JP2017145365A - Thermoplastic resin composition, method for producing the same, and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition capable of obtaining a molded product excellent in adhesion by an organic solvent, impact resistance, antistatic properties and color tone.SOLUTION: There is provided a thermoplastic resin composition which is obtained by blending a vinyl copolymer (A) obtained by copolymerization of a vinyl monomer mixture (a) containing at least an aromatic vinyl monomer (a1) of 5-40 wt.%, an unsaturated carboxylic acid alkyl ester monomer (a2) of 30-80 wt.% and a vinyl cyanide monomer (a3) of 10-50 wt.%, a graft copolymer (B) obtained by graft polymerization of a vinyl monomer mixture (b) containing at least an aromatic vinyl monomer (b1) of 10-30 wt.%, an unsaturated carboxylic acid alkyl ester monomer (b2) of 30-80 wt.% and a vinyl cyanide monomer (b3) of 1-10 wt.% in the presence of a rubbery polymer (r), and polyamide elastomer (C), where the thermoplastic resin composition is obtained by blending the vinyl copolymer (A) of 40-90 pts.wt., the graft copolymer (B) of 10-60 pts.wt. and the polyamide elastomer (C) of 3 pts.wt. or more with respect to 100 pts.wt. of the total of the vinyl copolymer (A) and the graft copolymer (B).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition containing a vinyl copolymer, a graft copolymer, and a polyamide elastomer, a method for producing the same, and a molded product thereof.

  ABS resin obtained by graft-copolymerizing aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile on rubbery polymers such as diene rubber is Since it is excellent in mechanical strength such as impact and rigidity, moldability and cost performance, it is widely used in application fields such as home appliances, communication equipment, transport containers, general goods and medical equipment. ABS resin has a high surface resistivity and tends to be easily charged. However, in electrical and electronic parts such as home appliances and communication-related equipment, in order to prevent static electricity failure, the surface resistivity is low and the electrostatic diffusion performance is high. There is a need for materials with excellent electrical properties.

  Also, taking a photomask case as an example of the transport container, in addition to the antistatic performance, especially in a very expensive large photomask case, the adhesive surface between the resin molded products forming the case is caused by vibration during transportation. From the viewpoint of preventing peeling and breaking, adhesion with an organic solvent is also required.

  So far, as a resin composition excellent in antistatic properties, for example, a transparent sustained antistatic thermoplastic resin composition composed of a transparent styrenic resin and a polyether ester amide (for example, see Patent Document 1) has been proposed. Yes. However, the transparent long-lasting antistatic thermoplastic resin disclosed in Patent Document 1 is insufficient in impact resistance of molded products and adhesion by organic solvents, and the usage is limited. .

  In addition, as another resin composition having excellent antistatic properties, a thermoplastic resin composition containing a styrene resin and a surface resistivity reducing substance (see, for example, Patent Document 2), a styrene resin, and an alkylene oxide unit are configured. An antistatic thermoplastic resin composition (for example, see Patent Document 3) obtained by blending a copolymer contained as components and an organic ionic conductive agent has been proposed. However, the thermoplastic resin compositions disclosed in Patent Documents 2 and 3 are excellent in impact resistance and antistatic properties, but are insufficient in adhesion with organic solvents.

  On the other hand, as a raw material for forming an antistatic resin container suitable for accommodating a photomask or the like, a graft copolymer obtained by graft-polymerizing an ethylenically unsaturated monomer to a rubber-like backbone polymer having an alkylene oxide group on a polyacrylonitrile-based resin. An antistatic resin composition comprising a polymer, a hydrophilic polymer compatible with a polyacrylonitrile-based resin, and a surfactant (for example, see Patent Document 4) has been proposed. However, the antistatic resin composition disclosed in Patent Document 4 is excellent in adhesion with the organic solvent acetonitrile, but has a problem that the molded product is easily colored yellow and the contents of the case are difficult to visually recognize. .

JP 2004-51845 A JP 2006-52378 A International Publication No. 2007/94195 International Publication No. 2006/117933

  In view of the above-described problems of the prior art, the present invention has an object to provide a thermoplastic resin composition capable of obtaining a molded product having excellent adhesion, impact resistance, antistatic property and color tone with an organic solvent. To do.

As a result of intensive studies to solve such problems, it has been found that the above problems can be solved by the following configuration.
(1) At least aromatic vinyl monomer (a1) 5 to 40% by weight, unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 80% by weight, and vinyl cyanide monomer (a3) 10 A vinyl copolymer (A) obtained by copolymerizing a vinyl monomer mixture (a) containing ˜50 wt%, and at least an aromatic vinyl monomer in the presence of the rubbery polymer (r) (B1) 10-30% by weight of vinyl, monocarboxylic monomer containing unsaturated carboxylic acid alkyl ester monomer (b2) 30-80% by weight and vinyl cyanide monomer (b3) 1-10% by weight A thermoplastic resin composition comprising a graft copolymer (B) obtained by graft copolymerization of a body mixture (b) and a polyamide elastomer (C), the vinyl copolymer (A) and Total of graft copolymer (B) 1 40 to 90 parts by weight of the vinyl copolymer (A), 10 to 60 parts by weight of the graft copolymer (B), and 3 parts by weight or more of the polyamide elastomer (C) with respect to 0 part by weight. Thermoplastic resin composition.
(2) The thermoplastic resin composition according to (1), wherein the polyamide elastomer (C) comprises poly (alkylene oxide) glycol having a number average molecular weight of 200 to 6,000 as a constituent component.
(3) The proportion of the triple sequence of acrylonitrile-derived units present in the acetone-soluble component of the vinyl copolymer (A) and the graft copolymer (B) is 10% in 100% by weight of the acetone-soluble component. % Of the thermoplastic resin composition according to (1) or (2).
(4) Two square plates having a plane dimension of 40 mm × 50 mm × thickness of 3 mm are injection-molded, and 20 mg of 2-butanone is applied to the square dimension of the plane dimension of 40 mm × 5 mm (area 200 mm ² ). Are held at 0.05 MPa for 10 minutes and stored for 2 days in an environment of temperature 23 ° C. and humidity 50% RH, and then the bonded portion is peeled or peeled off at a bending speed of 2 mm / min using a bending tester. The thermoplastic resin composition according to any one of (1) to (3), wherein the strength (solvent adhesive strength) when bent until the base material breaks is 10 MPa or more.
(5) by injection molding the thickness 3mm for square plate molded article, by the test method specified in JIS K7373 (established in 2006), yellowness index as measured by a reflection measuring method using a standard illuminant _{D 65} (YI) is 25 The thermoplastic resin composition according to any one of (1) to (4), which is as follows.
(6) At least aromatic vinyl monomer (a1) 5 to 40% by weight, unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 80% by weight, and vinyl cyanide monomer (a3) 10 A step of copolymerizing a vinyl monomer mixture (a) containing ˜50% by weight to obtain a vinyl copolymer (A), at least an aromatic vinyl monomer in the presence of the rubbery polymer (r); A vinyl system containing 10 to 30% by weight of the monomer (b1), 30 to 80% by weight of the unsaturated carboxylic acid alkyl ester monomer (b2) and 1 to 10% by weight of the vinyl cyanide monomer (b3). Graft copolymerization of the monomer mixture (b) to obtain the graft copolymer (B), and a total of 100 parts by weight of the vinyl copolymer (A) and the graft copolymer (B) , 40-90 weight of vinyl copolymer (A) 10 to 60 parts by weight of the graft copolymer (B), comprising the step of blending a polyamide elastomer (C) 3 parts by weight or more, the production method of the thermoplastic resin composition.
(7) A molded article comprising the thermoplastic resin composition according to any one of (1) to (5).

  With the thermoplastic resin composition of the present invention, it is possible to obtain a molded article excellent in adhesion with an organic solvent, impact resistance, antistatic property and color tone.

  The thermoplastic resin composition of the present invention comprises a vinyl copolymer (A) described later, a graft copolymer (B) described later, and a polyamide elastomer (C). By blending the vinyl copolymer (A), the color tone (yellowness (YI)) of the molded product obtained from the thermoplastic resin composition and the adhesiveness by the organic solvent can be improved, and the graft copolymer By blending (B), the impact resistance of the molded product can be improved. Moreover, the antistatic property of a molded article can be improved by mix | blending a polyamide elastomer (C).

  The thermoplastic resin composition of the present invention is 40 to 90 weight percent of the vinyl copolymer (A) with respect to 100 weight parts of the total of the vinyl copolymer (A) and the graft copolymer (B) described later. Part by weight, 10 to 60 parts by weight of the graft copolymer (B), and 3 parts by weight or more of the polyamide elastomer (C).

  The vinyl copolymer (A) constituting the thermoplastic resin composition of the present invention comprises at least 5 to 40% by weight of an aromatic vinyl monomer (a1), an unsaturated carboxylic acid alkyl ester monomer (a2). And a vinyl monomer mixture (a) containing 30 to 80% by weight and vinyl cyanide monomer (a3) 10 to 50% by weight. The vinyl monomer mixture (a) may further contain other monomers copolymerizable with the above (a1) to (a3).

  Examples of the aromatic vinyl monomer (a1) include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, vinyltoluene, and t-butylstyrene. Two or more of these may be contained. Among these, styrene is preferable from the viewpoint of improving the moldability of the thermoplastic resin composition and the rigidity of the molded product.

  The content of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (a) is from the viewpoint of further improving the moldability of the thermoplastic resin composition and the rigidity of the molded product. It is 5% by weight or more of the total 100% by weight of the body mixture (a), preferably 10% by weight or more, and more preferably 20% by weight or more. On the other hand, the content of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (a) is from the viewpoint of further improving the impact resistance and transparency of the molded product. It is 40% by weight or less, preferably 30% by weight or less, and more preferably 25% by weight or less in the total 100% by weight of (a).

