JP2005194369A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition causing no molding-related problems including laminar flaking-off phenomena even in undergoing thin-wall molding and cut processing, excellent in surface appearance, rigidity, heat resistance, chemical resistance, especially impact resistance both at room temperature and low temperatures, and good in fluidity as well. <P>SOLUTION: This thermoplastic resin composition is obtained by incorporating 100 pts.wt. of a resin composition with (iii) 0.5-60 pt(s).wt. of a copolymer, wherein the resin composition comprises (i) a rubber-reinforced styrene-based resin comprising (A-1) a graft (co)polymer obtained by graft (co)polymerization of a monomer or monomer mixture containing an aromatic vinyl monomer to a rubbery polymer and (A-2) a vinyl (co)polymer and (ii) a polyamide resin 2.0-4.0 in relative viscosity, and the ratio of the molar fraction (X) of the component (iii) to the molar fraction (Y) of vinyl cyanide-based monomer unit in the component (iii) is 0.90-1.25. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition obtained by adding a specific modified vinyl copolymer to a rubber-reinforced styrene resin and a polyamide resin having a specific relative viscosity. There are no molding problems such as delamination, surface appearance, rigidity, heat resistance, chemical resistance, especially impact resistance at room temperature and low temperature, and excellent fluidity in addition to the above characteristics. The present invention relates to a thermoplastic resin composition.

  Rubber-reinforced styrene resins have features such as high rigidity, good appearance, good dimensional stability, and low hygroscopicity, and are widely used as general-purpose thermoplastic resins. However, chemical resistance, wear resistance, and heat resistance are not sufficient, and use under severe conditions is limited.

  Polyamide resins are excellent in chemical resistance, wear resistance, and heat resistance, and are widely used as engineering plastics, but they have high water absorption and are insufficient in rigidity and dimensional stability.

  Therefore, in order to create a resin composition having both advantages of rubber-reinforced styrene resin and polyamide resin, a blend of ABS resin and polyamide resin, which is a typical rubber-reinforced styrene resin, has been proposed (for example, patents). Reference 1). However, a simple blend of an ABS resin and a polyamide resin has a poor compatibility and has a very low mechanical property.

  Therefore, as a compatibility improvement, a technique has been devised in which a monomer having a functional group having an affinity for a polyamide resin is graft copolymerized with a rubber-like polymer and blended with the polyamide resin. As one of the methods, a blend of a graft copolymer obtained by graft copolymerization of an α, β-unsaturated carboxylic acid anhydride and a rubbery polymer together with other monomers and a polyamide resin has been proposed ( For example, see Patent Document 2). However, the resin composition thus obtained has problems such as insufficient impact resistance, surface appearance, fluidity, and thermal stability.

  As another method, a blend of a graft copolymer obtained by graft copolymerization of an unsaturated carboxylic acid amide with a rubber polymer together with another polymer and a polyamide resin has been proposed (for example, see Patent Document 3). However, this resin composition has insufficient impact resistance and has a problem in mechanical properties upon water absorption.

  Therefore, for the purpose of improving impact resistance and mechanical properties at the time of water absorption, a three-component resin using a copolymer of styrene and an unsaturated dicarboxylic acid anhydride as a compatibilizer between a styrene resin and a polyamide resin. A composition has been proposed (see, for example, Patent Document 4). However, although the obtained resin composition has been improved in mechanical properties at the time of water absorption, the impact resistance is still insufficient.

In addition, by adding an α, β-unsaturated carboxylic acid-containing copolymer, such as a styrene-acrylonitrile-methacrylic acid copolymer, to ABS resin and polyamide resin, it has excellent impact resistance, chemical resistance and fluidity. It has been reported that a resin composition can be obtained (for example, see Patent Document 5). On the other hand, when considering large molded products such as automotive interior / exterior materials and electrical / electronic equipment housings / parts surrounding materials as application development of these resin compositions, in addition to excellent impact resistance and chemical resistance, Therefore, there is a demand for a resin composition having even higher rigidity and fluidity than conventional ones. Therefore, as a resin composition excellent in impact resistance, rigidity and fluidity, a styrene-acrylonitrile-methacrylic acid copolymer having a specific reduced viscosity is blended, and agglomeration hypertrophy formed by agglomerating small particle rubber having a specific particle diameter. A resin composition using a modified rubber has been reported (see, for example, Patent Document 6). However, the impact resistance, rigidity and fluidity of this resin composition are not yet sufficient for the above-mentioned applications, and in particular, a resin composition having a higher degree of balance between impact resistance and fluidity at room temperature and low temperature. Things are desired.
Japanese Patent Publication No. 38-23476 (Claims) JP-A-56-112957 (Claims) JP 58-93745 A (Claims) JP-A-60-195157 (Claims) JP 63-179957 A (Claims) JP 2000-17170 (Claims)

  In view of the background of such prior art, the present invention provides a high rigidity, good appearance, high dimensional stability and low water absorption of a rubber reinforced styrene resin when obtaining a resin composition comprising a rubber reinforced styrene resin and a polyamide resin. The interior and exterior of an automobile that has a high balance between the properties and the chemical resistance and heat resistance of polyamide resin, and exhibits excellent impact resistance at room temperature and low temperature. It is an object of the present invention to provide a thermoplastic resin composition useful as a material and a material around housings and parts of electric / electronic devices.

In order to solve the above problems, the present invention employs the following means. That is, the thermoplastic resin composition of the present invention comprises (i) a graft (co) polymer obtained by graft polymerization of a monomer or a monomer mixture containing an aromatic vinyl monomer to a rubbery polymer ( A-1) Vinyl (co) polymer (A-2) 0 to 95 wt% obtained by polymerizing 5 to 100 wt% and a monomer or monomer mixture containing an aromatic vinyl monomer The relative viscosity of a solution of 10% to 90% by weight of a rubber-reinforced styrene-based resin and (ii) 98% concentrated sulfuric acid at a concentration of 1 g / dl is 2.0 to 4.0 at 25 ° C. 100 parts by weight of a resin composition comprising 10 to 90% by weight of a certain polyamide resin
(iii) Modified vinyl copolymer (B-1) obtained by polymerizing aromatic vinyl monomer, vinyl cyanide monomer, α, β-unsaturated carboxylic acid monomer, and aromatic vinyl Modified vinyl copolymer (B-2) obtained by polymerizing a monomer, a vinyl cyanide monomer, an α, β-unsaturated carboxylic acid monomer and / or another unsaturated monomer A thermoplastic resin composition further containing 0.5 to 60 parts by weight of a copolymer selected from: and (iii) a mole fraction of aromatic vinyl monomer units in the copolymer (X) and (iii) X / Y, which is the ratio of molar fraction (Y) of vinyl cyanide monomer units in the copolymer, is 0.90 to 1.25, To do.

  By the present invention, molding problems such as delamination do not occur at the time of thin molding and cutting, surface appearance, rigidity, heat resistance, chemical resistance, especially excellent impact resistance at normal temperature and low temperature, and the above characteristics In addition, it is possible to provide a useful thermoplastic resin composition that also has excellent fluidity.

  Embodiments of the present invention will be described below.

  The present invention is excellent in surface appearance, rigidity, heat resistance, and chemical resistance, especially in normal temperature and low temperature, without the above problems, that is, molding problems such as delamination even during thin molding or cutting. With regard to the thermoplastic resin composition having excellent properties, the inventors studied diligently, and compared the rubber-reinforced styrene resin and polyamide resin with the mole fraction of the aromatic vinyl monomer unit and the mole of the vinyl cyanide monomer unit. When a specific copolymer having a fraction ratio in a specific range was added, it was found that such a problem could be solved all at once. Furthermore, the present inventors have found that a thermoplastic resin composition having excellent fluidity in addition to the above characteristics can be obtained by defining the relative viscosity of the polyamide resin used as a component within a specific range. It is.

  The (i) rubber-reinforced styrene resin used in the present invention is a graft (co) polymer (A) obtained by graft polymerization of a monomer or monomer mixture containing an aromatic vinyl monomer to a rubber polymer. -1) 5 to 100% by weight, and vinyl (co) polymer (A-2) 0 to 95% by weight obtained by polymerizing a monomer or monomer mixture containing an aromatic vinyl monomer It consists of

  Specific examples of such (i) rubber-reinforced styrene resin include, for example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylenepropylene rubber). -Styrene copolymer), MBS resin (methyl methacrylate-butadiene rubber-styrene copolymer), and the like.

  As the rubbery polymer constituting the graft (co) polymer (A-1), those having a glass transition temperature of 0 ° C. or lower are suitable, and diene rubber is preferably used. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, diene rubber such as butyl acrylate-butadiene copolymer, acrylic such as polybutyl acrylate, etc. Rubber, polyisoprene, ethylene-propylene-diene terpolymer, and the like. Among them, polybutadiene or butadiene copolymer is preferable. These may be used alone or in combination of two or more.

