JP2017149809A - Epoxy group-containing vinyl copolymer, thermoplastic resin composition, and molded article of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy group-containing vinyl copolymer capable of enhancing compatibility between a styrenic resin and a polyester resin, and to provide a thermoplastic resin composition which is excellent in flowability, can enhance impact resistance and surface glossiness of a molded article, and contains a styrenic resin and a polyester resin.SOLUTION: There is provided an epoxy group-containing vinyl copolymer which is a copolymer of a vinyl monomer (a) that contains at least 55-88 wt.% of an aromatic vinyl monomer (a1), 10-35 wt.% of a vinyl cyanide monomer (a2) and 2-25 wt.% of an epoxy group-containing vinyl monomer (a3), where the weight average molecular weight is 11,000 to 50,000 and the sulfur content exceeds 0.3 wt.%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an epoxy group-containing vinyl copolymer, a compatibilizer using the same, a thermoplastic resin composition, and a molded product thereof.

  Styrenic resins represented by acrylonitrile-butadiene-styrene (ABS) resin have excellent mechanical properties, molding processability, and electrical insulation, so they are used in various parts such as household electrical equipment, OA equipment and automobiles. It is used in a wide range of fields. On the other hand, polyester resins such as polyethylene terephthalate (PET) resin are widely used in various bottles, food trays, sheets and the like because of their excellent mechanical strength, chemical resistance, transparency and gas barrier properties.

  In recent years, a polymer alloy technique of mixing a plurality of different polymers has been studied as a means for improving the physical properties of polymer compounds. The purpose of the polymer alloy is to obtain a polymer having the characteristics of each constituent polymer by mixing a plurality of different polymers. Regarding the polymer alloying technology of the ABS resin and the PET resin described above, for example, a polyethylene terephthalate resin recycled material (A), a graft polymer (B) formed by polymerizing vinyl cyanide and aromatic vinyl on a rubber polymer, A thermoplastic resin composition obtained by blending a vinyl copolymer (C) and a polycarbonate resin (D) has been proposed (see, for example, Patent Document 1). However, it is known from the beginning that the compatibility between ABS resin and PET resin is not good, and the composition obtained by the method described in Patent Document 1 still has a problem of insufficient impact resistance. It was.

  Therefore, regarding the compatibility improvement technology of styrene resin and polyester resin, for example, at least one or more selected from the group consisting of rubber-reinforced styrene resin, saturated polyester resin, carboxyl group, epoxy group, amino group and amide group A thermoplastic resin composition containing a modified vinyl copolymer having a functional group (see, for example, Patent Document 2), a styrene resin, a polyethylene terephthalate resin, and an acrylic / styrene copolymer containing an epoxy group A thermoplastic resin composition containing a coalescence (for example, see Patent Document 3) has been proposed.

JP 2004-67728 A JP 2003-286382 A International Publication No. 2013/129547

  Although the compatibility described in Patent Documents 2 to 3 improves the compatibility and can improve the impact resistance, it is still insufficient for the high impact resistance required in recent years. There is a need for improved impact resistance. In addition, the thermoplastic resin compositions described in Patent Documents 2 to 3 may have impaired surface gloss and fluidity due to the formation of a crosslinked product in an extruder or a molding machine.

  An object of the present invention is to provide an epoxy group-containing vinyl copolymer that can improve the compatibility of a styrene resin and a polyester resin, and is excellent in fluidity, impact resistance and surface of a molded product. An object of the present invention is to provide a thermoplastic resin composition containing a styrene resin and a polyester resin that can improve glossiness.