  The unsaturated carboxylic acid alkyl ester monomer (a2) is not particularly limited, but is preferably an ester of an alcohol having 1 to 6 carbon atoms with acrylic acid or methacrylic acid. The ester of an alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid may further have a substituent such as a hydroxyl group or a halogen group. Examples of the ester of an alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acryl Examples include acid 2,3,4,5,6-pentahydroxyhexyl, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, and the like. Two or more of these may be contained. Among these, methyl (meth) acrylate is preferable from the viewpoint of improving the transparency of the molded product. “(Meth) acrylic acid” refers to acrylic acid or methacrylic acid.

  The content of the unsaturated carboxylic acid alkyl ester monomer (a2) in the vinyl monomer mixture (a) is that of the vinyl monomer mixture (a) from the viewpoint of improving the transparency of the molded product. It is 30% by weight or more in the total 100% by weight, preferably 50% by weight or more, more preferably 60% by weight or more. On the other hand, the content of the unsaturated carboxylic acid alkyl ester monomer (a2) in the vinyl monomer mixture (a) is from the viewpoint of improving the chemical resistance and transparency of the molded product. It is 80% by weight or less, preferably 75% by weight or less, and more preferably 70% by weight or less in the total 100% by weight of the body mixture (a).

  Examples of the vinyl cyanide monomer (a3) include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like. Two or more of these may be contained. Among these, acrylonitrile is preferable from the viewpoint of further improving the adhesion of the molded product with the solvent.

  The content of the vinyl cyanide monomer (a3) in the vinyl monomer mixture (a) is 10 to 50% by weight in a total of 100% by weight of the vinyl monomer mixture (a). is important. When the content of the vinyl cyanide monomer (a3) is less than 10% by weight, the adhesion due to the organic solvent is lowered. The content of the vinyl cyanide monomer (a3) is preferably 13% by weight or more. On the other hand, if the content of the vinyl cyanide monomer (a3) exceeds 50% by weight, the yellowness (YI) of the molded product increases and the color tone decreases. The content of the vinyl cyanide monomer (a3) is preferably 40% by weight or less, and more preferably 20% by weight or less.

  Other monomers copolymerizable with these include the above-mentioned aromatic vinyl monomer (a1), unsaturated carboxylic acid alkyl ester monomer (a2), vinyl cyanide monomer ( There is no particular limitation as long as it is a vinyl monomer other than a3) and does not impair the effects of the present invention. Specific examples include unsaturated fatty acids, acrylamide monomers, and maleimide monomers. Two or more of these may be contained. Examples of the unsaturated fatty acid include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid. Examples of the acrylamide monomer include acrylamide, methacrylamide, N-methylacrylamide and the like. Examples of maleimide monomers include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, Examples thereof include N-phenylmaleimide.

In the present invention, the solubility parameter of the vinyl copolymer (A) is preferably 20.4 to 25.6 (J / cm ³ ) ^1/2 . If the solubility parameter of the vinyl copolymer (A) is 20.4 (J / cm ³ ) ^1/2 or more, the adhesion with an organic solvent can be further improved. On the other hand, if the solubility parameter of the vinyl copolymer (A) is 25.6 (J / cm ³ ) ^1/2 or less, the compatibility with the graft component of the graft copolymer (B) described later is improved. Moreover, the adhesiveness by the organic solvent can be further improved. 25.2 (J / cm ³ ) ^1/2 or less is more preferable. The solubility parameter here can be calculated by the following formula (1).
δ = (ΣΔEi · X / ΣΔVm · X) ^1/2 (1)
δ: Solubility parameter of vinyl copolymer (A) ((J / cm ³ ) ^1/2 )
X: molar fraction (%) of the copolymer component constituting the vinyl copolymer (A)
ΔEi: Evaporation energy (J / mol) of the copolymer component constituting the vinyl copolymer (A)
ΔVm: molecular volume of the copolymer component constituting the vinyl copolymer (A) (cm ³ / mol)

  The numerical values of X, ΔEi, and ΔVm are H.264. Burrell, Offic. Dig. A. J. et al. Tortorello, M.M. A. Kinsella, J. et al. Coat. Technol. Can be quoted from

  The solubility parameter of the vinyl copolymer (A) can be adjusted to a desired range by selecting the composition of the vinyl monomer mixture (a).

  The number average molecular weight of the vinyl copolymer (A) is preferably 60,000 to 100,000. The vinyl-based copolymer (A) having a number average molecular weight of 60,000 to 100,000 is, for example, by using an initiator or a chain transfer agent described later, setting the polymerization temperature to a preferable range described later, and the like. It can be manufactured easily.

  Here, the number average molecular weight of the vinyl copolymer (A) was measured using GPC measured using a solution of about 0.2% by weight of about 0.03 g of the vinyl copolymer (A) dissolved in about 15 g of tetrahydrofuran. From the chromatogram, it can be determined by converting polymethyl methacrylate as a standard substance.

  In the present invention, the vinyl copolymer (A) preferably has a refractive index difference of 0.03 or less, more preferably 0.01 or less, with a rubbery polymer (r) described later. By setting the difference between the refractive index of the vinyl copolymer (A) and the refractive index of the rubbery polymer (r) to 0.03 or less, the transparency of the molded product can be improved.

Since the refractive index of the vinyl copolymer (A) mainly depends on the composition of the vinyl monomer as a raw material, the refractive index can be adjusted by appropriately selecting the type and composition ratio of the vinyl monomer. A desired range can be obtained. The refractive index of the vinyl copolymer (A) can be estimated from the refractive index and content of the vinyl monomer. For example, in the case of a copolymer of styrene, acrylonitrile, and methyl methacrylate. The refractive index of the vinyl copolymer (A) can be estimated from the following formula.
nD (A) = (1.510 × MA / 100) + (1.595 × MS / 100) + (1.490 × MM / 100)
Here, nD (A) is the refractive index of the vinyl copolymer (A), MA is the acrylonitrile content (% by weight), MS is the styrene content (% by weight), and MM is the methyl methacrylate content (% by weight). ). Further, 1.510 indicates the refractive index of acrylonitrile, 1.595 indicates the refractive index of styrene, and 1.490 indicates the refractive index of methyl methacrylate. The refractive indexes of polyacrylonitrile, polystyrene, and polymethyl methacrylate are respectively Abbe refracted. It can be calculated by measuring with a rate meter.

  The refractive index of the vinyl copolymer (A) is determined by dropping a small amount of 1-bromonaphthalene using a 30 ± 5 μm thick film obtained by heating and pressing the vinyl copolymer (A) at 230 ° C. as a measurement sample. The light can be measured using an Abbe refractometer under the conditions of light source: sodium lamp D line and measurement temperature: 23 ° C.

  In the present invention, the method for producing the vinyl-based copolymer (A) is not particularly limited, but improves the moldability of the resulting thermoplastic resin composition, the adhesion with an organic solvent, the transparency and the color stability, which will be described later. From the viewpoint of reducing the ratio of the triple sequence of the acrylonitrile-derived units of the vinyl copolymer (A), a continuous bulk polymerization method or a continuous solution polymerization method is preferably used.

  As a method for producing the vinyl copolymer (A) by a continuous bulk polymerization method or a continuous solution polymerization method, any method can be adopted. For example, the vinyl monomer mixture (a) is polymerized in a polymerization tank. Then, a method of demonomerization (desolvation / devolatilization) can be mentioned.

  Examples of the polymerization tank include a mixing type polymerization tank having stirring blades such as a paddle blade, a turbine blade, a propeller blade, a bull margin blade, a multistage blade, an anchor blade, a max blend blade, a double helical blade, and various tower types. Or the like can be used. In addition, a multi-tube reactor, a kneader reactor, a twin screw extruder, and the like can also be used as the polymerization reactor (for example, assessment of polymer production process 10 “assessment of high-impact polystyrene” Polymer Society, 1989 (See January 26th issue, etc.).

  Two or more (tank) of these polymerization tanks or polymerization reactors may be used, or two or more polymerization tanks or polymerization reactors may be combined as necessary. From the viewpoint of reducing the degree of dispersion of the vinyl copolymer (A), it is preferably 2 (tank) or less, and more preferably a 1 tank type fully mixed polymerization tank.

  The reaction mixture obtained by polymerization in these polymerization tanks or polymerization reactors is usually then subjected to a demonomer process to remove monomers, solvents and other volatile components. Demonomer removal methods include, for example, a method in which volatile components are removed from a vent hole under heating or normal pressure or reduced pressure with a single or twin screw extruder having a vent, or a plate fin type heater such as a centrifugal type drum. A method of removing volatile components with an evaporator built into the unit, a method of removing volatile components with a thin film evaporator such as a centrifugal type, etc., residual heat using a multi-tubular heat exchanger, foaming and flushing to a vacuum chamber to volatile components The method of removing is mentioned. Among these, a method of removing volatile components with a single-screw or twin-screw extruder having a vent is particularly preferably used.

  When manufacturing a vinyl-type copolymer (A), you may use an initiator as needed. Examples of the initiator include peroxides, azo compounds, and water-soluble potassium persulfate. Two or more of these may be combined.

  Examples of the peroxide include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl isopropyl carbonate, di-t-butyl peroxide, t-butyl peroctate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (T-Butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate, etc. are mentioned. Of these, cumene hydroperoxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, and 1,1-bis (t-butylperoxy) cyclohexane are particularly preferably used. It is done.

  Examples of the azo compound include azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazo. Formamide, 1,1′-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 1-t-butylazo-2 -Cyanobutane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane and the like. Of these, 1,1'-azobiscyclohexane-1-carbonitrile is particularly preferably used.

  There is no particular limitation on the amount of the initiator used to produce the vinyl copolymer (A), but from the viewpoint that the number average molecular weight of the vinyl copolymer (A) can be easily adjusted, 0.01-0.03 weight part is preferable with respect to a total of 100 weight part of a monomer mixture (a).

  When producing the vinyl copolymer (A), a chain transfer agent may be used. By using a chain transfer agent, the number average molecular weight of the vinyl copolymer (A) can be easily adjusted to a desired range. Examples of chain transfer agents include mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, and terpenes such as terpinolene. Two or more of these may be combined. Of these, n-octyl mercaptan and t-dodecyl mercaptan are preferably used.