  The rubber particle diameter of the rubber polymer is not particularly limited, but those having a weight average particle diameter of rubber particles of 0.15 to 0.6 μm, particularly 0.20 to 0.55 μm are preferable because of excellent impact resistance. Among them, a combination of a rubber having a particle diameter of 0.20 to 0.25 μm and a rubber having a particle diameter of 0.50 to 0.65 μm in a weight ratio of 90:10 to 60:40 is used for impact resistance and a thin molded product. The drop weight impact is extremely excellent and preferable.

  The weight average particle diameter of the rubber particles is creamed according to the sodium alginate method (sodium alginate concentration) described in “Rubber Age Vol. 88 p. 484 to 490 (1960) by E. Schmidt, PH Biddison”. Utilizing the fact that the polybutadiene particle diameter is different, it can be measured by a method of obtaining a particle diameter of 50% cumulative weight fraction from the creamed weight ratio and the cumulative weight fraction of sodium alginate concentration.

  The aromatic vinyl monomer in the graft (co) polymer (A-1) is styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, p-methylstyrene. , Chlorostyrene, bromostyrene and the like, and styrene is particularly preferable, and these may be used alone or in combination of two or more.

  Further, as necessary, monomers other than the aromatic vinyl monomer contained in the monomer mixture containing the aromatic vinyl monomer may be a vinyl cyanide monomer for the purpose of improving chemical resistance. For the purpose of improving the color tone and transparency of the monomer, a (meth) acrylic acid ester monomer is preferably used. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferable. Examples of the (meth) acrylic acid ester monomer include esterification products of acrylic acid and methacrylic acid with methyl, ethyl, propyl, n-butyl, isobutyl, and the like, and methyl methacrylate is particularly preferable. Also, (meth) acrylic acid, glycidyl (meth) acrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, Itaconic acid, itaconic anhydride, phthalic acid, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, (Meth) acrylic acid aminoethyl, (meth) acrylic acid propylaminoethyl, (meth) acrylic acid 2-dimethylaminoethyl, (meth) acrylic acid 2-diethylaminoethyl, (meth) acrylic 2-dibutylaminoethyl, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, N-vinyldiethylamine, Use N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline, etc. You can also. These may be used alone or in combination of two or more.

  The graft (co) polymer (A-1) in the present invention is preferably in the presence of 10 to 80 parts by weight of a rubbery polymer, more preferably 40 to 80 parts by weight, and even more preferably 55 to 80 parts by weight. The above monomer or monomer mixture is preferably obtained by (co) polymerizing 20 to 90 parts by weight, more preferably 20 to 60 parts by weight, and even more preferably 20 to 45 parts by weight. When the ratio of the rubbery polymer is less than 10 parts by weight, the impact strength tends to be lowered, and when it exceeds 80 parts by weight, the surface appearance tends to be lowered.

  The aromatic vinyl monomer in the monomer or monomer mixture used for the graft (co) polymer (A-1) is preferably 40 to 95% by weight, more preferably 50 to 80% by weight. %, More preferably 60% by weight to 75% by weight. In the case of mixing a vinyl cyanide monomer, the mixing ratio is preferably 5 to 50% by weight, more preferably 20 to 40% by weight, and further preferably 25 to 35% by weight. When the (meth) acrylic acid ester monomer is mixed, it is preferably mixed at 80% by weight or less, more preferably 75% by weight or less. When other vinyl monomers copolymerizable with these are mixed, the content is preferably 60% by weight or less, and more preferably 30% by weight or less. If the graft (co) polymer (A-1) contains at least an aromatic vinyl monomer unit and a vinyl cyanide monomer unit, it is contained in the graft (co) polymer (A-1). Molar ratio of aromatic vinyl monomer units to vinyl cyanide monomer units (<mole number of aromatic vinyl monomer units> / <mole number of vinyl cyanide monomer units>) The molar ratio is preferably 0.90 to 1.45, more preferably 0.90, from the viewpoint of the balance between impact resistance and molding processability of the resin composition obtained. To 1.35, more preferably 0.90 to 1.25, and most preferably 0.95 to 1.15.

The graft (co) polymer (A-1) includes an ungrafted (co) polymer formed when a monomer or a monomer mixture is grafted (co) polymerized to a rubbery polymer. May be. That is, the monomers of the monomer mixture may be bonded to each other and may contain an ungrafted (co) polymer, and usually obtained as a mixture with an ungrafted (co) polymer. use. This mixture is originally a composition, but in the present invention, it is collectively referred to as a graft (co) polymer (A-1) for convenience. Here, the graft rate is not particularly limited, but the graft rate is preferably 10 to 150% from the viewpoint of impact strength. The graft ratio is calculated by the following formula.
Graft rate (%) = <Amount of vinyl (co) polymer graft polymerized to rubbery polymer> / <Rubber content of graft (co) polymer> × 100
In addition, the intrinsic viscosity measured at 30 ° C. of a methylethylketone solvent of an ungrafted (co) polymer is not particularly limited, but 0.1 to 1.0 dl / g has a balance between impact strength and moldability. It is preferably used from the viewpoint, and more preferably 0.1 to 0.7 dl / g.

  There is no restriction | limiting in particular regarding the manufacturing method of a graft (co) polymer (A-1), Normal methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used. There is no particular limitation on the monomer charging method, and it may be added all at once, and part or all of the charged monomer is continuously charged or divided in order to prevent the formation of a copolymer composition distribution. Polymerization may be performed while charging. It is also possible to blend and use two or more of the graft (co) polymers (A-1) separately (grafted) copolymerized.

  The vinyl (co) polymer (A-2) in the present invention is not essential as a component constituting the (i) rubber-reinforced styrene resin used in the present invention, but is used as necessary. In that case, as the aromatic vinyl monomer used for the vinyl (co) polymer (A-2), styrene, α-methyl styrene, vinyl toluene, o-ethyl styrene, pt-butyl styrene, p -Aromatic vinyl monomers such as methylstyrene, chlorostyrene and bromostyrene are essential, and styrene is particularly preferable. These may be used alone or in combination of two or more.

  As a monomer other than the aromatic vinyl monomer, a vinyl cyanide monomer such as acrylonitrile, methacrylonitrile, ethacrylonitrile and the like is preferably used from the viewpoint of improving chemical resistance, and acrylonitrile is particularly preferable. In addition, maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide and the like are also preferable because of their improved heat resistance and flame retardancy. Maleimide is preferred. Other (meth) acrylic acid ester monomers such as esterified products of acrylic acid and methacrylic acid with methyl, ethyl, propyl, n-butyl, isobutyl, etc., (meth) acrylic acid, (meth) acrylic acid Glycidyl, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, maleic acid, maleic anhydride, maleic acid monoethyl ester, itaconic acid, itaconic anhydride, phthalic acid, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, (meth) acrylic acid 2- Ethylaminoethyl, 2-dibutylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, (meth) acrylic acid Cyclohexylaminoethyl, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and 2 -A styryl-oxazoline etc. can also be used. These may be used alone or in combination of two or more.

  The aromatic vinyl monomer in the monomer or monomer mixture used for the vinyl (co) polymer (A-2) is preferably 10 to 95% by weight, more preferably 50 to 80% by weight. More preferably, it is 60 to 75% by weight. When mixing a vinyl cyanide monomer, it is preferably 5 to 50% by weight, more preferably 20% to 40% by weight, and still more preferably 25% to 35% by weight. When mixing a maleimide-type monomer, 5 to 50 weight% is preferable, More preferably, it is 15 to 50 weight%. Moreover, when mixing a (meth) acrylic acid ester-type monomer, it is preferable to mix at 80 weight% or less, Furthermore, 75 weight% or less. When other vinyl monomers copolymerizable with these are mixed, the amount is preferably 60% by weight or less, more preferably 50% by weight or less. When the vinyl (co) polymer (A-2) contains at least an aromatic vinyl monomer unit and a vinyl cyanide monomer unit, the vinyl (co) polymer (A-2) Molar ratio of aromatic vinyl monomer units to vinyl cyanide monomer units contained in <(number of moles of aromatic vinyl monomer units> / <mole of vinyl cyanide monomer units) Number>) is not particularly limited, but from the viewpoint of rigidity, heat resistance, chemical resistance, molding processability, particularly impact resistance of the obtained resin composition, the molar ratio is 0.90 to 1. 30, preferably 0.90 to 1.25, more preferably 0.90 to 1.15, and most preferably 0.95 to 1.05.

  In the present invention, the intrinsic viscosity of the vinyl-based (co) polymer (A-2) measured at 30 ° C. of the vinyl (co) polymer (A-2) is not particularly limited, but 0.2 to 1.2 dl / g is the impact strength and molding process. It is preferably used from the viewpoint of balance of properties, and more preferably 0.3 to 0.9 dl / g.

  There is no restriction | limiting in particular about the manufacturing method of a vinyl type (co) polymer (A-2), and usual methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used. There is no particular limitation on the monomer charging method, and it may be added all at once, and part or all of the charged monomer is continuously charged or divided in order to prevent the formation of a copolymer composition distribution. Polymerization may be performed while charging. Moreover, it is also possible to blend and use 2 or more types of the graft | polymerization (co) polymer (A-2) polymerized separately.