As a result of intensive studies on the above problems, the present inventors have improved the compatibility between the styrene resin and the polyester resin by using an epoxy group-containing vinyl copolymer having a weight average molecular weight and a sulfur content within specific ranges. The present inventors have found that the fluidity of a thermoplastic resin composition containing them and the impact resistance and surface glossiness of a molded product obtained therefrom can be improved, leading to the present invention. That is, the present invention has the following configuration.
(1) At least aromatic vinyl monomer (a1) 55 to 88% by weight, vinyl cyanide monomer (a2) 10 to 35% by weight, and epoxy group-containing vinyl monomer (a3) 2 to 25 It is a copolymer of vinyl monomer (a) containing wt%, having an epoxy group containing a weight average molecular weight of 11,000 to 50,000 and a sulfur content exceeding 0.3 wt% Vinyl copolymer.
(2) The method for producing an epoxy group-containing vinyl copolymer according to (1), wherein the vinyl monomer (a) is subjected to suspension polymerization.
(3) A compatibilizing agent comprising the epoxy group-containing vinyl copolymer according to (1).
(4) A thermoplastic resin composition comprising the styrene resin (I), the polyester resin (II) and the epoxy group-containing vinyl copolymer according to (1), wherein the styrene resin (I) and A thermoplastic resin composition comprising 0.01 to 2 parts by weight of the epoxy group-containing vinyl copolymer according to (1) with respect to 100 parts by weight of the total of the polyester resin (II).
(5) 50 to 99 parts by weight of styrene resin (I) and 1 to 55 parts by weight of polyester resin (II) with respect to 100 parts by weight of the total of styrene resin (I) and polyester resin (II). The thermoplastic resin composition according to (4).
(6) The thermoplastic resin composition according to (4) or (5), wherein the polyester resin (II) contains a polyethylene terephthalate resin.
(7) A molded article comprising the thermoplastic resin composition according to any one of (4) to (6).

  The epoxy group-containing vinyl copolymer of the present invention can improve the compatibility between the styrene resin and the polyester resin. By using such an epoxy group-containing vinyl copolymer, the fluidity of a thermoplastic resin composition containing a styrene resin and a polyester resin is improved, and a molded article having excellent impact resistance and surface gloss is obtained. Can do.

FIG. 1 shows an SEM photograph in the compatibility evaluation of Example 1. FIG. 2 shows an SEM photograph in the compatibility evaluation of Comparative Example 3.

  The epoxy group-containing vinyl copolymer of the present invention is a vinyl containing at least an aromatic vinyl monomer (a1), a vinyl cyanide monomer (a2), and an epoxy group-containing vinyl monomer (a3). It can be obtained by copolymerizing the monomer (a). Such a copolymer can be preferably used as a compatibilizer between a styrene resin and a polyester resin, improves the fluidity of a thermoplastic resin composition containing the styrene resin and the polyester resin, and improves the thermoplastic resin composition. It is possible to improve the impact resistance and surface gloss of a molded article made of a product.

  Examples of the aromatic vinyl monomer (a1) include styrene, α-methylstyrene, orthomethylstyrene, paramethylstyrene, para-t-butylstyrene, and halogenated styrene. Two or more of these may be used. Among these, from the viewpoint of further improving the compatibility between the styrene resin and the polyester resin, styrene and α-methylstyrene are preferable, and styrene is more preferable.

  Examples of the vinyl cyanide monomer (a2) include acrylonitrile and methacrylonitrile. Two or more of these may be used. Among these, acrylonitrile is preferable from the viewpoint of further improving the compatibility between the styrene resin and the polyester resin.

  As the epoxy group-containing vinyl monomer (a3), a (meth) acrylic ester monomer having an epoxy group is preferable, and examples thereof include an epoxy group-containing methacrylate such as glycidyl methacrylate and an epoxy group-containing acrylate such as glycidyl acrylate. . Two or more of these may be used. Of these, glycidyl methacrylate is preferable.

  The vinyl monomer (a) is within the range not impairing the effects of the present invention, and the aromatic vinyl monomer (a1), the vinyl cyanide monomer (a2), and the epoxy group-containing vinyl system. Vinyl monomers other than the monomer (a3) may be included. Examples of vinyl monomers other than the above (a1) to (a3) include unsaturated carboxylic acid alkyl ester monomers and acrylamide monomers. Two or more of these may be used.

  Although there is no restriction | limiting in particular as an unsaturated carboxylic-acid alkylester type monomer, The ester of C1-C6 alcohol and acrylic acid or methacrylic acid is preferable. 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 and the like, and methyl (meth) acrylate is preferred. “(Meth) acrylic acid” refers to acrylic acid or methacrylic acid.

  Examples of the acrylamide monomer include acrylamide, methacrylamide, N-methylacrylamide and the like.