  The addition amount of the chain transfer agent used for producing the vinyl copolymer (A) is not particularly limited, but from the viewpoint that the number average molecular weight of the vinyl copolymer (A) can be easily adjusted. The amount is preferably 0.10 to 0.30 parts by weight based on 100 parts by weight of the total amount of the monomer mixture (a).

  When the vinyl copolymer (A) is produced by a continuous bulk polymerization method or a continuous solution polymerization method, the polymerization temperature is not particularly limited, but it is easy to adjust the number average molecular weight of the vinyl copolymer (A). From 120 to 140 ° C. is preferable.

  When the vinyl copolymer (A) is produced by a continuous solution polymerization method, the amount of the solvent is preferably 30% by weight or less, more preferably 20% by weight or less in the polymerization solution from the viewpoint of productivity. As the solvent, ethylbenzene or methyl ethyl ketone is preferable from the viewpoint of polymerization stability, and ethylbenzene is particularly preferably used.

  The graft copolymer (B) constituting the thermoplastic resin composition of the present invention comprises at least 10 to 30% by weight of the aromatic vinyl monomer (b1) in the presence of the rubbery polymer (r), unsaturated. Graft copolymerization of a vinyl monomer mixture (b) containing 30 to 80% by weight of a carboxylic acid alkyl ester monomer (b2) and 1 to 10% by weight of a vinyl cyanide monomer (b3) It is obtained. The vinyl monomer mixture (b) may further contain other monomers copolymerizable with the above (b1) to (b3).

  Examples of the rubber polymer (r) include polybutadiene, poly (butadiene-styrene) (SBR), poly (butadiene-acrylonitrile) (NBR), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene- Methyl methacrylate), poly (butyl acrylate-methyl methacrylate), poly (butadiene-ethyl acrylate), ethylene-propylene rubber, poly (ethylene-isoprene), poly (ethylene-methyl acrylate), natural rubber, etc. Can be mentioned. Two or more of these may be used. Of these, polybutadiene, SBR, NBR, ethylene-propylene rubber, and natural rubber are preferable from the viewpoint of further improving the impact resistance of the molded product.

  The content of the rubbery polymer (r) is 20 with respect to the total amount of the rubbery polymer (r) constituting the graft copolymer (B) and the vinyl monomer mixture (b) described later. ~ 80 wt% is preferred. When the content of the rubbery polymer (r) is 20% by weight or more, the impact resistance of the molded product can be further improved. The content of the rubbery polymer (r) is more preferably 35% by weight or more. On the other hand, if the content of the rubbery polymer (r) is 80% by weight or less, the moldability of the thermoplastic resin composition can be further improved. The content of the rubber-like polymer (r) is more preferably 60% by weight or less.

  The weight average particle diameter of the rubber polymer (r) is not particularly limited, but is preferably 0.1 μm or more and more preferably 0.15 μm or more from the viewpoint of further improving the impact resistance of the molded product. On the other hand, from the viewpoint of improving the transparency of the molded product, 1.5 μm or less is preferable, and 0.5 μm or less is more preferable.

  Examples of the aromatic vinyl monomer (b1) include those exemplified as the aromatic vinyl monomer (a1), and styrene is preferable.

  The content of the aromatic vinyl monomer (b1) in the vinyl monomer mixture (b) is from the viewpoint of further improving the moldability of the thermoplastic resin composition and the rigidity of the molded product. It is 10% by weight or more in the total 100% by weight of the body mixture (b), preferably 15% by weight or more, more preferably 20% by weight or more. On the other hand, the content of the aromatic vinyl monomer (b1) in the vinyl monomer mixture (b) is a vinyl monomer mixture from the viewpoint of further improving the impact resistance and transparency of the molded product. It is 30 weight% or less in the total 100 weight% of (b), Preferably it is 25 weight% or less.

  Examples of the unsaturated carboxylic acid alkyl ester monomer (b2) include those exemplified as the unsaturated carboxylic acid alkyl ester monomer (a2), and methyl (meth) acrylate is preferred.

  The content of the unsaturated carboxylic acid alkyl ester monomer (b2) in the vinyl monomer mixture (b) is that of the vinyl monomer mixture (b) from the viewpoint of improving the transparency of the molded product. It is 30% by weight or more of the total 100% by weight, preferably 50% by weight or more, and more preferably 70% by weight or more. On the other hand, the content of the unsaturated carboxylic acid alkyl ester monomer (b2) in the vinyl monomer mixture (b) is selected from the viewpoint of improving the transparency of the molded product. ) Is 100% by weight or less, preferably 75% by weight or less.

  Examples of the vinyl cyanide monomer (b3) include those exemplified as the vinyl cyanide monomer (a3), and acrylonitrile is preferred.

  The content of the vinyl cyanide monomer (b3) in the vinyl monomer mixture (b) is 1 to 10% by weight in a total of 100% by weight of the vinyl monomer mixture (b). is important. If the content of the vinyl cyanide monomer (b3) is less than 1% by weight, the adhesiveness and impact resistance of the molded product with an organic solvent are lowered. The content of the vinyl cyanide monomer (b3) is preferably 2% by weight or more. On the other hand, when the content of the vinyl cyanide monomer (b3) exceeds 10% by weight, the yellowness (YI) of the molded product increases and the color tone decreases. The content of the vinyl cyanide monomer unit (b3) is preferably 8% by weight or less, and more preferably 5% by weight or less.

  Other monomers copolymerizable with these include the above-mentioned aromatic vinyl monomer (b1), unsaturated carboxylic acid alkyl ester monomer (b2), vinyl cyanide monomer ( There is no particular limitation as long as it is a vinyl monomer other than b3) and does not impair the effects of the present invention. Specifically, what was illustrated as another monomer in a vinyl-type monomer mixture (a) is mentioned.

  The number average molecular weight of the acetone-soluble component of the graft copolymer (B) is preferably 30,000 to 50,000. The graft copolymer (B) having a number-average molecular weight of acetone-soluble fraction of 30,000 to 50,000 uses, for example, an initiator or a chain transfer agent described later, and brings the polymerization temperature into a preferable range described later. It can be manufactured easily.

  Here, the number average molecular weight of the acetone-soluble component of the graft copolymer (B) is obtained by adding 80 ml of acetone to about 1 g of the graft copolymer (B) and refluxing in a 70 ° C. water bath for 3 hours. 8000 r. p. After centrifuging at m (10000 G) for 40 minutes, the acetone-soluble component obtained by concentrating the filtrate obtained by filtering the insoluble component with a rotary evaporator can be measured in the same manner as the vinyl copolymer (A).

  The graft ratio of the graft copolymer (B) is not particularly limited, but is preferably 10 to 100% from the viewpoint of further improving the impact resistance of the molded product.

Here, the graft ratio of the graft copolymer (B) can be determined by the following method. First, 80 ml of acetone was added to about 1 g (m: sample mass) of the graft copolymer (B) and refluxed in a 70 ° C. hot water bath for 3 hours. p. After centrifuging at m (10000 G) for 40 minutes, the insoluble matter is filtered to obtain an acetone insoluble matter. The obtained acetone insoluble matter was dried under reduced pressure at 80 ° C. for 5 hours, its mass (n) was measured, and the graft ratio was calculated from the following formula. Here, X is the content (%) of the rubbery polymer (r) of the graft copolymer (B).
Graft ratio (%) = {[(n) − ((m) × X / 100)] / [(m) × X / 100]} × 100.

  In the present invention, the graft component (acetone-insoluble component) of the graft copolymer (B) preferably has a refractive index difference of 0.03 or less from the rubbery polymer (r), and is 0.01 or less. It is more preferable. By setting the difference between the refractive index of the graft copolymer (B) and the refractive index of the graft component and the rubbery polymer (r) to 0.03 or less, the transparency of the molded product can be improved.

Since the refractive index of the graft component of the graft copolymer (B) mainly depends on the composition of the vinyl monomer as the raw material, the refractive index can be determined by appropriately selecting the type and composition ratio of the vinyl monomer. The rate can be in the desired range. In particular, when the high molecular weight conversion rate is 95% or more by the emulsion polymerization method, the composition of the graft component is substantially the same as the composition of the vinyl monomer mixture (b). The refractive index of the graft component of the graft copolymer (B) can be estimated from the refractive index and content of the vinyl monomer. For example, in the case of a copolymer of styrene, acrylonitrile, methyl methacrylate The refractive index of the graft component of the graft copolymer (B) can be estimated from the following formula.
nD (G) = (1.510 × MA / 100) + (1.595 × MS / 100) + (1.490 × MM / 100)

  Here, nD (G) is the refractive index of the graft component of the graft copolymer (B), MA is the acrylonitrile content (% by weight), MS is the styrene content (% by weight), and MM is the methyl methacrylate content ( % By weight). Further, 1.510 indicates the refractive index of acrylonitrile, 1.595 indicates the refractive index of styrene, and 1.490 indicates the refractive index of methyl methacrylate. The refractive indexes of polyacrylonitrile, polystyrene, and polymethyl methacrylate are respectively Abbe refracted. It can be calculated by measuring with a rate meter.

The refractive index of the rubbery polymer (r) is generally shown in the literature, and is, for example, 1.516 in the case of polybutadiene rubber. When a copolymer rubber is used, the refractive index of the copolymer rubber can be estimated from the refractive index and content of the copolymer component. For example, in the case of styrene butadiene rubber, the refractive index of the copolymer rubber is expressed by the following formula. (ND (r)) can be estimated. In addition, a copolymerization component can be identified by FT-IR, a viscoelasticity measurement, etc.
nD (r) = (1.516 · MB / 100) + (1.595 · MS / 100)

  Here, nD (r) represents the refractive index of the rubber polymer (r), MB represents the butadiene content (% by weight), and MS represents the styrene content (% by weight). 1.516 represents the refractive index of butadiene, and 1.595 represents the refractive index of styrene.

  The refractive index of the graft component of the graft copolymer (B) is such that the graft component obtained by dissolving the graft copolymer (B) in acetone and drying the residue obtained by filtering the acetone-soluble component is vinyl. It can be measured in the same manner as the system copolymer (A).