  The mixing ratio of the graft (co) polymer (A-1) and the vinyl (co) polymer (A-2) constituting the rubber-reinforced styrene resin used in the present invention is as follows. The amount of the polymer (A-1) is 5 to 100 parts by weight, preferably 40 to 80 parts by weight, and the vinyl (co) polymer (A-2) is 0 to 95 parts by weight, preferably 20 to 60 parts by weight. If the graft (co) polymer (A-1) is less than 5 parts by weight, the impact resistance of the resin may be insufficient.

  The (ii) polyamide resin used in the present invention mainly comprises amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the raw material for the (ii) polyamide resin used in the present invention include aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, and lactams such as ε-caprolactam and ω-laurolactam. , Tetramethylenediamine, hexamethylenediamine, ethylenediamine, trimethylenediamine, pentamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4, 4-trimethylhexamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) Cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4- Aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and other aliphatic, alicyclic, and aromatic diamines, and adipic acid, peric acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3- Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydro Aliphatic and cycloaliphatic such as isophthalic acid And aromatic dicarboxylic acids.

  (ii) Polyamide resins are obtained from these raw materials by commonly known polycondensation, and in the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

  Examples of preferred polyamides include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polyhexamethylene sebacamide (nylon 610). ), Nylon 6/66 copolymer, nylon 6/66/610 copolymer, nylon 6/12 copolymer, nylon 66 / hexamethylene isophthalamide (6I) / 6 copolymer, nylon 6/66/610/12 copolymer, etc. Nylon 6, nylon 66 and a copolymer containing these as main components are preferable, and nylon 6 and a copolymer containing nylon 6 as main components are more preferable.

  The molecular weight of these (ii) polyamide resins is such that the relative viscosity of a solution usually dissolved in 98% concentrated sulfuric acid at a concentration of 1 g / dl is 2.0 to 4.0 at 25 ° C., that is, 98 g of polyamide resin 1 g / dl. The relative viscosity measured at 25 ° C. in a% concentrated sulfuric acid solution is 2.0 to 4.0, preferably 2.0 to 3.0, more preferably 2.0 to 2.8, most preferably 2.0 to 2.5. A relative viscosity exceeding 4.0 is not preferable because it leads to a decrease in fluidity and compatibility of the resin composition of the present invention. Moreover, when relative viscosity is less than 2.0, it leads to the fall of the mechanical characteristic of the resin composition of this invention, and is unpreferable. (ii) The melting point of the polyamide resin is the peak peak of crystal melting measured with a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer) in a nitrogen stream at a heating rate of 20 ° C./min. The melting point is preferably 150 to 280 ° C.

  The copolymer (iii) in the present invention is a modified vinyl copolymer obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, and an α, β-unsaturated carboxylic acid monomer ( B-1) and a modified vinyl system obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, an α, β-unsaturated carboxylic acid monomer and / or another unsaturated monomer A copolymer selected from the copolymer (B-2), and (iii) a molar fraction (X) of aromatic vinyl monomer units in the copolymer and (iii) in the copolymer The value of X / Y, which is the ratio of the molar fraction (Y) of the vinyl cyanide monomer unit, is 0.90 to 1.25, preferably 0.95 to 1.1. . In the present invention, the mole fraction (X) of the aromatic vinyl monomer unit and the mole fraction (Y) of the vinyl cyanide monomer unit are calculated by the following equations.

Mole fraction of aromatic vinyl monomer unit (X) = <number of moles of aromatic vinyl monomer unit in copolymer> / <mole of all monomer units contained in copolymer Sum of numbers>
Mole fraction of vinyl cyanide monomer units (Y) = <number of moles of vinyl cyanide monomer units in the copolymer> / <moles of all monomer units contained in the copolymer> Sum of numbers>
Further, (iii) the value of X / Y, which is the ratio of the molar fraction (X) of aromatic vinyl monomer units in the copolymer to the molar fraction (Y) of vinyl cyanide monomer units Is calculated using a Fourier transform infrared spectrophotometer (FTIR-8100A manufactured by Shimadzu Corporation) in the present invention, and is performed as follows.

  Aromatic vinyl monomers and vinyl cyanide monomers are mixed in various molar ratios, and infrared absorption spectra of these mixtures are measured. An infrared absorption spectrum calibration curve is created for the intensity ratio and molar ratio of a characteristic spectrum of vinyl cyanide monomer.

As a spectrum used when preparing an infrared absorption spectrum calibration curve, the present invention adopts a characteristic absorption peak (about 1495 cm ⁻¹ ) due to aromatic C═C in-plane vibration in an aromatic vinyl monomer, In the vinyl cyanide monomer unit, a characteristic absorption peak (about 2228 cm ⁻¹ ) due to the stretching vibration of the CN group was adopted.

These spectra show that in the copolymer (iii), in the aromatic vinyl monomer unit, the characteristic absorption peak (about 1495 cm ⁻¹ ) due to aromatic C═C in-plane vibration, vinyl cyanide monomer unit In the body unit, it can be confirmed as a peak of characteristic absorption (about 2238 cm ⁻¹ ) due to the stretching vibration of the CN group. (Iii) The infrared absorption spectrum of the copolymer is measured, and the aromatic vinyl monomer unit and The spectral intensity ratio of vinyl cyanide monomer units is derived.

  Next, using the prepared infrared absorption spectrum calibration curve, (iii) the ratio of the molar fraction of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit in the copolymer, X / The value of Y is calculated.

  The graft (co) polymer (A-1) and / or the vinyl (co) polymer (A-2) comprises at least an aromatic vinyl monomer unit and a vinyl cyanide monomer unit. In the case of deriving the molar ratio of the aromatic vinyl monomer unit and the vinyl cyanide monomer unit in each copolymer, the infrared absorption spectrum measurement was similarly performed, and the aromatic vinyl The intensity ratio of the spectrum of the monomer unit and the vinyl cyanide monomer unit is obtained and calculated by using an infrared absorption spectrum calibration curve.

  (iii) As the aromatic vinyl monomer used for the polymerization of the copolymer, styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, o-ethylstyrene, pt-butylstyrene, chlorostyrene, Examples include bromostyrene, and styrene is particularly preferable. These may be used alone or in combination of two or more.

  Examples of the vinyl cyanide monomer used for the polymerization of the copolymer (iii) include acrylonitrile, methacrylonitrile, ethacrylonitrile, and acrylonitrile is particularly preferable. These may be used alone or in combination of two or more.

  In the present invention, the α, β-unsaturated carboxylic acid monomer is not limited. For example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, Mesaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, methyl-1,2,3,6-tetrahydrophthalic acid, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid, 5 A monoalkyl ester of these dicarboxylic acids represented by norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid and monomethyl maleate, monoethyl maleate, and a metal salt of the above carboxylic acid, There are t-butyl (meth) acrylate, and acrylic acid and methacrylic acid are particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as another unsaturated monomer used for this invention, For example, (meth) methyl acrylate, (meth) acrylate ethyl, (meth) acrylate n-propyl, (meth) N-butyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( And (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2,3,4,5,6-pentahydroxyhexyl and (meth) acrylic acid 2,3,4,5-tetrahydroxypentyl, etc. , (Meth) acrylic acid, glycidyl (meth) acrylate, glycidyl ethacrylate, allyl glycidyl ether, styrene-p- Lysidyl ether, p-glycidyl styrene, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N- Propylmethacrylamide, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dibutyl (meth) acrylate Aminoethyl, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, -Vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline, etc. Among them, methyl (meth) acrylate, (meth) acrylic acid, N-methylmaleimide, and N-phenylmaleimide are preferably used, and methyl methacrylate and N-phenylmaleimide are particularly preferable. These may be used alone or in combination of two or more.

  There are no particular restrictions on the method of copolymerizing these monomers and obtaining the copolymer (iii), but the polymerization method is, for example, radical polymerization, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The known polymerization method can be used. In addition, regarding the charging method of each monomer at the time of polymerization, the molar fraction (X) of the aromatic vinyl monomer unit in the copolymer and the molar fraction of the vinyl cyanide monomer unit (Y ) Ratio and X / Y value within a range of 0.90 to 1.25 is not particularly limited, and may be added all at once in the initial stage. In order to prevent the formation of the polymer composition distribution, some or all of the charged monomers may be polymerized while continuously charged or dividedly charged. It is also possible to use a blend of two or more of the separately polymerized (iii) copolymers.

