylhexyl methacrylate; glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate, allyl glycidyl ether, ethylene glycol glycidyl ether; hydroxy such as hydroxy (meth) acrylate And group-containing vinyl monomers. Among these, (meth) acrylic acid alkyl ester is preferable, and methyl methacrylate is more preferable.

  For example, the core-shell elastic polymer (f) is obtained by radical polymerizing a vinyl monomer in one or more stages in the presence of the latex of the rubber component (f1) to produce an acid such as sulfuric acid, hydrochloric acid or phosphoric acid, or calcium chloride. It is obtained by coagulating using a coagulant such as sodium chloride, solidifying through heat treatment, and then dehydrating, washing and drying.

  The ratio of the vinyl monomer constituting the rubber component (f1) and the polymer component (f2) is 30 to 95% by mass of the rubber component (f1) based on the mass of the core-shell elastic polymer (f). The vinyl monomer is preferably 5 to 70% by mass, more preferably 40 to 90% by mass of the rubber component (f1) and 10 to 60% by mass of the vinyl monomer. If the content of the vinyl monomer (f1) is 5% by mass or more, the core-shell elastic polymer (f) is sufficiently dispersed in the resin composition, and if it is 70% by mass or less, the resin composition Impact strength is improved.

  The core-shell elastic polymer (f) is commercially available, and for example, “Metabrene” S2001 and W450A manufactured by Mitsubishi Rayon Co., Ltd., “Paralloid” EXL2314 and EXL2602 manufactured by Rohm and Haas can be used. It can also be produced by the method described in JP-A-2006-002110.

  The method for preparing the resin composition of the present invention is not particularly limited, but a melt-kneading method is preferable in order to improve the dispersibility of each component constituting the resin composition. Examples of the preparation method include a method of melt-kneading the thermoplastic resin composition (A) and the acrylic block copolymer (B), and if necessary, other polymers or additives described above. May be mixed simultaneously, or the acrylic block copolymer (B) may be mixed after the thermoplastic resin composition (A) is mixed with the other polymer or additive described above. The melt-kneading operation can be performed using a known mixing or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer. In particular, it is preferable to use a twin-screw extruder from the viewpoint of improving the kneadability and compatibility between the thermoplastic resin composition (A) and the acrylic block copolymer (B). The temperature at the time of melt-kneading can be appropriately adjusted according to the melting temperature of the thermoplastic resin composition (A) and acrylic block copolymer (B) to be used, and is usually in the range of 110 ° C to 300 ° C. At a temperature of Thus, the resin composition of this invention can be obtained with arbitrary forms, such as a pellet and powder. The resin composition in the form of pellets, powders and the like is suitable for use as a molding material.

  The resin composition of the present invention is excellent in melt fluidity and can be molded using a molding method or a molding apparatus generally used for thermoplastic resins. For example, it 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, a laminate including a layer made of the resin composition, etc. A molded product of any form can be obtained.

  The molded article made of the resin composition of the present invention is excellent in impact strength and heat resistance, and can be used in a wide range of applications such as electronic / electric equipment, OA equipment, mechanical equipment, and vehicles. Especially notebook computers, portable computers, printers, copiers, projectors, cameras, mobile phones, housings or chassis of optical disk drives such as DVDs, automobile center panels, door handles, malls, covers, etc. Applicable to various resin molded products. Further, the obtained molded product can be subjected to surface treatment such as printing, painting, plating, vapor deposition, and sputtering according to the purpose.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this 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)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of each acrylic block copolymer obtained in Reference Examples 2 to 5 are obtained as a standard polystyrene equivalent molecular weight by gel permeation chromatography (hereinafter referred to as GPC). From this, the molecular weight distribution (Mw / Mn) was calculated.
・ Apparatus: GPC equipment “HLC-8020” manufactured by Tosoh Corporation
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) Composition ratio of each polymer block in each acrylic block copolymer The composition ratio of each polymer block in the acrylic block copolymer obtained in Reference Examples 2 to 5 is determined by ¹ H-NMR measurement. It was.
・ Equipment: JEOL nuclear magnetic resonance apparatus “JNM-LA400”
Solvent: deuterated chloroform (CDCl ₃ )

(3) Bending elastic modulus of resin composition JIS K molded at a predetermined cylinder temperature and mold temperature by an injection molding machine using the resin compositions obtained in Examples 1-20 and Comparative Examples 1-10. The measurement was performed at 23 ° C. in accordance with JIS K 7171 using a multi-purpose test piece B-type dumbbell-shaped test piece in accordance with 7139.