  In the present invention, the method for producing the graft copolymer (B) is not particularly limited, and any method such as an emulsion polymerization method, a suspension polymerization method, a continuous bulk polymerization method, and a solution continuous polymerization method can be used. The emulsion polymerization method or the bulk polymerization method is preferable, the particle size of the rubbery polymer (r) can be easily adjusted to a desired range, and the polymerization stability can be easily adjusted by removing heat during polymerization. Therefore, the emulsion polymerization method is more preferable.

  When the graft copolymer (B) is produced by an emulsion polymerization method, the charging method of the rubber-like polymer (r) and the vinyl monomer mixture (b) is not particularly limited. For example, all of these may be initially charged all at once, or a part of the vinyl monomer mixture (b) may be continuously charged in order to adjust the distribution of the copolymer composition. A part or all of the monomer mixture (b) may be divided and charged. Here, continuously charging a part of the vinyl monomer mixture (b) means charging a part of the vinyl monomer mixture (b) in the initial stage and continuously charging the remainder over time. Means. In addition, dividing and charging part or all of the vinyl monomer mixture (b) means charging part or all of the vinyl monomer mixture (b) at a time after the initial charging. means.

  When the graft copolymer (B) is produced by an emulsion polymerization method, various surfactants may be added as an emulsifier. As the various surfactants, anionic surfactants such as carboxylate type, sulfate ester type, and sulfonate type are particularly preferably used. Two or more of these may be combined. In addition, as a salt said here, alkali metal salts, such as sodium salt, lithium salt, potassium salt, ammonium salt, etc. are mentioned.

  Examples of carboxylate type emulsifiers include caprylate, caprate, laurate, myristate, palmitate, stearate, oleate, linoleate, linolenate, and rosinate. , Behenate, dialkylsulfosuccinate and the like.

  Examples of the sulfate ester type emulsifier include castor oil sulfate ester, lauryl alcohol sulfate ester, polyoxyethylene lauryl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, and the like. .

  Examples of the sulfonate type emulsifier include dodecylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonate, naphthalene sulfonate condensate, and the like.

  When the graft copolymer (B) is produced by an emulsion polymerization method, an initiator or a chain transfer agent may be added as necessary. As an initiator and a chain transfer agent, the initiator and chain transfer agent which were illustrated in the manufacturing method of a vinyl-type copolymer (A) are mentioned. Initiators are also used in redox systems.

  The addition amount of the initiator used for producing the graft copolymer (B) is not particularly limited, but from the viewpoint that the number average molecular weight of the graft copolymer (B) can be easily adjusted, the rubbery polymer. 0.1-0.5 weight part is preferable with respect to a total of 100 weight part of (r) and a vinyl-type monomer mixture (b).

  The amount of chain transfer agent used to produce the graft copolymer (B) is not particularly limited, but from the viewpoint of easy adjustment of the number average molecular weight and graft ratio of the graft copolymer (B), The amount is preferably 0.2 to 0.7 parts by weight with respect to 100 parts by weight as a total of the rubber polymer (r) and the vinyl monomer mixture (b). 0.4 parts by weight or more is more preferable, while 0.6 parts by weight or less is more preferable.

  When the graft copolymer (B) is produced by emulsion polymerization, the polymerization temperature is not particularly limited, but 40 to 70 ° C. is preferable from the viewpoint of emulsion stability of the graft copolymer (B).

  When the graft copolymer (B) is produced by an emulsion polymerization method, it is general to add a coagulant to the graft copolymer latex and recover the graft copolymer (B). As the coagulant, an acid or a water-soluble salt is preferably used.

  Examples of the acid include sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and the like. Examples of the water-soluble salt include calcium chloride, magnesium chloride, barium chloride, aluminum chloride, magnesium sulfate, aluminum sulfate, aluminum ammonium sulfate, aluminum potassium sulfate, and sodium aluminum sulfate. Two or more of these may be combined. From the viewpoint of further improving the color tone of the molded article, it is preferable not to leave an emulsifier in the thermoplastic resin composition, and it is preferable to use an alkali fatty acid salt as the emulsifier and to perform acid coagulation. In this case, it is preferable to neutralize with an alkali such as sodium hydroxide to remove the emulsifier.

  In the thermoplastic resin composition of the present invention, the blending amount of the vinyl copolymer (A) is 40 to 90 with respect to a total of 100 parts by weight of the vinyl copolymer (A) and the graft copolymer (B). The compounding quantity of a weight part and a graft copolymer (B) is 10-60 weight part. When the blending amount of the vinyl copolymer (A) exceeds 90 parts by weight and the blending amount of the graft copolymer (B) is less than 10 parts by weight, the impact resistance of the molded product is lowered. On the other hand, when the blending amount of the vinyl copolymer (A) is less than 40 parts by weight and the blending amount of the graft copolymer (B) exceeds 60 parts by weight, the melt viscosity of the thermoplastic resin composition increases, Formability is reduced.

  In the thermoplastic resin composition of the present invention, the acrylonitrile-derived unit content in the acetone-soluble component (E) of the vinyl copolymer (A) and the graft copolymer (B) is preferably 8 to 50% by weight. Further, the acrylonitrile-derived unit content in the acetone-insoluble matter (F) of the vinyl copolymer (A) and the graft copolymer (B) is preferably 1 to 5% by weight.

  The acrylonitrile-derived unit content in the acetone-soluble component (E) indicates the content of the acrylonitrile-derived unit derived from the acetone-soluble component of the vinyl copolymer (A) or the graft copolymer (B). This contributes to further improvement of the adhesion by organic solvents. On the other hand, the acrylonitrile-derived unit content in the acetone insoluble matter (F) indicates the content of the acrylonitrile-derived unit derived from the graft component of the graft copolymer (B), and contributes to further improvement in the color tone of the molded product. To do.

  When the acrylonitrile-derived unit content in the acetone-soluble component (E) is 8% by weight or more, the adhesion with an organic solvent can be further improved. On the other hand, when the acrylonitrile-derived unit content in the acetone-soluble component (E) is 50% by weight or less, the color tone of the molded product can be further improved.

  Moreover, when the acrylonitrile-derived unit content in the acetone-insoluble component (F) is 1% by weight or more, the adhesiveness due to the organic solvent can be further improved. On the other hand, when the acrylonitrile-derived unit content in the acetone-insoluble component (F) is 5% by weight or less, the color tone of the molded product can be further improved.

The acrylonitrile-derived unit content in the acetone-soluble component (E) and the acetone-insoluble component (F) can be determined by the following method. First, 80 ml of acetone is added to about 1 g of a resin in which the vinyl copolymer (A) and the graft copolymer (B) are blended at the blending ratio in the thermoplastic resin composition of the present invention, and 3 ml in a 70 ° C. hot water bath. Reflux for hours and add 8000 r. p. After centrifugation at m (10000 G) for 40 minutes, the insoluble matter is filtered to obtain acetone insoluble matter (F). Further, the filtrate is concentrated with a rotary evaporator to obtain an acetone-soluble component (E). The obtained acetone-soluble component (E) and acetone-insoluble component (F) were each dried under reduced pressure at 80 ° C. for 5 hours, and a film having a thickness of 30 ± 5 μm prepared by a heating press set at 230 ° C. was subjected to FT-IR analysis. The acrylonitrile-derived unit content can be quantified from the intensity ratio of the following peaks appearing on the FT-IR chart.
Aromatic vinyl monomers (a1), (b1): 1605 cm ⁻¹ peak unsaturated carboxylic acid alkyl ester monomers (a2) attributed to vibration of the benzene nucleus (b2): carbonyl group of the ester 1730 cm ⁻¹ peak vinyl cyanide monomer (a3), (b3) attributed to C═O stretching vibration: 2240 cm ⁻¹ peak rubbery polymer (r) attributed to —C≡N stretching (r): C = peak at 960 cm ⁻¹ attributed to C.

  Examples of the method for setting the acrylonitrile-derived unit content in the acetone-soluble component (E) and the acrylonitrile-derived unit content in the acetone-insoluble component (F) within the above ranges include, for example, the vinyl copolymer (A) and the graft copolymer. The method etc. which make the composition of a polymer (B) into the above-mentioned preferable range are mentioned.

  In the thermoplastic resin composition of the present invention, the proportion of the triple sequence of acrylonitrile-derived units present in the acetone-soluble component (E) of the vinyl copolymer (A) and the graft copolymer (B) is particularly limited. However, 10% by weight or less is preferable in the total 100% by weight of the acetone-soluble component (E).

  The triple sequence of acrylonitrile-derived units is a segment represented by the following formula (1). When the copolymer having such a segment is exposed to a high temperature, the intramolecular cyclization reaction proceeds and tends to have a structure represented by the following formula (2) that causes coloration. If it is at most% by weight, coloring by heat can be suppressed and the color tone can be further improved. The proportion of the triple sequence is more preferably 8% by weight or less, and further preferably 5% by weight or less.

  As a method of setting the ratio of the triple sequence to 10% by weight or less, for example, when polymerizing the vinyl copolymer (A), 50% by weight or more of acrylonitrile used as the vinyl cyanide monomer (a3) is used. And a method of adding it to the polymerization system before the polymerization conversion rate reaches 30%. By this method, since the acrylonitrile content in the residual monomer at the end of the polymerization can be kept low, the proportion of the triple sequence of acrylonitrile-derived units in the acetone-soluble component of the thermoplastic resin composition can be reduced. More preferably, 70% by weight or more of acrylonitrile used as the vinyl cyanide monomer (a3) is added to the polymerization system before the polymerization conversion rate reaches 30%.