  (iii) The initial charge composition ratio of the aromatic vinyl-based monomer and the vinyl cyanide-based monomer before polymerization in producing the copolymer is the aromatic vinyl-based monomer unit in the copolymer. The ratio of the mole fraction (X) of the vinyl cyanide monomer unit to the mole fraction (Y) of the vinyl cyanide monomer unit, and (iii) a copolymer having an X / Y value in the range of 0.90 to 1.25 is obtained. For example, the aromatic vinyl monomer and the vinyl cyanide monomer in the charged mixture before polymerization <molar fraction of aromatic vinyl monomer> / The value of <molar fraction of vinyl cyanide monomer> is the same value as X / Y of the copolymer (iii) having the desired X / Y value, and the polymerization is close to 100%. (Iii) a copolymer having a desired X / Y value can be obtained. (Iii) During the production of the copolymer, the content in the polymerization system is sampled, and the modified vinyl copolymer produced by distilling off the solvent and residual monomer from the sampled content is isolated. . The polymer yield at the time of sampling is determined, and then the infrared absorption spectrum of the isolated modified vinyl copolymer is measured. For each monomer contained in the modified vinyl copolymer, prepare an infrared absorption spectrum calibration curve for the intensity ratio and molar ratio of the characteristic absorption peak in advance, and use this infrared absorption spectrum calibration curve. The molar ratio of each component unit in the modified vinyl copolymer at a certain polymer yield when sampled is derived. Thereby, the relationship between the polymer yield and the molar ratio of each component unit can be grasped, and the desired X / Y value is obtained by adjusting the polymer yield, the charging composition, and the charging method of each monomer ( iii) A copolymer can be obtained.

  The polymer yield (%) in the present invention is <weight of copolymer produced in the polymerization system> / <weight of all monomers charged> × 100.

  (iii) The intrinsic viscosity of the copolymer is not particularly limited, but the intrinsic viscosity measured at 30 ° C. after dissolving in a methyl ethyl ketone solvent is 0.2 to 1.2 dl / g and has impact resistance and molding processability. From the viewpoint of the balance, it is preferably 0.3 to 1.0 dl / g. (iii) The method for controlling the molecular weight of the copolymer is not particularly limited, and for example, generally known techniques can be applied. For example, controlled by the amount of radical polymerization initiators such as azo compounds and peroxides, or the amount of chain transfer agents such as alkyl mercaptans, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethylformamide, triethylamine, etc. can do. In particular, a method of controlling the amount of alkyl mercaptan added as a chain transfer agent can be preferably used from the viewpoint of stability of polymerization, ease of handling, and the like.

  Examples of the alkyl mercaptan used here include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, and t-dodecyl mercaptan is preferable. Used. Although there is no restriction | limiting in particular as addition amount of these alkyl mercaptans, Usually, it is 0.02-5.0 weight part with respect to 100 weight part of whole quantity of a monomer mixture, Preferably it is 0.03-4. 0 parts by weight.

  The preferred proportion of monomer units in these (iii) copolymers is the molar fraction of aromatic vinyl monomer units (X) and the molar fraction of vinyl cyanide monomer units (Y). As long as the value of X / Y which is the ratio of 0.90 to 1.25 is not particularly limited, the aromatic vinyl monomer unit is preferably 37.5 mol% to 54 mol%, More preferably, it is 40 mol% to 52 mol%, and the vinyl cyanide monomer unit is preferably 41 mol% to 53 mol%, more preferably 41.5 mol% to 49.5 mol%. The preferred ratio of the α, β-unsaturated carboxylic acid monomer unit in the (iii) copolymer is not particularly limited, but is preferably 0.1 to 30 mol%, more preferably 2 mol% to 20 The mol%, more preferably 4 mol% to 15 mol%, and most preferably 4.5 mol% to 12 mol%. In addition, when the amount of the (iii) α, β-unsaturated carboxylic acid monomer unit in the copolymer is less than 0.1 mol%, the impact resistance of the resulting resin composition tends to decrease. is there. On the other hand, when the amount of the α, β-unsaturated carboxylic acid monomer unit exceeds 30 mol%, the moldability tends to be lowered. (iii) The proportion of other monomer units or monomer mixture units in the copolymer is not particularly limited, but is preferably 0 to 21 mol%.

For the quantification of each component unit in the (iii) copolymer of the present invention, a quantification method using an infrared spectrophotometer is adopted in the present invention. (iii) The quantitative determination method of the α, β-unsaturated carboxylic acid monomer unit in the copolymer is carried out as follows. The α, β-unsaturated carboxylic acid monomer and aromatic vinyl monomer are mixed at various molar ratios, and the infrared absorption spectrum is measured to obtain the α, β-unsaturated carboxylic acid monomer and aromatic. An infrared absorption spectrum calibration curve for the peak intensity ratio and the molar ratio of the characteristic absorption with the aromatic vinyl monomer is prepared. Next, (iii) infrared absorption spectrum measurement of the copolymer is performed, and by using the prepared calibration curve, the reaction is added and (iii) an α, β-unsaturated carboxylic acid monomer contained in the copolymer The molar ratio between the unit and the aromatic vinyl monomer unit is calculated. Next, by calculating the molar ratio of the other component units of the copolymer (iii) with the aromatic vinyl monomer in the same manner, the moles of the α, β-unsaturated carboxylic acid monomer units are calculated. Calculate the fraction. The aromatic vinyl monomer exhibits a characteristic absorption peak (about 1495 cm ⁻¹ ) due to aromatic C═C in-plane vibration, and the α, β-unsaturated carboxylic acid monomer is due to stretching vibration of the carbonyl group. An infrared spectrum calibration curve was prepared using the characteristic absorption peak (about 1715 cm ⁻¹ ), and these characteristic absorption peaks were obtained from (iii) about 1495 cm ⁻¹ aromatic vinyl monomer units in the copolymer. In addition, the α, β-unsaturated carboxylic acid monomer unit is confirmed at about 1732 cm ⁻¹ .

  The thermoplastic resin composition of the present invention comprises (iii) 100 parts by weight of a resin composition comprising (i) 10 to 90% by weight of a rubber-reinforced styrene resin and (ii) 90 to 10% by weight of a polyamide resin. ) Copolymer 0.5-60 parts by weight is further contained. In the above resin composition, (i) if the rubber-reinforced styrene resin is less than 10% by weight, the impact resistance and dimensional stability of the final composition are not sufficient, and if it exceeds 90% by weight, the chemical resistance of the final composition is insufficient. Is low. On the other hand, (ii) when the polyamide resin is less than 10% by weight, the chemical resistance of the final composition is not sufficient, and when it exceeds 90% by weight, the dimensional stability of the molded product is poor and the water absorption is increased. In addition, the ratio of (iii) copolymer in the total resin composition is 0.5 to 60% by weight with respect to 100 parts by weight of the resin composition comprising (i) rubber-reinforced styrene resin and (ii) polyamide resin. If the copolymer (iii) is less than 0.5 parts by weight, the effect of addition as a compatibilizing agent is poor, and the impact resistance of the resulting composition is poor. When it exceeds 60 parts by weight, the moldability of the final composition is lowered. (iii) A preferable addition ratio of the copolymer is 1 to 30 parts by weight, and more preferably 2 to 25 parts by weight.

  Regarding the method for producing the thermoplastic resin composition of the present invention, for example, (i) a rubber-reinforced styrene resin, (ii) a polyamide resin, and (iii) a copolymer in a pellet, powder, strip state, etc. And then kneading using a Banbury mixer or rubber roll machine, and a melt kneading method using a uniaxial or multiaxial extruder having sufficient kneading ability and a vent heated to 220-300 ° C. A method etc. can be adopted. The mixing order and state of (i) rubber reinforced styrene resin, (ii) polyamide resin and (iii) copolymer are not limited, and (i) rubber reinforced styrene resin, (ii) polyamide resin. And (iii) batch co-mixing of the copolymer, and a method of mixing the components remaining after pre-mixing specific two components.

  The thermoplastic resin composition of the present invention comprises (i) a rubber-reinforced styrene resin and (ii) a polyamide resin, as required, such as polymethyl methacrylate, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polylactic acid, etc. Mixing thermoplastic resin as appropriate, polypropylene, ethylene / propylene copolymer, ethylene / propylene / diene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer Polypropylene rubber such as coalescence and acid or acid anhydride modified rubber of the polypropylene rubber, ethylene, ethylene / butene-1 copolymer, ethylene / vinyl acetate copolymer, ethylene / butyl acrylate copolymer, ethylene / Acrylic acid, ethylene / butyl acrylate Polyethylene / maleic anhydride copolymer, polyethylene rubber such as ethylene / methyl methacrylate / monomethyl maleate, ethylene / methyl methacrylate / monoethyl maleate, polybutyl acrylate, butyl acrylate / allyl acrylate copolymer, By suitably mixing acrylic rubber such as acrylic acid / butyl acrylate copolymer, it is possible to adjust to more preferable physical properties and characteristics.

  Moreover, the thermoplastic resin composition of the present invention can greatly improve strength, rigidity, heat resistance, and the like by further adding a filler.

  Such fillers may be fibrous or non-fibrous, such as granules. Specific examples thereof include glass fibers, carbon fibers, metal fibers, aramid fibers, asbestos, potassium titanate whiskers, straws. Examples include stenite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.

  These addition amounts differ depending on the type of filler, and thus cannot be defined unconditionally. However, (i) the rubber-reinforced styrene resin, (ii) the polyamide resin, and (iii) the copolymer together with 100 parts by weight, The amount is preferably 1 to 150 parts by weight, particularly preferably 10 to 100 parts by weight.