(4) Impact strength of molded product Using the resin composition or thermoplastic resin obtained in Examples 1 to 20 and Comparative Examples 1 to 10, a length of 100 mm at a predetermined cylinder temperature and mold temperature by an injection molding machine. A test piece having a width of 10 mm and a thickness of 4.0 mm was molded, and a test piece having a length of 80 mm, a width of 10 mm, a thickness of 4.0 mm, and a notch depth of 2.0 mm was prepared using a notching machine. Using this test piece, Charpy impact strength was measured under the condition of 23 ° C. with a notch in accordance with JIS K 7111.

(5) Melt fluidity of molded article The melt flow rate (MFR) of the resin composition or thermoplastic resin obtained in Examples 1 to 20 and Comparative Examples 1 to 10 is 260 ° C. according to JIS K 7210. The measurement was performed under a load of 2.16 kg for 10 minutes and used as an index of melt fluidity.

(6) Thin wall formability (spiral flow)
Spiral when the spiral flow length of the resin composition or thermoplastic resin of Examples 1 to 20 or Comparative Examples 1 to 10 is injection-molded using a spiral flow mold having a channel thickness of 1 mm and a channel width of 8 mm. The flow length was measured. The evaluation conditions were a cylinder temperature of 240 or 260 ° C., a mold temperature of 60 ° C., an injection pressure of 100 or 200 MPa, an injection speed of 20 to 100 mm / sec, and an injection molding machine using SE180DU manufactured by Sumitomo Heavy Industries, Ltd.

The symbols described in Tables 1 to 4 indicate the following components. (Hereinafter described with the following symbols.)
A-1: Polycarbonate / ABS resin (“Multilon TN7500” manufactured by Teijin Chemicals Ltd.)
A-2: Polycarbonate / ABS resin ("Scicoloy C6600" manufactured by Sabic Innovative Plastics)
A′-1: Polycarbonate / ABS resin (“Multilon TN7500” manufactured by Teijin Chemicals Ltd.) left at 168 ° C. and 95% RH for 168 hours to promote hydrolysis (considered as recycled resin)
A′-2: Polycarbonate / ABS resin (“Scicoloy C6600” manufactured by Sabic Innovative Plastics Co., Ltd.) was allowed to stand for 168 hours at 80 ° C. and 95% RH to promote hydrolysis (considered as a recycled resin)
Table 1 shows the flexural modulus, melt flow rate, and melt flow rate ratio (A ′ / A) of A-1, A-2, A′-1, and A′-2.

[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-tert-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 resulting 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 / min. A toluene solution containing a concentration of g was prepared.

[Reference Example 2] [Synthesis of acrylic block copolymer (B-1)]
The inside of the 2 liter three-necked flask was replaced with nitrogen, and 1040 g of dry toluene at room temperature, 100 g of 1,2-dimethoxysilane, and isobutyl bis (2,6-di-t-butyl-) obtained by the method of Reference Example 1 were used. 30 g of toluene solution containing 21 mmol of 4-methylphenoxy) aluminum was added, and 8.0 mmol of sec-butyllithium was further added. After adding 52 g of methyl methacrylate to this liquid mixture and making it react at room temperature for 1 hour, 0.1 g of reaction liquid was extract | collected (sampling sample 1). Subsequently, the internal temperature of the reaction solution 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 2). Subsequently, 52 g of methyl methacrylate was added, and the reaction solution was returned to room temperature and stirred for 8 hours. The polymerization was stopped by adding 4 g of methanol to the reaction solution. The reaction solution after termination of the polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 3). ¹ H-NMR measurement and GPC measurement were performed using sampling samples 1 to 3, and based on the results, Mw (weight average molecular weight), Mw / of the obtained acrylic block copolymer (B-1) When the weight ratio of Mn (molecular weight distribution), methyl methacrylate polymer (PMMA) block and n-butyl acrylate polymer (PnBA) block was determined, etc., triblock copolymer consisting of PMMA block-PnBA block-PMMA block The PMMA block part has an Mw of 8,900 and an Mw / Mn of 1.05, and the acrylic block copolymer (B-1) is a composite (PMMA-b-PnBA-b-PMMA). The total Mw is 76,000, Mw / Mn is 1.08, and the ratio of each polymer block is PMMA (12% by mass) -PnBA (76% by mass). ) - it was (12 wt%).