The ratio of the triple sequence of acrylonitrile-derived units in the acetone-soluble component (E) can be determined by the following method. First, 80 ml of acetone is added to about 1 g of a resin in which the vinyl copolymer (A) and the graft copolymer (B) are blended at the blending ratio in the thermoplastic resin composition of the present invention, and 3 ml in a 70 ° C. hot water bath. Reflux for hours and add 8000 r. p. After centrifugation at m (10000 G) for 40 minutes, the insoluble matter is filtered, and the filtrate is concentrated by a rotary evaporator to obtain an acetone-soluble matter (E). The obtained acetone-soluble component (E) is subjected to ¹³ C-NMR analysis. Utilizing the fact that the signal shift of α-carbon of the acrylonitrile-derived unit appearing in ¹³ C-NMR is slightly different depending on the type of the adjacent monomer, the ratio of the triple sequence was quantified from the signal integral value, By calculating the weight fraction of the acrylonitrile-derived unit at the center of the triple sequence, the ratio of the triple sequence can be calculated.

  As the polyamide elastomer (C) constituting the thermoplastic resin composition of the present invention, for example, an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms, and a number average A graft copolymer or block copolymer with a poly (alkylene oxide) glycol having a molecular weight of 200 to 6,000 is preferred. Polyethylene oxide glycol is preferably used as the poly (alkylene oxide) glycol.

  Here, the aminocarboxylic acid or lactam having 6 or more carbon atoms, or the salt of diamine and dicarboxylic acid having 6 or more carbon atoms specifically includes ω-aminocaproic acid, ω-aminoenanthic acid, ω-amino. Caprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, aminocarboxylic acids such as 12-aminododecanoic acid, caprolactam, enanthractam, capryllactam, laurolactam and other lactams, hexamethylenediamine-adipine And nylon salts such as acid salt, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate. Two or more of these may be used.

  Examples of the poly (alkylene oxide) glycol include polyethylene oxide glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, and poly (hexamethylene oxide). ) Glycol, ethylene oxide and propylene oxide block or random copolymer, ethylene oxide and tetrahydrofuran block or random copolymer, and the like. Two or more of these may be used. Furthermore, bisphenol A, an alkylene oxide adduct of fatty acid, and the like may be copolymerized. The number average molecular weight of the poly (alkylene oxide) glycol is preferably 200 or more and more preferably 300 or more from the viewpoint of improving the mechanical properties of the polyamide elastomer (C). On the other hand, the number average molecular weight of the poly (alkylene oxide) glycol is preferably 6,000 or less and more preferably 4,000 or less from the viewpoint of further improving the antistatic property. Both ends of the poly (alkylene oxide) glycol may be aminated or carboxylated as necessary.

  In the present invention, an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a bond between a diamine having 6 or more carbon atoms and a dicarboxylic acid salt and poly (alkylene oxide) glycol is usually an ester bond and an amide bond. In particular, it is not limited only to these.

  It is also possible to use a third component such as dicarboxylic acid or diamine as a reaction component. As a specific example, an example in which terephthalic acid (dicarboxylic acid) is added to bind nylon 6 and polyethylene glycol can be given.

  As the dicarboxylic acid in the case where a third component such as dicarboxylic acid or diamine is used as a reaction component, a dicarboxylic acid having 4 to 20 carbon atoms is preferable from the viewpoint of further improving the polymerizability, color tone and physical properties, for example, terephthalic acid. , Aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid Aliphatic dicarboxylic acid such as acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, aliphatic dicarboxylic acid such as succinic acid, oxalic acid, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid An acid etc. are mentioned.

  On the other hand, as the diamine, aromatic, alicyclic and aliphatic diamines are used, and among them, the aliphatic diamine hexamethylenediamine is preferably used.

  It does not specifically limit about the manufacturing method of a polyamide elastomer (C), A well-known manufacturing method can be utilized. For example, in the case of a graft copolymer or block copolymer containing poly (alkylene oxide) glycol as a constituent component, an aminocarboxylic acid or lactam or a diamine having 6 or more carbon atoms and a dicarboxylic acid salt (I) and a dicarboxylic acid ( (B) is reacted to form a polyamide prepolymer having carboxylic acid groups at both ends, and this is reacted with poly (alkylene oxide) glycol (c) under vacuum, the above (a), (b) and (c) ) In the presence or absence of water, and the reaction is heated at a high temperature to produce a carboxylic acid-terminated polyamide elastomer, followed by polymerization under normal pressure or reduced pressure. (B), (b) and (c) are simultaneously charged into a reaction vessel, melt polymerized, and then polymerized at once under high vacuum. Such as the way to proceed, and the like.

  In the thermoplastic resin composition of the present invention, the amount of the polyamide elastomer (C) is 3 parts by weight or more with respect to 100 parts by weight in total of the vinyl copolymer (A) and the graft copolymer (B). It is. When the blending amount of the polyamide elastomer (C) is less than 3 parts by weight, the surface specific resistance value of the molded product is increased and the electrostatic diffusion performance is lowered, so that the antistatic property is lowered. The amount of the polyamide elastomer (C) is preferably 5 parts by weight or more, more preferably 6 parts by weight or more, and still more preferably 8 parts by weight or more. On the other hand, from the viewpoint of improving the rigidity of the molded product, the amount of the polyamide elastomer (C) is preferably 50 parts by weight or less, more preferably 45 parts by weight or less, and still more preferably 40 parts by weight or less.

  Moreover, you may mix | blend a modified vinyl type copolymer (D) with the thermoplastic resin composition of this invention as needed, and can improve the impact resistance of a molded article more. The modified vinyl copolymer (D) in the present invention is a vinyl copolymer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an oxazoline group, The thing other than the above-mentioned vinyl copolymer (A) is pointed out.

  The method for introducing a carboxyl group into the modified vinyl copolymer (D) is not particularly limited. For example, acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, maleic anhydride, phthalic acid and itaconic acid A method of copolymerizing a vinyl monomer having a carboxyl group or an anhydrous carboxyl group with a predetermined vinyl monomer, γ, γ′-azobis (γ-cyanovaleric acid), α, α′-azobis (α -Cyanoethyl) -p-benzoic acid and polymerization generators having a carboxyl group such as peroxysuccinic acid and / or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, α-mercapto-isobutyric acid and 2, Using a polymerization degree regulator having a carboxyl group such as 3 or 4-mercaptobenzoic acid, a vinyl monomer Method of (co) polymerization, Copolymerization of (meth) acrylic acid ester monomers such as methyl methacrylate and methyl acrylate with aromatic vinyl monomers, and optionally vinyl cyanide monomers Examples include a method of saponifying the coalescence with an alkali.

  The method for introducing a hydroxyl group into the modified vinyl copolymer (D) is also not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, methacrylic acid 3 -Hydroxypropyl, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans- - a method of (co) polymerizing a vinyl monomer containing a vinyl monomer having a hydroxyl group such as hydroxy-2-pentene and 4-dihydroxy-2-butene can be mentioned.

  The method for introducing an epoxy group into the modified vinyl copolymer (D) is not particularly limited. For example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p- Examples thereof include a method of (co) polymerizing a vinyl monomer containing a vinyl monomer having an epoxy group such as glycidyl ether and p-glycidyl styrene.

  There is no particular limitation on the method for introducing an amino group into the modified vinyl copolymer (D). For example, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate Propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methyl Examples thereof include a method of (co) polymerizing a vinyl monomer including a vinyl monomer having an amino group such as allylamine or p-aminostyrene or a derivative thereof.

  The method for introducing an oxazoline group into the modified vinyl copolymer (D) is not particularly limited, and examples thereof include 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and 2-styryl-oxazoline. And a method of (co) polymerizing a vinyl monomer containing a vinyl monomer having an oxazoline group.

  When polymerizing a vinyl monomer containing a vinyl monomer having the aforementioned functional group, the blending amount of the vinyl monomer having the aforementioned functional group in the vinyl monomer is the amount of the modified vinyl copolymer. 0.01-20 weight% is preferable in 100 weight% of the total of the vinyl-type monomer which comprises a polymer (D).

  The intrinsic viscosity [η] of the modified vinyl copolymer (D) at 30 ° C. in a methyl ethyl ketone solvent is preferably 0.20 dl / g or more from the viewpoint of further improving the impact resistance of the molded article, and is 0.35 dl / g or more is more preferable. On the other hand, from the viewpoint of further improving the moldability of the thermoplastic resin composition, 0.65 dl / g or less is preferable, and 0.60 dl / g or less is more preferable. The modified vinyl copolymer (D) has an intrinsic viscosity [η] at 30 ° C. in an N, N-dimethylformamide solvent of 0.30 dl / g or more from the viewpoint of further improving the impact resistance of the molded product. Is preferable, and 0.40 dl / g or more is more preferable. On the other hand, from the viewpoint of further improving the moldability of the thermoplastic resin composition, 0.90 dl / g or less is preferable, and 0.75 dl / g or less is more preferable.

  In the thermoplastic resin composition of the present invention, the amount of the modified vinyl copolymer (D) is 0 with respect to a total of 100 parts by weight of the vinyl copolymer (A) and the graft copolymer (B). .1 to 20 parts by weight is preferable. By making the blending amount of the modified vinyl polymer (D) 0.1 parts by weight or more, the impact resistance of the molded product can be further improved. The amount of the modified vinyl polymer (D) is more preferably 1 part by weight or more. On the other hand, the impact resistance of the molded product can be further improved by setting the blending amount of the modified vinyl copolymer (D) to 20 parts by weight or less. The blending amount of the modified vinyl polymer (D) is more preferably 15 parts by weight or less.

  The thermoplastic resin composition of the present invention includes hindered phenol-based, sulfur-containing organic compound-based, phosphorus-containing organic compound-based antioxidants, phenol-based, acrylate-based, etc., as long as the effects of the present invention are not impaired. Various stabilizers such as heat stabilizers, UV absorbers such as benzotriazoles, benzophenones, salicylates, light stabilizers such as organic nickels, hindered amines, lubricants such as higher fatty acid metal salts, higher fatty acid amides, Plasticizers such as phthalates and phosphates, anti-drip agents such as polytetrafluoroethylene, nonionic, anionic, cationic or amphoteric surfactants, carbon black, titanium oxide, pigments and dyes Liquids such as water, silicone oil, and liquid paraffin can also be blended. Moreover, a filler can also be mix | blended.