  Further, the thermoplastic resin composition of the present invention can contain a conductive filler and / or a conductive polymer in order to impart conductivity. The material is not particularly limited, but the conductive filler is not particularly limited as long as it is a conductive filler that is usually used for conductive resin. Specific examples thereof include metal powder, metal flakes, and metal ribbons. , Metal fiber, metal oxide, inorganic filler coated with a conductive substance, carbon powder, graphite, carbon fiber, carbon flake, scaly carbon, and the like.

  Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

  Specific examples of the metal species of the metal fiber include iron, copper, stainless steel, aluminum, and brass. Such metal powders, metal flakes, metal ribbons, and metal fibers may be subjected to surface treatment with a surface treatment agent such as titanate, aluminum, or silane.

Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope), ZnO (aluminum dope), etc., and these are the surface of titanate, aluminum, silane coupling agents, etc. Surface treatment may be performed with a treating agent.

Specific examples of the conductive material in the inorganic filler coated with the conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped), and In ₂ O ₃ (antimony doped). Examples of the inorganic filler to be coated include mica, glass beads, glass fiber, carbon fiber, potassium titanate whisker, barium sulfate, zinc oxide, titanium oxide, aluminum borate whisker, zinc oxide whisker, titanic acid whisker, carbonized. Examples include silicon whiskers. Examples of the coating method include vacuum deposition, sputtering, electroless plating, and baking. These may be surface-treated with a surface treatment agent such as a titanate, aluminum or silane coupling agent.

  Carbon powders are classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc., depending on the raw materials and production method. The carbon powder that can be used in the present invention is not particularly limited in its raw material and production method, but acetylene black and furnace black are particularly preferably used. Various carbon powders having different characteristics such as particle diameter, surface area, and ash content are produced. The carbon powder that can be used in the present invention is not particularly limited in these properties, but the average particle size is preferably 500 nm or less, more preferably 5 to 100 nm, particularly preferably from the viewpoint of balance between strength and electrical conductivity. 10-70 nm. Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane. It is also possible to use a granulated product to improve melt kneading workability.

  Specific examples of the conductive polymer include polyaniline, polypyrrole, polyacetylene, poly (paraphenylene), polythiophene, polyphenylene vinylene and the like.

  Two or more kinds of the conductive filler and / or conductive polymer may be used in combination. Among these conductive fillers and conductive polymers, carbon black is particularly preferably used in terms of strength and economy.

  Although the content of the conductive filler and / or conductive polymer used in the present invention varies depending on the type of conductive filler and / or conductive polymer used, it cannot be specified unconditionally. However, conductivity, fluidity, and mechanical strength are not possible. From the viewpoint of balance with the above, the amount is preferably 1 to 250 parts by weight, particularly preferably 3 to 100 parts by weight in total of (i) rubber-reinforced styrene resin, (ii) polyamide resin and (iii) copolymer. It is in the range of ˜100 parts by weight. However, the blending of the conductive filler and conductive polymer generally tends to cause deterioration of strength and fluidity. Therefore, if the target conductivity level is obtained, it is desirable that the amount of the conductive filler and the conductive polymer is as small as possible.

  In addition, the thermoplastic resin composition of the present invention includes other components such as antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites, and substituted products thereof as long as the effects of the present invention are not impaired. Etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents (stearamide, ethylene wax, etc.), lubricants (higher fatty acids such as montanic acid and their metal salts, esters thereof) , Its half esters, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene wax, higher alcohols, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black etc.), dyes (eg nigrosine etc.), phosphites, hypophosphorous acid Anti-coloring agents such as acid salts, crystal nucleating agents (t , Silica, kaolin, clay, etc.), plasticizer (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agent (alkyl sulfate type anionic antistatic agent, quaternary ammonium salt type cationic charging) Nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, etc.) Oxide flame retardant, phosphorus flame retardant such as ammonium polyphosphate and triphenyl phosphate, silicone non-halogen flame retardant, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, decabromo Halogen flame retardants such as diphenyl oxide, or these Combination of androgenic flame retardant and antimony trioxide), may be added to other polymers.

  The thermoplastic resin composition of the present invention is excellent in rigidity, heat resistance, chemical resistance, surface appearance, particularly impact resistance at room temperature and low temperature, and also has excellent fluidity. The present invention can be used for various molded articles, and particularly useful for automobile interior / exterior materials and molded articles around housings and parts of electric / electronic devices.

  Hereinafter, the configuration and effects of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Prior to the description of each example, various physical property measurement methods employed in the example will be described.

  Izod impact strength: Notched Izod impact strength was measured according to ASTM D256 using an injection molded product having a thickness of 1/8 inch. The impact strength measurement was performed at normal temperature (23 ° C.) and low temperature (−30 ° C.).

  Flexural modulus: measured according to ASTM D-790.

Heat resistance: The deflection temperature under load (HDT) was measured at a load of 4.6 kgf / cm ² using an injection molded product having a thickness of 1/4 inch according to ASTM D-648 (no annealing).

  Flowability: According to JIS K7210 B method, the melt flow rate was measured at a load of 10 kgf and at a temperature of (ii) melting point of polyamide resin used + 25 ° C.

  Chemical resistance: As shown in FIG. 1, after the injection-molded strip-shaped test piece 2 (129 mm × 12.6 mm × 1.5 mm) is fixed along the 1/4 elliptical jig 1, After applying a chemical solution and leaving it in a 23 ° C. environment for 24 hours, the presence or absence of crazing and cracking was confirmed, and the critical strain (%) was calculated from the following formula (1). Methanol and gasoline were used as chemicals.

ε: Critical strain (%)
a: Long axis of jig (mm) [123 mm]
b: Minor axis of jig (mm) [47mm]
t: Test piece thickness (mm) [1.5 mm]
X: Long axis direction length of the crack occurrence point (mm)
Layered peeling prevention: For the evaluation of layered peeling prevention, an injection-molded ASTM D-638 No. 1 dumbbell was broken and the state of the fracture surface was visually observed. Judgment criteria were: ○: good, Δ: slightly bad, x: extremely bad.

[Reference Example 1]
<(I) Rubber reinforced styrene resin>
(1) Preparation of (A-1) graft copolymer (a-1):
The following substances were charged into a polymerization vessel and heated to 65 ° C. with stirring. When the internal temperature reached 65 ° C., polymerization was started, and 40 parts by weight of a mixture comprising 73 parts by weight of styrene, 27 parts by weight of acrylonitrile and 0.3 parts by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours.
Polybutadiene latex (weight average particle diameter 0.2 μm): 60 parts by weight (in terms of solid content)
Potassium oleate: 0.5 parts by weight Glucose: 0.5 parts by weight Sodium pyrophosphate: 0.5 parts by weight Ferrous sulfate: 0.005 parts by weight Deionized water: 120 parts by weight In parallel, cumene hydroperoxide 0 An aqueous solution comprising 25 parts by weight, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously added dropwise over 7 hours to complete the reaction. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a graft copolymer (a-1). The composition determined by infrared absorption spectrum measurement of the graft copolymer (a-1) was 58.0 mol% of styrene units and 42.0 mol% of acrylonitrile units, and the graft copolymer (a-1) The molar ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit is 1.38.

  Acetone was added to a predetermined amount (m) of this graft copolymer (a-1) and refluxed for 4 hours. This solution was centrifuged at 8800 rpm (centrifugal force 10,000 G) for 40 minutes, and then the insoluble matter was filtered. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, then the weight (n) was measured, and the graft ratio = [(n) − (m) × L] / [(m) × L] × 100 was calculated. The grafting rate was 37%. Here, L is the rubber content of the graft copolymer.

The filtrate of the acetone solution was concentrated with a rotary evaporator to obtain a precipitate (acetone soluble matter). This soluble matter was dried under reduced pressure at 70 ° C. for 5 hours, adjusted to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.40 dl / g. there were.
(2) Preparation of (A-1) graft copolymer (a-2):
The following substances were charged into a polymerization vessel and heated to 65 ° C. with stirring. When the internal temperature reached 65 ° C., polymerization was started, and 58 parts by weight of a mixture composed of 73 parts by weight of styrene, 27 parts by weight of acrylonitrile and 0.3 parts by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours.
Polybutadiene latex (weight average particle diameter 0.2 μm): 42 parts by weight (in terms of solid content)
Potassium oleate: 0.5 parts by weight Glucose: 0.5 parts by weight Sodium pyrophosphate: 0.5 parts by weight Ferrous sulfate: 0.005 parts by weight Deionized water: 120 parts by weight In parallel, cumene hydroperoxide 0 An aqueous solution comprising 25 parts by weight, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously added dropwise over 7 hours to complete the reaction.

The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a graft copolymer (a-2). The composition determined by infrared absorption spectrum measurement of the graft copolymer (a-2) was 57.9 mol% of styrene units and 42.1 mol% of acrylonitrile units, and the graft copolymer (a-2) The molar ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit is 1.38. The graft ratio calculated by the same method as that for the graft copolymer (a-1) was 48%, and the intrinsic viscosity was 0.46 dl / g.
(3) Preparation of (A-1) graft copolymer (a-3):
A powdery graft copolymer (a-3) was prepared in the same manner as the method for producing the graft copolymer (a-1) except that the charged monomers were changed to 66 parts by weight of styrene and 34 parts by weight of acrylonitrile.