[Reference Example 3] [Synthesis of acrylic block copolymer (B-2)]
The inside of the 2 liter three-necked flask was replaced with nitrogen, and 1040 g of dry toluene at room temperature, 100 g of 1,2-dimethoxysilane, and isobutyl bis (2,6-di-t-butyl-) obtained by the method of Reference Example 1 were used. 66 g of toluene solution containing 46 mmol of 4-methylphenoxy) aluminum was added, and 10 mmol of sec-butyllithium was further added. After adding 68 g of methyl methacrylate to this mixed solution and reacting at room temperature for 1 hour, 0.1 g of the reaction solution was collected (sampling sample 4). Subsequently, the internal temperature of the reaction solution was cooled to −25 ° C., and 249 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 5). Subsequently, 68 g of methyl methacrylate was added, and the reaction solution was returned to room temperature and stirred for 8 hours. The polymerization was stopped by adding 4 g of methanol to the reaction solution. The reaction liquid after termination of the polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 6). Using the sampling samples 4 to 6, ¹ H-NMR measurement and GPC measurement were performed, and based on the results, Mw (weight average molecular weight) of the obtained acrylic block copolymer (B-2), Mw / When the weight ratio of Mn (molecular weight distribution), methyl methacrylate polymer (PMMA) block and n-butyl acrylate polymer (PnBA) block was determined, etc., triblock copolymer consisting of PMMA block-PnBA block-PMMA block The PMMA block part has a Mw of 9,700 and Mw / Mn of 1.07, and an acrylic block copolymer (B-2) is a composite (PMMA-b-PnBA-b-PMMA). The total Mw is 65,000 and Mw / Mn is 1.11. The ratio of each polymer block is PMMA (15% by mass) -PnBA (70% by mass). ) - it was (15 mass%).

[Reference Example 4] [Synthesis of acrylic block copolymer (B-3)]
The inside of the 2 liter three-necked flask was replaced with nitrogen, and 1040 g of dry toluene at room temperature, 100 g of 1,2-dimethoxysilane, and isobutyl bis (2,6-di-t-butyl-) obtained by the method of Reference Example 1 were used. 66 g of toluene solution containing 46 mmol of 4-methylphenoxy) aluminum was added, and 10 mmol of sec-butyllithium was further added. After adding 69 g of methyl methacrylate to this mixed solution and reacting at room temperature for 1 hour, 0.1 g of the reaction solution was collected (sampling sample 7). Subsequently, the internal temperature of the reaction solution was cooled to −25 ° C., and 194 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, 173 g of methyl methacrylate was added, and the reaction solution was returned to room temperature and stirred for 8 hours. The polymerization was stopped by adding 4 g of methanol to the reaction solution. The reaction solution after the termination of the polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 9). ¹ H-NMR measurement and GPC measurement of the obtained acrylic block copolymer (B-3) were performed using the sampling samples 7 to 9, and Mw (weight average molecular weight), Mw / When the weight ratio of Mn (molecular weight distribution), methyl methacrylate polymer (PMMA) block and n-butyl acrylate polymer (PnBA) block was determined, etc., triblock copolymer consisting of PMMA block-PnBA block-PMMA block The PMMA block part has a Mw of 98,000 and Mw / Mn of 1.07, and an acrylic block copolymer (B-3) is a combined (PMMA-b-PnBA-b-PMMA). The total Mw is 70,000, Mw / Mn is 1.13, and the ratio of each polymer block is PMMA (14% by mass) -PnBA (50% by mass). %)-(36 mass%).