  Examples of the filler include fibers, plates, powders, granules, and the like, and any of them may be used in the present invention. Specifically, polyacrylonitrile (PAN) and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia Fibrous or whisker-like fillers such as fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, glass fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, Mica, talc, kaolin, silica, calcium carbonate, glass flakes, glass beads, glass microballoons, clay, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, barium sulfate, calcium polyphosphate Powder such as graphite, and the like granular or platy filler. Two or more of these may be used. Among these, glass fiber is preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resin, and examples thereof include long fiber type, short fiber type chopped strands, and milled fiber. The surface of the filler may be treated with any coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. Further, it may be coated or focused with a thermoplastic resin such as ethylene / vinyl acetate copolymer, or a thermosetting resin such as epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. Good.

  The blending amount of the filler is preferably 0.01 to 100 parts by weight with respect to a total of 100 parts by weight of the vinyl copolymer (A) and the graft copolymer (B). By setting the blending amount of the filler within this range, the rigidity and heat resistance of the molded product can be further improved. The blending amount of the filler is more preferably 0.05 parts by weight or more, and further preferably 0.1 parts by weight or more. On the other hand, the blending amount of the filler is more preferably 50 parts by weight or less, and further preferably 30 parts by weight or less.

In the thermoplastic resin composition of the present invention, two square plates having a plane size of 40 mm × 50 mm × thickness of 3 mm are injection-molded, and 20 mg of 2-butanone is added to a portion of the square plate having a plane size of 40 mm × 5 mm (area 200 mm ² ). Apply and paste two square plates, hold at 0.05 MPa for 10 minutes, store for 2 days in a temperature 23 ° C., humidity 50% RH environment, then use a bending tester to bend at a rate of 2 mm / min. It is preferable that the strength (solvent adhesive strength) when bent until the bonded portion peels or the base material breaks is 10 MPa or more. For example, as an example of the use of a thermoplastic resin composition, if a photomask case that requires impact resistance and antistatic properties is given, a resin molded product made of the thermoplastic resin composition may be a 2-butanone, acetonitrile, or the like. In general, they are used by being bonded together using an organic solvent. In such an application, it is preferable that the surface where the resin molded products are bonded to each other is excellent in adhesiveness with an organic solvent in order to suppress peeling and breaking due to vibration during transportation. Therefore, in the present invention, as an index of adhesiveness by such an organic solvent, the bending strength after two square plates injection-molded with a thermoplastic resin composition are applied and held together by applying 2-butanone is used. Pay attention. In addition, the bonding condition of the square plate is experimentally selected as a condition for reliably bonding the square plate. The higher the solvent adhesive strength, the better the adhesion to organic solvents.

  The thermoplastic resin composition having the above-mentioned solvent adhesive strength of 10 MPa or more includes, for example, the above-mentioned preferable vinyl copolymer (A), graft copolymer (B) and polyamide elastomer (C), respectively, as described above. It can obtain by mix | blending in the range.

The thermoplastic resin composition of the present invention, injection molded square plate molded article having a thickness of 3 mm, the test method prescribed in JIS K7373 (established in 2006), when measured by the reflection measuring method using a standard illuminant D ₆₅ The yellowness (YI) is preferably 25 or less. For example, as an example of the use of the thermoplastic resin composition, when a photomask case that requires impact resistance and antistatic properties is given, it is preferable that coloring is difficult from the viewpoint of the visibility of the contents. Therefore, in the present invention, attention is paid to yellowness (YI) as a coloring index. The thickness of the test piece for measuring the yellowness (YI) was selected to be 3 mm because it is hardly affected by variations in molding conditions and is close to the thickness of a large photomask case.

  Although there is no restriction | limiting in particular in the manufacturing method of a thermoplastic resin composition, The process of obtaining the said vinyl type copolymer (A), the process of obtaining the said graft copolymer (B), and a vinyl type copolymer (A) 40 to 90 parts by weight of vinyl copolymer (A), 10 to 60 parts by weight of graft copolymer (B), polyamide elastomer (C It is preferable to have a step of blending 3 parts by weight or more). From the viewpoint of productivity, a method of melt-kneading the vinyl copolymer (A), the graft copolymer (B), the polyamide elastomer (C) and other components as necessary is common. When the above-mentioned additives are blended, the blending method is not particularly limited, and various methods can be used.

  The thermoplastic resin composition of the present invention can be molded by known methods such as injection molding, extrusion molding, calendar molding, blow molding, vacuum molding, compression molding, gas assist molding and the like.

  The thermoplastic resin composition of the present invention can provide a molded product excellent in adhesion with an organic solvent, impact resistance, antistatic property and color tone. Utilizing such characteristics, it can be suitably used for photomask cases, electrical / electronic parts, parts for transporting electrical / electronic parts, parts for transporting display-related parts, etc. that require impact resistance and anti-static characteristics. .

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. First, the evaluation method in an Example is demonstrated.

(1) Refractive index of vinyl copolymer and refractive index of acetone insoluble matter (graft component) of graft copolymer Vinyl copolymer (A) or (A ′) obtained by Reference Examples 1 to 5 The film was dried under reduced pressure at 80 ° C. for 5 hours, and heated and pressurized with a heating press set at 230 ° C. to produce a film with a thickness of 30 ± 5 μm.

  To about 1 g of the sample of the graft copolymer (B) or (B ′) obtained in Reference Examples 6 to 7, 80 ml of acetone was added and refluxed in a 70 ° C. water bath for 3 hours. p. After centrifuging at m (10000 G) for 40 minutes, the insoluble matter was filtered to obtain an acetone insoluble matter. The obtained acetone-insoluble matter was dried under reduced pressure at 80 ° C. for 5 hours, and heated and pressurized with a heating press set at 230 ° C. to produce a film with a thickness of 30 ± 5 μm.

A small amount of 1-bromonaphthalene was dropped on the film obtained by the above method, and the refractive index was measured under the following conditions using an Abbe refractometer.
Light source: Sodium lamp D-ray measurement temperature: 23 ° C.

(2) Solubility parameter of vinyl copolymer The solubility parameter of the vinyl copolymer (A) or (A ') obtained in Reference Examples 1 to 5 is calculated by the following formula (1) from the copolymer composition ratio. did.
δ = (ΣΔEi · X / ΣΔVm · X) ^1/2 (1)
δ: Solubility parameter of vinyl copolymer (A) ((J / cm ³ ) ^1/2 )
X: molar fraction (%) of the copolymer component constituting the vinyl copolymer (A)
ΔEi: Evaporation energy (J / mol) of the copolymer component constituting the vinyl copolymer (A)
ΔVm: molecular volume of the copolymer component constituting the vinyl copolymer (A) (cm ³ / mol)

  However, the numerical values of X, ΔEi, and ΔVm are H.264. Burrell, Offic. Dig. A. J. et al. Tortorello, M.M. A. Kinsella, J. et al. Coat. Technol. Quoted from.

(3) Number average molecular weight of vinyl copolymer and number average molecular weight of acetone-soluble portion of graft copolymer Graft copolymer (B) or (B ′) obtained by Reference Examples 6 to 7 in about 1 g 80 ml of acetone was added and refluxed in a 70 ° C. water bath for 3 hours. p. After centrifuging at m (10000 G) for 40 minutes, the insoluble matter was filtered, and the filtrate was concentrated by a rotary evaporator to obtain an acetone-soluble precipitate.

The vinyl copolymer (A) or (A ′) obtained by Reference Examples 1 to 5 or the graft copolymer (B) or (B ′) obtained by the method described in (1) above can be acetone. About the solution, about 0.03 g of each sample was dissolved in about 15 g of tetrahydrofuran to prepare a solution of about 0.2% by weight. From the GPC chromatogram measured under the following conditions, the number average molecular weight converted using polymethyl methacrylate as a standard substance was calculated.
Equipment: Waters 2695
Column temperature: 40 ° C
Detector: RI2414 (differential refractometer)
Carrier eluent flow rate: 0.3 ml / min (solvent: tetrahydrofuran)
Column: TSKgel SuperHZM-M (6.0 mm ID × 15 cm), TSKgel SuperHZM-N (6.0 mm ID × 15 cm) in series (both Tosoh).

(4) Graft ratio of graft copolymer 80 ml of acetone was added to about 1 g (m: sample mass) of the graft copolymer (B) or (B ′) obtained in Reference Examples 6 to 7, Reflux in a hot water bath for 3 hours and add 8000 r. p. After centrifugation at m (10000 G) for 40 minutes, the insoluble matter was filtered. The obtained acetone insoluble matter was dried under reduced pressure at 80 ° C. for 5 hours, its mass (n) was measured, and the graft ratio was calculated from the following formula. Here, X is the rubbery polymer content of the graft copolymer (B).
Graft ratio (%) = {[(n) − (m) × X] / [(m) × X]} × 100.

(5) Acrylonitrile-derived unit content in acetone-soluble component (E) and acetone-insoluble component (F) Vinyl copolymer (A) or (A ′) and graft copolymer (B) or (B ′ 80 ml of acetone was added to about 1 g of the resin blended at the blending ratio in each Example and Comparative Example, and refluxed in a 70 ° C. hot water bath for 3 hours. p. After centrifugation at m (10000 G) for 40 minutes, the insoluble matter was filtered to obtain an acetone insoluble matter (F). On the other hand, the filtrate was concentrated with a rotary evaporator to obtain a precipitate of acetone-soluble matter (E). The acetone-insoluble component (F) and the acetone-soluble component (E) were each dried under reduced pressure at 80 ° C. for 5 hours, and heated and pressurized with a heating press set at 230 ° C. to produce a film with a thickness of 30 ± 5 μm. About the obtained film, FT-IR analysis was performed and the acrylonitrile origin unit content was calculated | required from the intensity ratio of the following peak which appeared on the FT-IR chart.
Aromatic vinyl monomers (a1), (b1): 1605 cm ⁻¹ peak unsaturated carboxylic acid alkyl ester monomers (a2) attributed to vibration of the benzene nucleus (b2): carbonyl group of the ester 1730 cm ⁻¹ peak vinyl cyanide monomer (a3), (b3) attributed to C═O stretching vibration: 2240 cm ⁻¹ peak rubbery polymer (r) attributed to —C≡N stretching (r): C = peak at 960 cm ⁻¹ attributed to C.