The composition obtained by measuring the infrared absorption spectrum of this graft copolymer (a-3) was 50.0 mol% of styrene units and 50.0 mol% of acrylonitrile units, and vinyl copolymer (a-3). The molar ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit in) is 1.00. The graft ratio calculated by the same method as that for the graft copolymer (a-1) was 37%, and the intrinsic viscosity was 0.41 dl / g.
(4) Preparation of (A-2) vinyl copolymer (a-4):
80 parts by weight of acrylamide, 20 parts by weight of methyl methacrylate, 0.3 parts by weight of potassium persulfate, and 1500 parts by weight of ion-exchanged water were charged into the reactor, and the gas phase in the reactor was replaced with nitrogen gas and stirred at 70 ° C. Kept. The reaction was continued until the monomer was completely converted to a polymer and was obtained as an aqueous solution of acrylamide and methyl methacrylate binary copolymer. Dilution with ion-exchanged water gave a solution in which 0.05 part of methyl methacrylate / acrylamide copolymer was dissolved in 165 parts of ion-exchanged water.

A solution prepared by dissolving 0.05 parts of the obtained methyl methacrylate / acrylamide copolymer in 165 parts of ion-exchanged water in a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade was stirred at 400 rpm. The inside of the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate suspension polymerization.
Styrene: 73 parts by weight Acrylonitrile: 27 parts by weight t-dodecyl mercaptan: 0.2 parts by weight 2,2′-azobisisobutyronitrile: 0.4 parts by weight The reaction temperature was raised to 65 ° C. over 15 minutes. Thereafter, the temperature was raised to 90 ° C. over 2 hours, and the polymerization was terminated while maintaining 90 ° C. for 2 hours. The reaction system was cooled, the polymer was separated, washed, and dried to obtain a bead-like vinyl copolymer (a-4). The polymer yield was 96%.

The composition obtained by measuring the infrared absorption spectrum of this vinyl copolymer (a-4) was 58.1 mol% of styrene units and 41.9 mol% of acrylonitrile units, and the vinyl copolymer (a- In 4), the molar ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit is 1.39. This copolymer was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured using an Ubbelohde viscometer was 0.51 dl / g.
(5) (A-2) Vinyl copolymer (a-5)
The same methyl methacrylate / acrylamide copolymer 0.05 used in the preparation of the vinyl copolymer (a-4) in a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade. A solution prepared by dissolving 165 parts in ion-exchanged water was stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate suspension polymerization.
Styrene: 67 parts by weight Acrylonitrile: 33 parts by weight t-dodecyl mercaptan: 0.3 part by weight 2,2′-azobisisobutyronitrile: 0.4 part by weight The reaction temperature was raised to 65 ° C. over 15 minutes. Thereafter, the temperature was raised to 90 ° C. over 3 hours, and the polymerization was terminated while maintaining 90 ° C. for 3 hours. The reaction system was cooled, the polymer was separated, washed, and dried to obtain a bead-like vinyl copolymer (a-5). The polymer yield was 97%.

  The composition obtained by measuring the infrared absorption spectrum of this vinyl copolymer (a-5) was 50.2 mol% of styrene units and 49.8 mol% of acrylonitrile units, and the vinyl copolymer (a- The molar ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit in 5) is 1.01. This copolymer was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured using an Ubbelohde viscometer was 0.51 dl / g.

<(Iii) Copolymer>
(6) (iii) Preparation of copolymer (c-1) In a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a fiddle-type stirring blade, the vinyl copolymer (a-4) was prepared. A solution prepared by dissolving 0.05 part of the same methyl methacrylate / acrylamide copolymer as used in 165 parts of ion-exchanged water was stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate suspension polymerization.
Styrene: 64.0 parts by weight Acrylonitrile: 31.0 parts by weight Methacrylic acid: 5.0 parts by weight t-dodecyl mercaptan: 0.3 parts by weight 2,2′-azobisisobutyronitrile: 0.3 parts by weight 15 After raising the reaction temperature to 65 ° C. over a period of time, the temperature was raised to 90 ° C. over 2 hours and maintained at 90 ° C. for 2 hours to complete the polymerization. Next, separation, washing and drying of the polymer were carried out to obtain a bead-like (iii) copolymer (c-1). The polymer yield was 97%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 48.8 mol% of styrene units, 46.5 mol% of acrylonitrile units, and 4.7 mol% of methacrylic acid. Met. (iii) The ratio of the molar fraction (X) of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit (Y) in the copolymer (c-1) is X / Y = 1.05. Further, (iii) the copolymer (c-1) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.55 dl / g. It was.
(7) (iii) Preparation of copolymer (c-2) 43.0 parts by weight of styrene, 32.0 parts by weight of acrylonitrile, 3.0 parts by weight of methacrylic acid, 0.2 part by weight of t-dodecyl mercaptan, A stainless steel autoclave equipped with a baffle containing 80 parts by weight of methyl ethyl ketone and 0.3 parts by weight of 2′-azobisisobutyronitrile was charged into a stainless steel autoclave, and the temperature was raised to 80 ° C. while stirring the solution at 400 rpm. The temperature rose. Next, a solution obtained by dissolving 20.0 parts by weight of styrene, 2.0 parts by weight of methacrylic acid, and 0.1 parts by weight of 2,2′-azobisisobutyronitrile in 25 parts by weight of methyl ethyl ketone was continuously added in 5 hours. did. After the addition, the temperature was further maintained at 80 ° C. for 3 hours to complete the polymerization. After cooling, the solution was poured into 5 equivalents of methanol, purified by reprecipitation, and the solvent was completely distilled off by drying to obtain (iii) copolymer (c-2).

The polymer yield was 95%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 47.7 mol% of styrene units, 47.6 mol% of acrylonitrile units, and 4.7 mol% of methacrylic acid units. It was a thing. (iii) The ratio of the molar fraction (X) of the aromatic vinyl monomer unit to the molar fraction (Y) of the vinyl cyanide monomer unit of the copolymer (c-2) is X / Y = 1.00. In addition, (iii) copolymer (c-2) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.70 dl / g. It was.
(8) (iii) Preparation of copolymer (c-3) 41.4 parts by weight of styrene, 32.6 parts by weight of acrylonitrile, 4.0 parts by weight of methacrylic acid, 0.25 parts by weight of t-dodecyl mercaptan, A stainless steel autoclave equipped with a baffle containing 80 parts by weight of methyl ethyl ketone and 0.3 parts by weight of 2′-azobisisobutyronitrile was charged into a stainless steel autoclave, and the temperature was raised to 80 ° C. while stirring the solution at 400 rpm. The temperature rose. Next, a solution prepared by dissolving 20 parts by weight of styrene, 2.0 parts by weight of methacrylic acid, and 0.1 parts by weight of 2,2′-azobisisobutyronitrile in 20 parts by weight of methyl ethyl ketone was continuously added in 6 hours. After the addition, the temperature was further maintained at 80 ° C. for 3 hours to complete the polymerization. After cooling, the solution was poured into 5-fold equivalent of methanol, purified by reprecipitation, and the solvent was completely distilled off by drying to obtain (iii) copolymer (c-3).

The polymer yield was 97%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 46.1 mol% of styrene units, 48.1 mol% of acrylonitrile units, and 5.8 mol% of methacrylic acid units. It was a thing. (iii) The ratio of the molar fraction (X) of the aromatic vinyl monomer units to the molar fraction (Y) of the vinyl cyanide monomer units in the copolymer (c-3) is X / Y = 0.96. In addition, (iii) copolymer (c-3) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.65 dl / g. It was.
(9) (iii) Preparation of copolymer (c-4) Styrene 65.5 parts by weight, acrylonitrile 29.5 parts by weight, methacrylic acid 5.0 parts by weight, t-dodecyl mercaptan 0.3 parts by weight, 2, A bead-like (iii) copolymer (c-) is produced in the same manner as in the production method of the copolymer (c-1) except that the amount is changed to 0.4 parts by weight of 2'-azobisisobutyronitrile. 4) was prepared.

The polymer yield was 98%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 50.8 mol% of styrene units, 44.4 mol% of acrylonitrile units, and 4.8 mol% of methacrylic acid units. It was a thing. (iii) The ratio of the molar fraction (X) of the aromatic vinyl monomer units of the copolymer (c-4) to the molar fraction (Y) of the vinyl cyanide monomer units is X / Y = 1.14. In addition, (iii) copolymer (c-4) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.55 dl / g. It was.
(10) (iii) Preparation of copolymer (c-5) Styrene 56 parts by weight, acrylonitrile 27.5 parts by weight, methyl methacrylate 12 parts by weight, methacrylic acid 4.5 parts by weight, t-dodecyl mercaptan 0.35 (Iii) The bead-like (iii) co-polymer is produced in the same manner as the production method of the copolymer (c-1) except that the weight is changed to 0.4 part by weight of 2,2′-azobisisobutyronitrile. A polymer (c-5) was prepared.