  The vinyl monomer (a) is 55 to 88% by weight of the aromatic vinyl monomer (a1) and 10 to 35% by weight of the vinyl cyanide monomer (a2) in a total of 100% by weight. %, And 2 to 25% by weight of the epoxy group-containing vinyl monomer (a3). When the content of the aromatic vinyl monomer (a1) is less than 55% by weight, the compatibility between the styrene resin and the polyester resin is lowered, and the thermoplastic resin composition containing the styrene resin and the polyester resin is used. The impact resistance of the molded product is reduced. The content of the aromatic vinyl monomer (a1) is preferably 60% by weight or more, and more preferably 65% by weight or more. On the other hand, when the content of the aromatic vinyl monomer (a1) exceeds 88% by weight, the compatibility between the styrene resin and the polyester resin is lowered, and the thermoplastic resin composition containing the styrene resin and the polyester resin. The impact resistance of the molded product made of is reduced. The content of the aromatic vinyl monomer (a1) is preferably 80% by weight or less, and more preferably 75% by weight or less. Further, when the content of the vinyl cyanide monomer (a2) is less than 10% by weight, the compatibility between the styrene resin and the polyester resin is lowered, and the thermoplastic resin composition containing the styrene resin and the polyester resin. The impact resistance of the molded product made of is reduced. The content of the vinyl cyanide monomer (a2) is preferably 15% by weight or more, and more preferably 20% by weight or more. On the other hand, when the content of the vinyl cyanide monomer (a2) exceeds 35% by weight, the compatibility between the styrene resin and the polyester resin decreases, and the thermoplastic resin composition containing the styrene resin and the polyester resin. In addition to the impact resistance of the molded product made of, the yellow color of the molded product becomes stronger. The content of the vinyl cyanide monomer (a2) is preferably 30% by weight or less, and more preferably 28% by weight or less. In addition, when the content of the epoxy group-containing vinyl monomer (a3) is less than 2% by weight, the epoxy group content is decreased, so the reactivity between the epoxy group-containing vinyl copolymer and the polyester resin is poor. The compatibility between the styrene resin and the polyester resin is lowered, and the impact resistance of a molded article made of a thermoplastic resin composition containing the styrene resin and the polyester resin is lowered. The content of the epoxy group-containing vinyl monomer (a3) is more preferably 2.5% by weight or more. On the other hand, when the content of the epoxy group-containing vinyl monomer (a3) exceeds 25% by weight, the epoxy group content increases. Therefore, the epoxy group-containing vinyl copolymer and the polyester resin are cross-linked by excessive reaction. A product is easily generated, and the fluidity of a thermoplastic resin composition containing a styrene resin and a polyester resin and the impact resistance and surface gloss of a molded article made of the thermoplastic resin composition are lowered. The content of the epoxy group-containing vinyl monomer (a3) is preferably 20% by weight or less, and more preferably 15% by weight or less.

  The epoxy group-containing vinyl copolymer of the present invention has a weight average molecular weight of 11,000 to 50,000. When the weight average molecular weight is less than 11,000, the compatibility between the styrene resin and the polyester resin is lowered, and the impact resistance of the molded article made of the thermoplastic resin composition containing the styrene resin and the polyester resin is lowered. To do. On the other hand, when the weight average molecular weight exceeds 50,000, the epoxy group content in one molecule of the epoxy group-containing vinyl copolymer increases, so the excess of the epoxy group-containing vinyl copolymer and the polyester resin. A cross-linked product is generated by the reaction, and the impact resistance and surface gloss of a molded article made of a thermoplastic resin composition containing a styrene resin and a polyester resin are lowered. The weight average molecular weight of the epoxy group-containing vinyl copolymer is preferably 30,000 or less.

The weight average molecular weight of the epoxy group-containing vinyl copolymer in the present invention indicates a value in terms of polystyrene measured by gel permeation chromatography (GPC). By converting polystyrene as a standard substance from a GPC chromatogram measured using a solution of about 0.2% by weight of about 0.03 g of an epoxy group-containing vinyl copolymer sample dissolved in about 15 g of tetrahydrofuran, Average molecular weight can be determined. The GPC measurement can be performed under the following conditions.
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).

  Examples of the means for setting the weight average molecular weight of the epoxy group-containing vinyl copolymer in the above range include a method of setting the addition amount of the chain transfer agent and the polymerization initiator in a preferable range described later.