[Reference Example 5] [Synthesis of acrylic block copolymer (B-4)]
The interior of the three-necked flask with a volume of 2 liters was replaced with nitrogen, and 1040 g of dry toluene at room temperature, 100 g of 1,2-dimethoxysilane, and isobutyl bis (2,6-di-t-butyl-4) obtained by the method of Reference Example 1 -Methylphenoxy) 66 g of a toluene solution containing 46 mmol of aluminum was added, and 10 mmol of sec-butyllithium was further added. After adding 69 g of methyl methacrylate to this mixed solution and reacting at room temperature for 1 hour, 0.1 g of the reaction solution was collected (sampling sample 10). Subsequently, the internal temperature of the reaction solution was cooled to −25 ° C., and 492 g of n-butyl acrylate was added dropwise over 3 hours. After completion of dropping, 0.1 g of the reaction solution was collected (sampling solution 11). Subsequently, 69 g of methyl methacrylate was added, and the reaction solution was returned to room temperature and stirred for 8 hours. The polymerization was stopped by adding 4 g of methanol to the reaction solution. The reaction solution after the termination of polymerization was poured into a large amount of methanol to obtain a deposited precipitate (sampling sample 12). Using the sampling samples 10 to 12, ¹ H-NMR measurement and GPC measurement of the acrylic block copolymer (B-4) were performed, and based on the results, Mw (weight average molecular weight), Mw / Mn (molecular weight) Distribution), the weight ratio of the methyl methacrylate polymer (PMMA) block to the n-butyl acrylate polymer (PnBA) block, etc., and the triblock copolymer (PMMA block comprising PMMA block-PnBA block-PMMA block). -B-PnBA-b-PMMA), the MMMA of the PMMA block portion is 98,000, Mw / Mn is 1.06, and the Mw of the entire acrylic block copolymer (B-4) Is 111,000, Mw / Mn is 1.10, and the ratio of each polymer block is PMMA (9 mass%)-PnBA (80 mass%). -(11% by mass).

  Weight average molecular weight Mw, molecular weight distribution Mw / Mn of acrylic block copolymers (B-1) to (B-4), n-butyl acrylate unit content (acrylic block copolymer of polymer block (b1)) Table 2 shows the ratio to the combined (B).

[Examples 1 to 23, Comparative Examples 1 to 12]
Thermoplastic resin compositions (A-1), (A-2), (A'-1) and (A'-2), and the acrylic block copolymer (B-1) obtained in the above reference example To (B-4) and a core-shell type impact resistance modifier (“Metbrene S2001” manufactured by Mitsubishi Rayon Co., Ltd.) at a blending ratio shown in Tables 3 and 4 below at 230 ° C. by a twin-screw extruder. After melt-kneading, the resin composition pellets were produced by extrusion and cutting. The impact resistance, melt flowability, and thin-wall moldability of this resin composition and its molded product were evaluated by the methods described above. The results are shown in Table 3 and Table 4.

  From Tables 3 and 4, the molded products obtained from the resin compositions of Examples 1 to 23 have impact strengths as compared to the case of only the resins (A-1) or (A-2) of Comparative Examples 1 and 2. Excellent fluidity. Especially, the resin composition of Example 2, Example 4, and Examples 7-17 improved more notably. Moreover, when Example 2 and Example 4 and Example 6, Example 10, and Example 12 and Example 14 are compared, respectively, a polymer block (b1) is 40 mass% as an acryl-type block copolymer (B). It can be seen that when more are used, the impact strength and fluidity are more excellent. Moreover, when Example 2 and Example 8 or Example 10 and Example 16 are compared, respectively, when an acrylic block copolymer (B) having a weight average molecular weight (Mw) of 100,000 or less is used. It can be seen that the impact strength and fluidity are superior.

  In addition, the resin compositions of Examples 1 to 5 and Examples 7 to 17 were those of Comparative Examples 3 to 7 in which “methabrene” S2001 (manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the acrylic block copolymer (B). Compared to the resin composition, it has high fluidity, and the molded product has equivalent impact strength.

  Also, the resin compositions containing the recycled thermoplastic resin compositions (A′-1) or (A′-2) of Examples 18 to 23 and molded articles obtained therefrom were Comparative Example 8 or Comparative Example 9. As compared with the case of only the recycled thermoplastic resin composition (A′-1) or (A′-2), the fluidity and impact strength are excellent. Among these, the resin compositions of Example 22 and Example 23 were significantly improved. In addition, the resin compositions of Examples 18 to 20 and Examples 22 to 23 were comparative examples 11 in which “methabrene” S2001 (manufactured by Mitsubishi Rayon Co., Ltd.) was used in the same ratio instead of the acrylic block copolymer (B). Compared with the case of ~ 12, it had high fluidity, and the molded product had an impact strength equal to or higher than that.