The polymer yield was 98%. The composition determined by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve was 41.1 mol% of styrene units, 44.6 mol% of acrylonitrile units, 10.0 mol% of methyl methacrylate units, methacrylic units. The acid unit contained 4.3 mol%. (iii) The ratio of the molar fraction (X) of the aromatic vinyl monomer units of the copolymer (c-5) to the molar fraction (Y) of the vinyl cyanide monomer units is X / Y = 0.92. Further, (iii) the copolymer (c-5) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.42 dl / g. It was.
(11) (iii) Preparation of copolymer (c-6) 12.9 parts by weight of α-methylstyrene, 50.1 parts by weight of styrene, 31.0 parts by weight of acrylonitrile, 3.5 parts by weight of methacrylic acid, t- A solution of 0.35 part by weight of dodecyl mercaptan and 0.3 part by weight of 2,2′-azobisisobutyronitrile was charged into a stainless steel autoclave equipped with a baffle containing 100 parts by weight of methyl ethyl ketone and a fudra-type stirring blade. The temperature was raised to 80 ° C. with stirring at 400 rpm. Next, a solution prepared by dissolving 2.5 parts of methacrylic acid and 0.1 parts by weight of 2,2′-azobisisobutyronitrile in 15 parts by weight of methyl ethyl ketone was continuously added in 5 hours. After the addition, the temperature was further maintained at 80 ° C. for 3 hours to complete the polymerization. After cooling, the solution was poured into 5 equivalents of methanol, purified by reprecipitation, and the solvent was completely distilled off by drying to obtain (iii) copolymer (c-6).

The polymer yield was 96%. The composition determined by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve was 9.6 mol% α-methylstyrene unit, 38.3 mol% styrene unit, 46.4 mol% acrylonitrile unit, The methacrylic acid unit contained 5.7 mol%. (iii) The ratio of the molar fraction (X) of the aromatic vinyl monomer units of the copolymer (c-6) to the molar fraction (Y) of the vinyl cyanide monomer units is X / Y = 1.03. Further, (iii) the copolymer (c-6) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.44 dl / g. It was.
(12) (iii) Preparation of copolymer (c-7) 64.0 parts by weight of styrene, 30.8 parts by weight of acrylonitrile, 5.2 parts by weight of acrylic acid, 0.25 parts by weight of t-dodecyl mercaptan, A bead-like (iii) copolymer (c-) is produced in the same manner as in the production method of the copolymer (c-1) except that the amount is changed to 0.4 parts by weight of 2'-azobisisobutyronitrile. 7) was prepared.

The polymer yield was 98%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 48.1 mol% of styrene units, 47.2 mol% of acrylonitrile units, and 4.7 mol% of acrylic acid units. It was a thing. (iii) The ratio of the molar fraction (X) of the aromatic vinyl monomer unit of the copolymer (c-7) to the molar fraction (Y) of the vinyl cyanide monomer unit is X / Y = 1.02. Further, (iii) the copolymer (c-7) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.64 dl / g. It was.
(13) Preparation of copolymer (c-8) Styrene 73.7 parts by weight, acrylonitrile 21.3 parts by weight, methacrylic acid 5.0 parts by weight, t-dodecyl mercaptan 0.28 parts by weight, 2,2'- A bead-shaped copolymer (c-8) was prepared in the same manner as in the production method of the copolymer (c-1) except that the amount was changed to 0.35 parts by weight of azobisisobutyronitrile.

The polymer yield was 97%. The composition determined by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 60.0 mol% of styrene units, 35.3 mol% of acrylonitrile units, and 4.7 mol% of methacrylic acid units. It was a thing. The ratio of the molar fraction (X) of the aromatic vinyl monomer units of the copolymer (c-8) to the molar fraction (Y) of the vinyl cyanide monomer units is X / Y = 1. 70. The intrinsic viscosity of the copolymer (c-8) prepared at 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.) and measured at 30 ° C. using an Ubbelohde viscometer was 0.58 dl / g.
(14) Preparation of copolymer (c-9) 71.3 parts by weight of styrene, 23.7 parts by weight of acrylonitrile, 5.0 parts by weight of methacrylic acid, 0.40 parts by weight of t-dodecyl mercaptan, 2,2′- A bead-shaped copolymer (c-9) was prepared in the same manner as in the production method of the copolymer (c-1) except that the amount was changed to 0.35 parts by weight of azobisisobutyronitrile.

The polymer yield was 96%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 57.5 mol% of styrene units, 37.8 mol% of acrylonitrile units, and 4.7 mol% of methacrylic acid units. It was a thing. The ratio of the molar fraction (X) of the aromatic vinyl monomer units of the copolymer (c-9) to the molar fraction (Y) of the vinyl cyanide monomer units is X / Y = 1. 52. The intrinsic viscosity of the copolymer (c-9) prepared at 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.) and measured at 30 ° C. using an Ubbelohde viscometer was 0.48 dl / g.
(15) Preparation of copolymer (c-10) Styrene 38.1 parts by weight, acrylonitrile 36.9 parts by weight, methacrylic acid 3.0 parts by weight, t-dodecyl mercaptan 0.3 parts by weight, 2,2'- A stainless steel autoclave equipped with a baffle containing 80 parts by weight of methylethylketone and 80 parts by weight of methyl ethyl ketone was charged into a stainless steel autoclave, and the temperature was raised to 80 ° C. while stirring the solution at 400 rpm. . Next, a solution prepared by dissolving 20.5 parts by weight of styrene, 1.5 parts by weight of methacrylic acid, and 0.05 parts by weight of 2,2′-azobisisobutyronitrile in 30 parts by weight of methyl ethyl ketone was continuously added over 7 hours. did. After the addition, the temperature was further maintained at 80 ° C. for 3 hours to complete the polymerization. After cooling, the solution was poured into 5 equivalents of methanol, purified by reprecipitation, and the solvent was completely distilled off by drying to obtain a copolymer (c-10).

  The polymer yield was 95%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 42.8 mol% of styrene units, 52.9 mol% of acrylonitrile units, and 4.3 mol% of methacrylic acid units. It was a thing. The ratio of the molar fraction (X) of the aromatic vinyl monomer units of the copolymer (c-10) to the molar fraction (Y) of the vinyl cyanide monomer units is X / Y = 0. 81. The intrinsic viscosity of the copolymer (c-10) prepared at 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.) and measured at 30 ° C. using an Ubbelohde viscometer was 0.55 dl / g.

<(Ii) Polyamide resin>
(ii) Polyamide resin (b-1): Nylon 6 having a melting point of 225 ° C. and a relative viscosity of 2.3 at 25 ° C. in a solution of 1 g / dl in 98% concentrated sulfuric acid.
(ii) Polyamide resin (b-2): Nylon 6 having a melting point of 225 ° C. and a relative viscosity of 2.7 at 25 ° C. at a concentration of 1 g / dl in 98% concentrated sulfuric acid.
(ii) Polyamide resin (b-3): Nylon 66 having a melting point of 260 ° C. and a relative viscosity of 2.4 at 25 ° C. in a solution of 1 g / dl in 98% concentrated sulfuric acid.
(ii) Polyamide resin (b-4): Nylon 6 component and nylon having a melting point of 210 ° C. and a relative viscosity of 2.7 at 25 ° C. in a solution of 1 g / dl in 98% concentrated sulfuric acid. A copolymer comprising 66 components.
Polyamide resin (b-5): Nylon 6 having a melting point of 225 ° C. and a relative viscosity of 4.2 at 25 ° C. in a solution of 1 g / dl in 98% concentrated sulfuric acid.

Examples 1-9
(I) Rubber reinforced polystyrene resin prepared in Reference Example 1, (ii) Polyamide resin, and (iii) Copolymer prepared in Reference Example 1 were mixed at the compounding ratio shown in Table 1, and the screw diameter was 30 mm, L Pellets were produced by melt kneading and extruding at a resin temperature of 250 ° C. and a screw rotation speed of 150 rpm in a same-direction rotating twin screw extruder (PCM-30 manufactured by Ikekai Tekko Co., Ltd.) having a / D of 25.
Each pellet was subjected to injection molding under the conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare each test piece, and the physical properties of the test piece were evaluated. These results are shown in Table 1.

Comparative Examples 1-6
(I) rubber reinforced polystyrene resin prepared in Reference Example 1, (ii) polyamide resin and (iii) copolymer (c-1), copolymer (c-8), (c) prepared in Reference Example 1 -9) and (c-10) were mixed at the blending ratio shown in Table 1, and the resin temperature was 250 using a co-rotating twin-screw extruder (PCM-30 manufactured by Ikegai Iron Works) with a screw diameter of 30 mm and L / D of 25. Pellets were produced by melt kneading and extruding at a temperature of 150 ° C. and a screw rotation speed of 150 rpm. Each pellet was subjected to injection molding under the conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare each test piece, and the physical properties of the test piece were evaluated. These results are shown in Table 1.

Examples 10-17, 19
(I) Rubber reinforced polystyrene resin prepared in Reference Example 1, (ii) Polyamide resin, and (iii) Copolymer prepared in Reference Example 1 were mixed in the mixing ratio shown in Table 2, and the screw diameter was 30 mm, L Pellets were produced by melt kneading and extruding at a resin temperature of 250 ° C. and a screw rotation speed of 150 rpm in a same-direction rotating twin screw extruder (PCM-30 manufactured by Ikekai Tekko Co., Ltd.) having a / D of 25. Each pellet was subjected to injection molding under the conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare each test piece, and the physical properties of the test piece were evaluated. These results are shown in Table 2.