  The epoxy group-containing vinyl copolymer of the present invention contains sulfur, and the sulfur content in 100% by weight (including sulfur) of the epoxy group-containing vinyl copolymer exceeds 0.3% by weight. Features. By containing sulfur in the epoxy group-containing vinyl-based copolymer, the compatibility of the styrene-based resin and the polyester-based resin is improved, and a molded article comprising a thermoplastic resin composition containing the styrene-based resin and the polyester-based resin is improved. Impact resistance can be improved. If the sulfur content is 0.3% by weight or less, the compatibility between the styrene resin and the polyester resin is lowered, and the impact resistance of the molded product comprising the thermoplastic resin composition containing the styrene resin and the polyester resin is reduced. Decreases. In addition, when the epoxy group-containing vinyl copolymer is polymerized by a suspension polymerization method, the surface gloss is lowered due to the influence of the chain transfer agent. The sulfur content in the epoxy group-containing vinyl copolymer is preferably 0.32% by weight or more. On the other hand, the sulfur content of the epoxy group-containing vinyl copolymer is preferably 0.7% by weight or less.

The sulfur content of the epoxy group-containing vinyl copolymer in the present invention indicates a value measured by fluorescent X-ray analysis and quantified by a fundamental parameter (FP) method. The fluorescent X-ray analysis can be performed under the following conditions.
Equipment: Shimadzu EDX-72
X-ray tube: Rh target tube voltage: 50 kV
Tube current: Automatic collimator: 10 mm diameter detector: Si (Li) detector Integration time: 100 seconds Dead time: 39%
Atmosphere: Vacuum quantitative method: Bulk FP method.

  As a means for making the sulfur content of the epoxy group-containing vinyl copolymer in the above range, for example, a preferable chain transfer agent or polymerization initiator described later is used, and the addition amount of the chain transfer agent or polymerization initiator is described later. The method of making it into a preferable range is mentioned.

  The epoxy group-containing vinyl copolymer of the present invention is obtained by subjecting the aforementioned vinyl copolymer (a) to a known polymerization method such as a bulk polymerization method, a solution polymerization method, an emulsion polymerization method or a suspension polymerization method. It can be obtained by copolymerization. Among these, the suspension polymerization method is preferred because the polymerization control is easy and the removal step of unreacted components, reaction solvent, emulsifier and the like is unnecessary.

  In the method for producing an epoxy group-containing vinyl copolymer, a polymerization initiator may be used. Examples of the polymerization initiator include peroxides, azo compounds, and persulfates. Two or more of these may be used. The polymerization initiator can also be used in a redox system.

  Specific 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.

  Specific examples of the azo compound include 2,2′-azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2- Cyano-2-propylazoformamide, 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.

  Specific examples of the persulfate include potassium persulfate, sodium persulfate, and ammonium persulfate.

  Of these, 2,2'-azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), and the like are preferably used.

  The addition amount of the polymerization initiator is preferably 0.1 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of the vinyl monomer (a).

  In the method for producing an epoxy group-containing vinyl copolymer, a chain transfer agent is preferably used, and the weight average molecular weight of the epoxy group-containing vinyl copolymer can be adjusted to a desired range. As the chain transfer agent, mercaptans are preferable, and specific examples thereof include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and the like. Two or more of these may be used. Of these, n-octyl mercaptan and t-dodecyl mercaptan are preferably used.

  The addition amount of the chain transfer agent is preferably 1.5 to 4.0 parts by weight with respect to 100 parts by weight of the total amount of the vinyl monomer (a). By using 1.5 parts by weight or more of the chain transfer agent, the epoxy group-containing vinyl copolymer can be easily adjusted to have a weight average molecular weight of 50,000 or less and a sulfur content of 0.3% by weight or more. it can. On the other hand, by using 4.0 parts by weight or less of the chain transfer agent, the weight average molecular weight of the epoxy group-containing vinyl copolymer can be easily adjusted to 11,000 or more.

  When producing an epoxy group-containing vinyl copolymer by suspension polymerization, it is preferable to use a suspension stabilizer. Suspension stabilizers include inorganic suspension stabilizers such as clay, barium sulfate, and magnesium hydroxide, and organic suspensions such as polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, and methyl methacrylate / acrylamide copolymer. Examples include turbid stabilizers. Two or more of these may be used. Of these, organic suspension stabilizers are preferably used in terms of color stability.