(6) Ratio of triple sequence of acrylonitrile-derived monomer units in acetone-soluble component (E) Acetone-soluble component (E) obtained by the procedure described in (5) as a sample, ¹³ C-NMR Using the fact that the α-carbon signal shift of the acrylonitrile monomer unit appearing in Fig. 2 is slightly different depending on the type of adjacent monomer, the ratio of the triple sequence was quantified from the signal integration value, The weight fraction of the acrylonitrile-derived unit at the center of the continuous sequence was calculated. ^{The 13} C-NMR measurement conditions are as follows.
Equipment: JEOL J NM-GSX400 type Observation frequency: 100.5 MHz
Solvent: DMSO-d ₆
Concentration: 445 mg / 2.5 ml
Chemical shift criteria: Me ₄ Si
Temperature: 110 ° C
Observation width: 20000Hz
Data point: 32K
flip angle: 90 ° (21 μs)
pul sedel aytime: 5.0s
Integration count: 8400
Decoupling: gated decoupling (without NOE)
Acrylonitrile sequence assignment (A: acrylonitrile, S: styrene): -A-A-A-118.6 to 119.2 ppm, -A-A-S-119.3 to 120.2 ppm, -S-A-S- 120.2-121.3 ppm.

(7) Transparency (haze value)
SE-50DU manufactured by Sumitomo Heavy Industries, Ltd. with the cylinder temperature set to 230 ° C. after drying the thermoplastic resin composition pellets obtained in each Example and Comparative Example for 5 hours in a hot air dryer at 80 ° C. The molding machine was filled and a square plate molded product having a thickness of 3 mm was immediately injection molded. Using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., the haze value (%) was measured for each of the obtained square plate molded products, and the number average value was calculated.

(8) Color tone (Yellowness YI)
SE-50DU manufactured by Sumitomo Heavy Industries, Ltd. with the cylinder temperature set to 230 ° C. after drying the thermoplastic resin composition pellets obtained in each Example and Comparative Example for 5 hours in a hot air dryer at 80 ° C. The molding machine was filled and a square plate molded product having a thickness of 3 mm was immediately injection molded. About five obtained square plate molded products, YI value was measured based on JIS K7373 (established in 2006), and the number average value was computed.

(9) Impact resistance (Charpy impact strength)
SE-50DU manufactured by Sumitomo Heavy Industries, Ltd. with the cylinder temperature set to 230 ° C. after drying the thermoplastic resin composition pellets obtained in each Example and Comparative Example for 5 hours in a hot air dryer at 80 ° C. The molding machine was filled and a 4 mm thick dumbbell specimen was immediately injection molded. About five obtained dumbbell test pieces, Charpy impact strength was measured by a method based on ISO179, and the number average value was calculated.

(10) Formability (melt flow rate (MFR))
After the thermoplastic resin composition pellets obtained in each Example and Comparative Example were dried in a hot air dryer at 80 ° C. for 5 hours, MFR was measured by a method based on ISO 113 under the conditions of a measurement temperature of 220 ° C. and a load of 98 N. It was measured.

(11) Surface specific resistance value After the thermoplastic resin composition pellets obtained in each of the examples and comparative examples were dried in a hot air dryer at 80 ° C. for 5 hours, Nissei Plastic Industry (Cylinder temperature set at 230 ° C.) A PS60E molding machine manufactured by Co., Ltd. was filled, and a square plate molded product having a thickness of 40 mm × 50 mm × 3 mm was immediately injection molded. The obtained square plate molded article was allowed to stand for 24 hours in an environment of temperature 23 ° C. and humidity 50% Rh, and after 1 minute from application under the condition of applied voltage 500 V in accordance with ASTM D257 (1990). The surface resistivity was measured.

(12) Static electricity diffusion performance (charge voltage decay half-life)
SE-50DU manufactured by Sumitomo Heavy Industries, Ltd. with the cylinder temperature set to 230 ° C. after drying the thermoplastic resin composition pellets obtained in each Example and Comparative Example for 5 hours in a hot air dryer at 80 ° C. The mold was filled in a molding machine, and a square plate having a plane size of 40 mm × 50 mm × thickness of 3 mm was immediately injection molded. Using a static Honest meter (manufactured by Cishido electrostatic Co., Ltd.), the distance between the square plate and the applied electrode was 15 mm, the distance from the detection electrode was 10 mm, and a voltage of 8 kV was applied for 1 minute. The time (seconds) until V (volt) was halved was read and defined as the half-life of the voltage decay. It can be said that the shorter the charged voltage decay half-life, the better the electrostatic diffusion performance.

(13) Adhesiveness with organic solvent 2-butanone The thermoplastic resin composition pellets obtained in each Example and Comparative Example were dried in a hot air dryer at 80 ° C. for 5 hours, and then the cylinder temperature was set to 230 ° C. The product was filled into a SE-50DU molding machine manufactured by Sumitomo Heavy Industries, Ltd., and two square plates having a plane size of 40 mm × 50 mm × thickness of 3 mm were injection molded. 20 mg of organic solvent 2-butanone was applied to a square plate having a plane dimension of 40 mm × 5 mm (area 200 mm ² ), and two square plates were bonded together and held at 0.05 MPa for 10 minutes, temperature 23 ° C., humidity 50 After storing in a% RH environment for 2 days, the strength (solvent adhesive strength) was measured using a bending tester until the bonded portion peels or breaks the base material at a bending speed of 2 mm / min. It can be said that the higher the solvent adhesive strength, the better the adhesiveness. Moreover, it can be said that the direction which destroyed the base material is excellent in adhesiveness rather than peeling a bonded part.

(Reference Example 1) Vinyl-based copolymer (A-1)
A continuous bulk polymerization apparatus comprising a 2 m ³ complete mixing polymerization tank having a condenser for evaporating carbonization of monomer vapor and a helical ribbon blade, a single-screw extruder type preheater, and a twin-screw extruder type demonomer The vinyl copolymer was produced by the following method.

  First, a simple composition comprising 22 parts by weight of styrene, 15 parts by weight of acrylonitrile, 63 parts by weight of methyl methacrylate, 0.11 part by weight of n-octyl mercaptan and 0.015 part by weight of 1,1-bis (t-butylperoxy) cyclohexane. The monomer mixture (a) was continuously supplied to a fully mixed polymerization tank at 150 kg / hour, and continuous bulk polymerization was performed while maintaining the polymerization temperature at 130 ° C. and the tank internal pressure at 0.08 MPa. The polymerization rate of the polymerization reaction mixture at the outlet of the complete mixing type polymerization tank was controlled to 65 ± 3%.

  The polymerization reaction mixture was preheated by a single screw extruder type preheater, then supplied to a twin screw extruder type demonomer machine, and unreacted monomer was recovered by evaporation from the vent port of the twin screw extruder type demonomer machine. . The recovered unreacted monomer was continuously refluxed to the complete mixing polymerization tank. A styrene / acrylonitrile / methyl methacrylate copolymer with an apparent polymerization rate of 99% or more from the downstream end of the twin-screw extruder type demonomer at a rate of 1/3 of the total length is discharged in strands. And cut with a cutter to produce a vinyl copolymer (A-1). The number average molecular weight of the obtained vinyl copolymer (A-1) was 95,000.

(Reference Example 2) Vinyl-based copolymer (A-2)
A vinyl copolymer (A-2) was produced in the same manner as in Reference Example 1 except that the amount of n-octyl mercaptan was 0.21 part by weight. The number average molecular weight of the obtained vinyl copolymer (A-2) was 65,000.

Reference Example 3 Vinyl copolymer (A′-3)
24 parts by weight of styrene, 4 parts by weight of acrylonitrile, 72 parts by weight of methyl methacrylate, 0.12 parts by weight of n-octyl mercaptan and 1,1-bis (t -Vinylperoxy) A vinyl copolymer (A'-3) was produced in the same manner as in Reference Example 1 except that the amount of cyclohexane was 0.015 part by weight. The molecular weight of the obtained vinyl copolymer (A′-3) was 95,000.

Reference Example 4 Vinyl copolymer (A′-4)
24 parts by weight of styrene, 7 parts by weight of acrylonitrile, 69 parts by weight of methyl methacrylate, 0.18 parts by weight of n-octyl mercaptan and 1,1-bis (t -Vinylperoxy) A vinyl copolymer (A'-4) was produced in the same manner as in Reference Example 1 except that the amount of cyclohexane was 0.015 part by weight. The number average molecular weight of the obtained vinyl copolymer (A′-4) was 65,000.

Reference Example 5 Vinyl copolymer (A′-5)
80 parts by weight of acrylamide, 20 parts by weight of methyl methacrylate, 0.3 parts by weight of potassium persulfate and 1800 parts by weight of pure water were charged into the reaction vessel, the gas phase in the reaction vessel was replaced with nitrogen gas, Kept at ℃. After the reaction was continued until the monomer was completely converted to a polymer, 20 parts by mass of sodium hydroxide and 2000 parts by weight of pure water were added, stirred at 70 ° C. for 2 hours, and then cooled to room temperature. A methyl methacrylate-acrylamide binary copolymer aqueous solution as a suspension polymerization medium was obtained.

  In a 20 liter autoclave, a solution prepared by dissolving 0.05 parts by weight of the methyl methacrylate / acrylamide binary copolymer aqueous solution in 165 parts by weight of pure water was stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, a mixed solution of 30 parts by weight of acrylonitrile, 10 parts by weight of styrene, 0.3 part by weight of azobisisobutyronitrile and 0.5 part by weight of t-dodecyl mercaptan was added while stirring the reaction system, and the mixture was heated to 60 ° C. The copolymerization reaction was started, and the temperature was raised to 70 ° C. over 30 minutes. 30 minutes after the start of polymerization, 30 parts by weight of acrylonitrile was added. Thereafter, methyl methacrylate was added to the reaction system at an interval of 30 minutes each 15 parts by weight × 2 times. The temperature was raised to 100 ° C. over 60 minutes after the addition of all the monomers. After reaching the temperature, the temperature was controlled at 100 ° C. for 30 minutes, and then cooling, polymer separation, washing, and drying were performed to obtain a bead-shaped copolymer. The number average molecular weight of the obtained vinyl copolymer (A′-5) was 65,000.