Example 18 and Comparative Example 12
Table 2 shows (i) rubber-reinforced polystyrene resin prepared in Reference Example 1, (ii) polyamide resin and (iii) copolymer (c-1) and copolymer (c-8) prepared in Reference Example 1. Were mixed at the blending ratio shown in FIG. 1 and melt-kneaded and extruded at a resin temperature of 280 ° C. and a screw rotation speed of 150 rpm using a co-rotating twin screw extruder (PCM-30, manufactured by Ikekai Tekko) with a screw diameter of 30 mm and an L / D of 25. Pellets were produced by doing. Each pellet was subjected to injection molding under the conditions of a molding temperature of 280 ° C. and a mold temperature of 70 ° C. to prepare each test piece, and the physical properties thereof were evaluated. These results are shown in Table 2.

Comparative Examples 7-11
(I) Rubber reinforced polystyrene resin prepared in Reference Example 1, (ii) Polyamide resin and copolymers (c-8) and (c-9) prepared in Reference Example 1 were blended at the compounding ratios shown in Table 2. Pellets are produced by mixing, melt kneading and extruding at a resin temperature of 250 ° C. and a screw rotation speed of 150 rpm with a co-rotating twin screw extruder (PCM-30 manufactured by Ikekai Tekko Co., Ltd.) having a screw diameter of 30 mm and an L / D of 25. did. Each pellet was subjected to injection molding under the conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare each test piece, and the physical properties of the test piece were evaluated. These results are shown in Table 2.

  From the examples and comparative examples, the following is clear.

  From Table 1, the ratio of the molar fraction of the aromatic vinyl monomer units to the molar fraction of the vinyl cyanide monomer units is within a specific range in the present invention (iii) Implementation in which a copolymer was added For the resin compositions of Examples 1 to 9, a copolymer having a ratio of the molar fraction of aromatic vinyl monomer units different from that of the present invention to the molar fraction of vinyl cyanide monomer units was used. Compared to the resin compositions of Comparative Examples 1 to 5, it can be seen that the resin composition is excellent in rigidity, heat resistance, chemical resistance and delamination prevention, and particularly excellent in impact resistance and fluidity. In addition, the resin compositions of Examples 1 to 9 use (iii) a copolymer in addition to (iii) a copolymer, and further use (ii) a polyamide resin whose relative viscosity is in a specific range defined in the present invention. Therefore, compared with the resin compositions of Comparative Examples 5 and 6 using a polyamide resin whose relative viscosity is not in the specific range defined in the present invention, it is excellent in impact resistance, rigidity, chemical resistance, and delamination prevention, It can be seen that in addition to the above characteristics, the fluidity is particularly excellent.

  From Table 2, the ratio of the molar fraction of the aromatic vinyl monomer units to the molar fraction of the vinyl cyanide monomer units is within a specific range in the present invention (iii) Implementation in which a copolymer was added The resin compositions of Examples 10 to 17 and 19 are copolymers having a ratio of the molar fraction of aromatic vinyl monomer units different from that of the present invention to the molar fraction of vinyl cyanide monomer units. Compared to the resin compositions of Comparative Examples 7 to 11 used, it can be seen that the balance of rigidity, heat resistance, fluidity, and chemical resistance is excellent, and in particular, excellent in impact resistance and delamination prevention. Further, from Example 18 and Comparative Example 12, when (66) nylon 66 is used as the polyamide resin, the resin composition to which the copolymer (iii) of the present invention is added does not cause delamination, and is rigid and heat resistant. It can be seen that it has excellent properties, fluidity, and delamination prevention properties, and particularly excellent impact resistance.

  From the above, the value of X / Y, which is the ratio of the molar fraction (X) of aromatic vinyl monomer units in the copolymer to the molar fraction (Y) of vinyl cyanide monomer units, is 0. The thermoplastic resin composition of the present invention in which (iii) a copolymer of 90 to 1.25 is added, and the relative viscosity of the polyamide resin used as a component is defined within a specific range has a value of X / Y and Compared with a thermoplastic resin composition in which the relative viscosity of the polyamide resin is not within the specific range specified in the present invention, delamination does not occur, and a high balance of rigidity, heat resistance, and chemical resistance is achieved. It can be seen that it has excellent impact resistance and fluidity at room temperature and low temperature.

  It is possible to provide a thermoplastic resin composition useful as an automobile interior / exterior material or a housing / part surrounding material of an electric / electronic device.

The schematic plan view of the 1/4 ellipse jig used for a chemical-resistance test is shown.

Explanation of symbols

1: Jig 2: Specimen a: Jig long axis b: Jig short axis t: Specimen thickness X: Longitudinal length of crack occurrence point

Claims (11)

(i) 5 to 100% by weight of a graft (co) polymer (A-1) obtained by graft polymerization of a monomer or a monomer mixture containing an aromatic vinyl monomer to a rubber polymer; Rubber-reinforced styrenic resin 10 to 90 comprising 0 to 95% by weight of vinyl (co) polymer (A-2) obtained by polymerizing a monomer or monomer mixture containing an aromatic vinyl monomer And (ii) a resin composition comprising 10 to 90% by weight of a polyamide resin having a relative viscosity of 2.0 to 4.0 at 25 ° C. dissolved in 98% concentrated sulfuric acid at a concentration of 1 g / dl. For 100 parts by weight
(iii) Modified vinyl copolymer (B-1) obtained by polymerizing aromatic vinyl monomer, vinyl cyanide monomer, α, β-unsaturated carboxylic acid monomer, and aromatic vinyl Modified vinyl copolymer (B-2) obtained by polymerizing a monomer, a vinyl cyanide monomer, an α, β-unsaturated carboxylic acid monomer and / or another unsaturated monomer A thermoplastic resin composition further containing 0.5 to 60 parts by weight of a copolymer selected from: and (iii) a mole fraction of aromatic vinyl monomer units in the copolymer (X) and (iii) X / Y, which is the ratio of molar fraction (Y) of vinyl cyanide monomer units in the copolymer, is 0.90 to 1.25, A thermoplastic resin composition. The graft (co) polymer (A-1) is 10 to 80 parts by weight of diene rubber, 40 to 95% by weight of aromatic vinyl monomer, 5 to 60% by weight of vinyl cyanide monomer, and The thermoplastic resin composition according to claim 1, obtained by grafting 20 to 90 parts by weight of a monomer mixture comprising 0 to 30% by weight of a copolymerizable vinyl monomer. The graft (co) polymer (A-1) is 40 to 80 parts by weight of diene rubber, 40 to 95% by weight of aromatic vinyl monomer, 5 to 60% by weight of vinyl cyanide monomer, and The thermoplastic resin composition according to claim 2, obtained by grafting 20 to 60 parts by weight of a monomer mixture comprising 0 to 30% by weight of a copolymerizable vinyl monomer. (iii) The thermoplastic resin composition according to any one of claims 1 to 3, wherein the α, β-unsaturated carboxylic acid monomer in the copolymer (B-1) or (B-2) is methacrylic acid. Stuff. (ii) The heat according to any one of claims 1 to 4, wherein the relative viscosity of a solution of polyamide resin dissolved in 98% concentrated sulfuric acid at a concentration of 1 g / dl is 2.0 to 3.0 at 25 ° C. Plastic resin composition. (ii) The thermoplastic resin composition according to any one of claims 1 to 5, wherein the polyamide resin is nylon 6. (iii) The ratio of the mole fraction (X) of the aromatic vinyl monomer units in the copolymer to the mole fraction (Y) of the vinyl cyanide monomer units in the copolymer (iii) The thermoplastic resin composition according to any one of claims 1 to 6, wherein the X / Y value is 0.95 to 1.10. (iii) The thermoplastic resin composition according to any one of claims 1 to 7, wherein the intrinsic viscosity measured at 30 ° C after dissolving the copolymer in a methyl ethyl ketone solvent is 0.3 to 1.0 dl / g. (iii) Further containing 1-30 parts by weight of a copolymer with respect to 100 parts by weight of a resin composition comprising 10-90% by weight of a rubber-reinforced styrene resin and (ii) 90-10% by weight of a polyamide resin The thermoplastic resin composition according to any one of claims 1 to 8, which is caulked. The vinyl (co) polymer (A-2) is obtained by polymerizing at least an aromatic vinyl monomer and a vinyl cyanide monomer, and the vinyl (co) polymer (A-2 The thermoplastic resin composition according to any one of claims 1 to 9, wherein the value of the molar ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit is 0.90 to 1.25. Stuff. The graft (co) polymer (A-1) is obtained by graft polymerization of at least an aromatic vinyl monomer and a vinyl cyanide monomer, and the graft (co) polymer (A-1) The thermoplastic resin composition according to any one of claims 1 to 10, wherein the molar ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit is 0.90 to 1.35. .

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