  A slurry of an epoxy group-containing vinyl copolymer is obtained by suspension polymerization, and then a bead-like epoxy group-containing vinyl copolymer is obtained through dehydration and drying.

  Next, the thermoplastic resin composition of the present invention will be described. The thermoplastic resin composition of the present invention includes a styrene resin (I), a polyester resin (II) and the epoxy group-containing vinyl copolymer, and the epoxy group-containing vinyl copolymer is a styrene resin ( It acts as a compatibilizing agent that improves the compatibility between I) and the polyester resin (II).

  The styrene resin (I) in the present invention refers to a polymer of an aromatic vinyl monomer, and may be a copolymer of an aromatic vinyl monomer and another monomer. By containing the styrene resin (I) in the thermoplastic resin composition of the present invention, the impact resistance of the molded product can be improved.

  The styrene resin (I) may be obtained by graft polymerization of a monomer component containing an aromatic vinyl monomer on a rubber polymer. In addition to the graft copolymer obtained by graft polymerization of a monomer component containing an aromatic vinyl monomer to a rubber polymer, a polymer of a monomer component not grafted to the rubber polymer may be included. As such a styrene resin (I), for example, a monomer component containing an aromatic vinyl monomer (A1) and a vinyl cyanide monomer (A2) is grafted onto the rubber polymer (R). A graft copolymer (A) obtained by copolymerization and a vinyl copolymer (B) that is a copolymer of at least an aromatic vinyl monomer (A1) and a vinyl cyanide monomer (A2). ). The monomer component may include another vinyl monomer (A3) copolymerizable with the aromatic vinyl monomer (A1) and the vinyl cyanide monomer (A2).

  Examples of the rubbery polymer (R) used for the graft copolymer (A) include diene rubber, acrylic rubber, and ethylene rubber. Examples of the diene rubber include polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), polyisoprene, and the like. Examples of the acrylic rubber include poly (butyl acrylate-methyl methacrylate), poly (butadiene-butyl acrylate), poly (butadiene-methyl methacrylate), poly (butadiene-ethyl acrylate), and the like. Examples of the ethylene rubber include ethylene-propylene rubber, ethylene-propylene-diene rubber, poly (ethylene-isoprene), poly (ethylene-methyl acrylate), and the like. Two or more of these may be used. Of these rubbery polymers (R), polybutadiene, poly (butadiene-styrene), from the viewpoint of further improving the impact resistance of a molded article comprising a thermoplastic resin composition containing a styrene resin and a polyester resin. Poly (butadiene-acrylonitrile) and ethylene-propylene rubber are preferably used.

  The weight average particle diameter of the rubber polymer (R) 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 further improving the appearance of the molded product, 0.5 μm or less is preferable, and 0.4 μm or less is more preferable. Here, the weight average particle diameter of the rubber polymer (R) is the particle diameter distribution measured by a laser scattering diffraction particle size distribution analyzer after diluting and dispersing the latex containing the rubber polymer (R) in an aqueous medium. The weight average particle diameter calculated from LS 13 320 (manufactured by Beckman Coulter, Inc.) can be used as a laser scattering diffraction particle size distribution measuring apparatus.

  The aromatic vinyl monomer (A1) and vinyl cyanide monomer (A2) used in the graft copolymer (A) are aromatic vinyl monomers used in the epoxy group-containing vinyl copolymer. Examples of the monomer (a1) and the vinyl cyanide monomer (a2) include those exemplified above.

  Examples of other copolymerizable vinyl monomers (A3) used in the graft copolymer (A) include unsaturated carboxylic acid ester monomers, acrylamide monomers, and maleimide compounds. It is done. Examples of the unsaturated carboxylic acid ester monomer and the acrylamide monomer include those exemplified above as the vinyl monomers used in the epoxy group-containing vinyl copolymer. Two or more of these may be used. Examples of the maleimide compound include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like.