  Table 1 shows the monomer mixture composition, refractive index, solubility parameter, and number average molecular weight of the vinyl copolymers (A) and (A ′) obtained in Reference Examples 1 to 5.

Reference Example 6 Graft copolymer (B-1)
In a four-necked flask with an internal volume of 5 liters equipped with a stirring blade, 50 parts by weight (in terms of solid content) of polybutadiene latex (weight average particle diameter of rubber 0.30 μm, gel content 85%, refractive index 1.516), 130 parts by weight of pure water, 0.4 parts by weight of sodium laurate, 0.2 parts by weight of glucose, 0.2 parts by weight of sodium pyrophosphate and 0.01 parts by weight of ferrous sulfate While stirring and stirring the temperature, a monomer mixture of 3.6 parts by weight of styrene, 0.6 parts by weight of acrylonitrile, 10.8 parts by weight of methyl methacrylate and 0.15 parts by weight of t-dodecyl mercaptan was added over 45 minutes. Initial addition.

  Subsequently, an initiator mixture of 0.3 parts by weight of cumene hydroperoxide, 1.6 parts by weight of sodium laurate as an emulsifier and 25 parts by weight of pure water was continuously dropped over 5 hours. At the same time, a monomer mixture of 8.4 parts by weight of styrene, 1.4 parts by weight of acrylonitrile, 25.2 parts by weight of methyl methacrylate and 0.36 parts by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours. did. After the monomer mixture was added dropwise, the polymerization was terminated by maintaining for 1 hour. The obtained graft copolymer latex was coagulated with 1.5% by weight sulfuric acid, neutralized with sodium hydroxide, washed, centrifuged and dried to obtain a powdery graft copolymer (B-1) ( Monomer ratio: 24% by weight of styrene, 4% by weight of acrylonitrile, 72% by weight of methyl methacrylate). The obtained graft copolymer (B-1) had an acetone insoluble refractive index of 1.517, and the refractive index difference from the rubbery polymer was 0.001. The graft rate was 47%. Moreover, the number average molecular weight of the acetone-soluble component was 34,000.

Reference Example 7 Graft copolymer (B′-2)
The monomer mixture added initially was 3.15 parts by weight of styrene, 3 parts by weight of acrylonitrile, and 8.85 parts by weight of methyl methacrylate. Graft copolymer in the same manner as in Reference Example 6 except that the amount of styrene contained was 7.35 parts by weight, the amount of acrylonitrile was 7 parts by weight, and the amount of methyl methacrylate was 20.65 parts by weight. (B′-2) (monomer ratio: 21% by weight of styrene, 20% by weight of acrylonitrile, 59% by weight of methyl methacrylate) was obtained. The resulting graft copolymer (B′-2) had an acetone insoluble refractive index of 1.516, and the refractive index difference from the rubbery polymer was 0.000. The graft rate was 50%. Moreover, the number average molecular weight of the acetone-soluble matter was 65,000.

  Properties of rubbery polymers of graft copolymers (B) and (B ′) obtained in Reference Examples 6 to 7, monomer mixture composition, refractive index of acetone insoluble matter, number average of acetone soluble matter Table 2 shows the molecular weight and the graft ratio.

(Reference Example 8) Polyamide elastomer (C)
45 parts by weight of ε-caprolactam, 45 parts by weight of an ethylene oxide adduct of bisphenol A having a number average molecular weight of 1,800, 5 parts by weight of polyethylene glycol having a number average molecular weight of 1,800, 5.2 parts by weight of terephthalic acid, and “Irganox "0.2 parts by weight of (registered trademark) 1098 (antioxidant) was charged into a reaction vessel, purged with nitrogen, heated and stirred at a temperature of 260 ° C for 60 minutes to obtain a transparent homogeneous solution, and then 0.07 kPa or less. Depressurized to pressure. To this, 0.1 part by weight of tetrabutyl titanate was added, the pressure was adjusted to 0.07 kPa or less, and the reaction was carried out at 260 ° C. for 2 hours. The obtained polymer was discharged in a strand shape and cut to prepare a pellet-shaped polyamide elastomer (C).

(Reference Example 9) Modified vinyl copolymer having carboxyl group (D)
A monomer mixture consisting of 70% by weight of styrene, 25% by weight of acrylonitrile, and 5% by weight of methacrylic acid was prepared at 65 ° C. to 95 ° C. using an initiator (azodiisobutyronitrile) and a chain transfer agent (t-dodecyl mercaptan). Suspension polymerization was performed at the temperature of 5 hours to prepare a bead-like modified vinyl polymer (D). The intrinsic viscosity at this time (in methyl ethyl ketone, 30 ° C.) was 0.60 dl / g.

(Examples 1-6, Comparative Examples 1-6)
The vinyl copolymer prepared in Reference Examples 1 to 5, the graft copolymer prepared in Reference Examples 6 to 7, the polyamide elastomer (C) prepared in Reference Example 8, and the modified vinyl copolymer prepared in Reference Example 9 The polymers (D) were blended at the blending ratios shown in Tables 3 to 4, respectively, and mixed at 23 ° C. with a Henschel mixer. The obtained mixture was melt-kneaded at an extrusion temperature of 230 ° C. by a 30 mmφ twin-screw extruder, extruded into a strand shape, and pelletized. The result evaluated by the above-mentioned method using the pellet of the obtained thermoplastic resin composition is shown to Tables 3-4.

  As Example 1-6, the thermoplastic resin composition of this invention can obtain the molded article excellent in the adhesiveness, impact resistance, antistatic property, and color tone by the organic solvent 2-butanone.

  On the other hand, in Comparative Example 1, since the blending amount of the polyamide elastomer (C) was small, the surface specific resistance value was high, the electrostatic diffusion performance was low, and the antistatic property was poor. In Comparative Example 2, since the amount of the vinyl copolymer (A) was large and the amount of the graft copolymer (B) was small, the impact resistance was inferior. In Comparative Examples 3 and 4, since the content of the vinyl cyanide monomer (a3) in the monomer mixture constituting the vinyl copolymer is small, the adhesion with the organic solvent 2-butanone is poor. there were. In Comparative Example 5, since the content of the vinyl cyanide monomer (b3) in the monomer mixture constituting the graft copolymer (B) was large, the color tone was inferior. In Comparative Example 6, since the content of the vinyl cyanide monomer (a3) in the monomer mixture constituting the vinyl copolymer was large, the color tone was inferior.

  The thermoplastic resin composition of the present invention can provide a molded product excellent in adhesion with an organic solvent, impact resistance, antistatic property and color tone. Utilizing such characteristics, it can be suitably used for photomask cases, electrical / electronic parts, parts for transporting electrical / electronic parts, parts for transporting display-related parts, etc. that require impact resistance and anti-static characteristics. .

Claims (7)

  At least aromatic vinyl monomer (a1) 5 to 40% by weight, unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 80% by weight, and vinyl cyanide monomer (a3) 10 to 50% by weight % Vinyl copolymer (A) obtained by copolymerizing a vinyl monomer mixture (a), and at least an aromatic vinyl monomer (b1) in the presence of a rubbery polymer (r). A vinyl monomer mixture containing 10 to 30 wt%, unsaturated carboxylic acid alkyl ester monomer (b2) 30 to 80 wt% and vinyl cyanide monomer (b3) 1 to 10 wt% ( b) a thermoplastic resin composition comprising a graft copolymer (B) obtained by graft copolymerization and a polyamide elastomer (C), wherein the vinyl copolymer (A) and the graft copolymer Combined (B) total 100 layers 40 to 90 parts by weight of the vinyl copolymer (A), 10 to 60 parts by weight of the graft copolymer (B), and 3 parts by weight or more of the polyamide elastomer (C). Resin composition.   The thermoplastic resin composition according to claim 1, wherein the polyamide elastomer (C) comprises a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 6,000 as a constituent component.   The proportion of the triple sequence of acrylonitrile-derived units present in the acetone-soluble component of the vinyl copolymer (A) and the graft copolymer (B) is 10% by weight or less in 100% by weight of the acetone-soluble component. The thermoplastic resin composition according to claim 1 or 2. Two square plates with a plane size of 40 mm x 50 mm x thickness of 3 mm are injection-molded, and 20 mg of 2-butanone is applied to the square plate with a plane dimension of 40 mm x 5 mm (area 200 mm ² ) and the two square plates are bonded together. Held at 0.05 MPa for 10 minutes and stored for 2 days in an environment of temperature 23 ° C. and humidity 50% RH, then the bonded part peels off or breaks the base material using a bending tester at a bending speed of 2 mm / min. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the strength (solvent adhesive strength) when bent until it is 10 MPa or more. A 3 mm-thick square plate product is injection-molded, and the yellowness (YI) when measured by a reflection measurement method using a standard illuminant D ₆₅ is 25 or less by a test method defined in JIS K7373 (established in 2006). The thermoplastic resin composition in any one of Claims 1-4.   At least aromatic vinyl monomer (a1) 5 to 40% by weight, unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 80% by weight, and vinyl cyanide monomer (a3) 10 to 50% by weight % Vinyl monomer mixture (a) is copolymerized to obtain vinyl copolymer (A), at least aromatic vinyl monomer (r) in the presence of rubber polymer (r). b1) vinyl monomer containing 10 to 30% by weight, unsaturated carboxylic acid alkyl ester monomer (b2) 30 to 80% by weight and vinyl cyanide monomer (b3) 1 to 10% by weight A step of graft-copolymerizing the mixture (b) to obtain a graft copolymer (B) and a total of 100 parts by weight of the vinyl copolymer (A) and the graft copolymer (B) 40 to 90 parts by weight of copolymer (A), 10-60 parts by weight shift copolymer (B), comprising the step of blending a polyamide elastomer (C) 3 parts by weight or more, the production method of the thermoplastic resin composition.   A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 5.