  The resin compositions of Examples 18 to 23 and the molded articles obtained therefrom were compared with Comparative Example 1 or Comparative Example 2 consisting only of the virgin raw material of the thermoplastic resin composition (A-1) or (A-2). Excellent fluidity and impact strength.

  Moreover, the resin composition of Examples 1-4, Example 6, Example 8, and Examples 18-21 is superior to Comparative Example 1, Comparative Examples 3-5, Comparative Example 8, and Comparative Examples 10-11. It has a thin formability. Furthermore, the thin-wall formability at 240 ° C. of Examples 1 to 4 is superior to the thin-wall formability at 260 ° C. of Comparative Example 1 and Comparative Examples 3 to 5 consisting only of the thermoplastic resin composition (A). It can be seen that when the system block copolymer (B) is contained, the molding temperature can be lowered as compared with the conventional one. Similarly, the thin-wall moldability at 240 ° C. of Examples 18 to 20 is superior to the thin-wall moldability at 260 ° C. of Comparative Example 8 and Comparative Examples 10 to 11 made of the recycled resin composition (A ′). It has been found that when the acrylic block copolymer (B) is contained, the molding temperature can be lowered as compared with the conventional one. That is, thermal deterioration of the molded product can be prevented. Further, by adding the acrylic block copolymer (B) and the core-shell elastic polymer (f) as in Example 21, only the acrylic block copolymer (B) is maintained while maintaining excellent fluidity. As a result, a molded article having further excellent impact strength was obtained.

  1 is a TEM image of a molded article made of the resin composition of Example 2, and FIG. 2 is a TEM image of Comparative Example 1. From these figures, in Example 2, the acrylonitrile-butadiene-styrene copolymer inside was dispersed with a smaller dispersion diameter than in Comparative Example 1, and the acrylonitrile-styrene copolymer component in the acrylonitrile-butadiene-styrene copolymer was dispersed. It was confirmed that a component derived from the acrylic block copolymer (B) was present at the interface. From this, the acrylic block copolymer (B) uniformly disperses the components in the thermoplastic resin composition (A), which contributes to moldability such as impact strength, fluidity, and thin moldability. It is estimated that

  The molded article made of the resin composition of the present invention is excellent in impact strength, fluidity and heat resistance, and can be used in a wide range of applications such as electronic / electric equipment, OA equipment, mechanical equipment, and vehicles. Especially notebook computers, portable computers, printers, copiers, projectors, cameras, mobile phones, housings or chassis of optical disk drives such as DVDs, automobile center panels, door handles, malls, covers, etc. Applicable to various resin molded products. Further, the obtained molded product can be subjected to surface treatment such as printing, painting, plating, vapor deposition, and sputtering according to the purpose.

1. Acrylic block copolymer (B)
2. 2. Polycarbonate resin 3. Acrylonitrile-styrene copolymer component in acrylonitrile-butadiene-styrene copolymer Polybutadiene component in acrylonitrile-butadiene-styrene copolymer

Claims (9)

  An acrylic block copolymer having an acrylic ester polymer block (b1) and a methacrylic ester polymer block (b2) with respect to 100 parts by mass of the thermoplastic resin composition (A) having a flexural modulus of 2000 MPa or more ( A resin composition containing 0.01 to 20 parts by mass of B).   The resin composition according to claim 1, wherein the thermoplastic resin composition (A) contains a rubber-reinforced resin.   The thermoplastic resin composition (A) is a recycled thermoplastic resin composition (A ′), which is a virgin raw material thermoplastic resin composition (A) and a recycled thermoplastic resin composition (A ′). The resin composition of Claim 1 or 2 whose ratio (A '/ A) of the melt flow rate in 260 degreeC and 2.16 kgf is 2.00 or less.   The resin composition of any one of Claims 1-3 in which the said thermoplastic resin composition (A) contains a polycarbonate-type resin.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin composition (A) contains a polycarbonate-based resin and an acrylonitrile-butadiene-styrene copolymer (ABS resin).   Furthermore, the resin composition of any one of Claims 1-5 containing a core-shell elastic polymer (f).   The content of the acrylic block copolymer (B) with respect to 100 parts by mass of the thermoplastic resin composition (A) is 0.1 to 4.8 parts by mass, according to any one of claims 1 to 6. Thermoplastic resin composition.   The molded article which consists of a resin composition of any one of Claims 1-7.   The molded article according to claim 7, which is a casing.