The graft copolymer (A) is mixed with the aromatic vinyl monomer (A1), the vinyl cyanide monomer (A2) and, if necessary, with the rubbery polymer (R). It can be obtained by graft copolymerizing a monomer component containing another polymerizable vinyl monomer (A3). Here, it is not necessary that all the monomer components are graft copolymerized with the rubber polymer (R), and the monomer components are not graft copolymerized with the rubber polymer (R). The copolymer may be included. The graft ratio of the graft copolymer (A) is 10 from the viewpoint of further improving the compatibility of the graft copolymer (A) and the vinyl copolymer (B) and further improving the impact resistance of the molded product. % Or more is preferable, and 20% or more is more preferable. On the other hand, from the viewpoint of further improving the dispersibility of the graft copolymer (A) in the thermoplastic resin composition and further improving the impact resistance of the molded product, 100% or less is preferable, and 50% or less is more preferable. Here, the graft ratio is a value calculated by the following equation.
Graft ratio (%) = [<Vinyl copolymer grafted onto rubber polymer (weight)> / <Rubber polymer content (weight) in graft copolymer>] × 100.

  The rubbery polymer (R) in the raw material constituting the graft copolymer (A), the aromatic vinyl monomer (A1), the vinyl cyanide monomer (A2), and others copolymerizable therewith The amount of the vinyl monomer (A3) is not particularly specified, but from the viewpoint of further improving the impact resistance of the molded product, the rubber polymer (R) is 10% in a total of 100% by weight. %, And the total of (A1) to (A3) is preferably 90% by weight or less, the rubbery polymer (R) is 20% by weight or more, and the total of (A1) to (A3) is 80% by weight or less. The rubbery polymer (R) is more preferably 30% by weight or more, and the total of (A1) to (A3) is further preferably 70% by weight or less. On the other hand, from the viewpoint of molding processability, the rubber polymer (R) is preferably 80% by weight or less, and the total of (A1) to (A3) is preferably 20% by weight or more. 70% by weight or less, and the total of (A1) to (A3) is more preferably 30% by weight or more, the rubbery polymer (R) is 65% by weight or less, and the total of (A1) to (A3) is 35 More preferably, it is at least wt%.

  Further, the blending amount of the monomers (A1) to (A3) in the raw material constituting the graft copolymer (A) is not particularly specified, but aromatics are included in the total 100% by weight of (A1) to (A3). The vinyl monomer (A1) is 20 to 99% by weight, the vinyl cyanide monomer (A2) is 1 to 40% by weight, and the other vinyl monomers (A3) copolymerizable therewith are 0%. ˜79 wt% is preferable, and the molding processability of the thermoplastic resin composition and the impact resistance of the molded product can be further improved.

The reduced viscosity (η _sp / c) of the acetone-soluble component of the graft copolymer (A) is preferably 0.1 dl / g or more from the viewpoint of further improving the impact resistance of the molded product, and is preferably 0.3 dl / g. The above is more preferable. On the other hand, from the viewpoint of further improving the fluidity of the thermoplastic resin composition, it is preferably 0.6 dl / g or less, and more preferably 0.5 dl / g or less.

  The acetone-soluble content of the graft copolymer (A) was obtained by centrifuging a solution obtained by adding 200 ml of acetone to 1 g of a sample of the graft copolymer (A) and refluxing for 3 hours, and filtering the insoluble matter. Can be obtained as a precipitate. After drying the obtained precipitate, a methyl ethyl ketone solution having a concentration of 0.4 g / 100 ml can be prepared, and the reduced viscosity can be measured using an Ubbelohde viscometer.

  As a method for producing the graft copolymer (A), the weight average particle diameter of the rubber polymer (R) can be easily adjusted to the above-mentioned preferable range, and the polymerization stability can be easily controlled by removing heat during polymerization. The emulsion polymerization method is preferred. When the graft copolymer (A) is produced by an emulsion polymerization method, various surfactants may be added as an emulsifier.

  As the surfactant, anionic surfactants such as a carboxylate type, a sulfate ester type, and a sulfonate type are preferably used. Two or more of these may be used. In addition, as a salt 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, and condensates thereof.

  In the method for producing the graft copolymer (A), a polymerization initiator may be used. As a polymerization initiator, what was illustrated previously as a polymerization initiator in the manufacturing method of an epoxy-group-containing vinyl-type copolymer can be mentioned.

  In the method for producing the graft copolymer (A), a chain transfer agent may be used, and the degree of polymerization and the graft ratio can be easily adjusted to a desired range. As a chain transfer agent, what was illustrated previously as a chain transfer agent in the manufacturing method of an epoxy-group-containing vinyl-type copolymer can be mentioned.

  When the graft copolymer (A) is produced by an emulsion polymerization method, it is preferable to add a coagulant to the graft copolymer latex obtained by emulsion polymerization to recover the graft copolymer (A). 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 used. In order to improve the color tone of the graft copolymer (A), it is preferable not to leave an emulsifier in the graft copolymer (A), 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.

  The aromatic vinyl monomer (A1) and vinyl cyanide monomer (A2) used in the vinyl copolymer (B) are aromatic vinyl monomers used in the epoxy group-containing vinyl copolymer. Examples of the monomer (a1) and the vinyl cyanide monomer (a2) include those exemplified above. Further, as the other copolymerizable vinyl monomer (A3) used in the vinyl copolymer (B), other vinyl monomers (A3) used in the graft copolymer (A) are used. As mentioned above, those exemplified above can be mentioned.

The reduced viscosity (η _sp / c) of the vinyl (co) polymer (B) is preferably 0.1 dl / g or more, more preferably 0.3 dl / g or more, from the viewpoint of further improving the impact resistance of the molded product. More preferred. On the other hand, from the viewpoint of further improving the fluidity of the thermoplastic resin composition, it is preferably 0.6 dl / g or less, and more preferably 0.5 dl / g or less.

  The acetone-soluble content of the vinyl copolymer (B) is obtained by centrifuging a solution obtained by adding 200 ml of acetone to 1 g of a sample of the vinyl copolymer (B) and refluxing for 3 hours, and then filtering the insoluble content. The filtrate can be concentrated to obtain a precipitate. After drying the obtained precipitate, a methyl ethyl ketone solution having a concentration of 0.4 g / 100 ml can be prepared, and the reduced viscosity can be measured using an Ubbelohde viscometer.

  As a method for producing the vinyl copolymer (B), a continuous bulk polymerization method and a suspension polymerization method are preferable in view of ease of polymerization control, ease of post-treatment, and productivity.

  When the vinyl copolymer (B) is produced by suspension polymerization, it is preferable to use a suspension stabilizer. Examples of the suspension stabilizer include those exemplified above as the suspension stabilizer in the method for producing an epoxy group-containing vinyl copolymer.

  In the method for producing the vinyl copolymer (B), a polymerization initiator may be used. As a polymerization initiator, what was illustrated previously as a polymerization initiator in the manufacturing method of an epoxy-group-containing vinyl-type copolymer can be mentioned. Moreover, in the manufacturing method of a vinyl-type copolymer (B), you may use a chain transfer agent and can adjust a polymerization degree to a desired range easily. As a chain transfer agent, what was illustrated previously as a chain transfer agent in the manufacturing method of an epoxy-group-containing vinyl-type copolymer can be mentioned.

  When the vinyl (co) polymer (B) is produced by suspension polymerization, the vinyl (co) polymer (B) slurry obtained by suspension polymerization is preferably dehydrated and dried. A vinyl-based copolymer (B) is obtained.

  When using a blend of the graft copolymer (A) and the vinyl copolymer (B) as the styrene resin (I), the graft copolymer (A) is used from the viewpoint of further improving the impact resistance of the molded product. ) And vinyl copolymer (B) in total 100 parts by weight, it is preferable to blend 10 parts by weight or more of graft copolymer (A) and 90 parts by weight or less of vinyl copolymer (B). More preferably, 20 parts by weight or more of the graft copolymer (A) and 80 parts by weight or less of the vinyl copolymer (B) are blended. On the other hand, from the viewpoint of further improving the fluidity of the thermoplastic resin composition, it is preferable to blend 50 parts by weight or less of the graft copolymer (A) and 50 parts by weight or more of the vinyl copolymer (B). More preferably, 40 parts by weight or less of copolymer (A) and 60 parts by weight or more of vinyl copolymer (B) are blended.

  Specific examples of the styrene resin (I) used in the present invention include, for example, acrylonitrile-butadiene-styrene (ABS) resin, high impact polystyrene (HIPS), acrylonitrile-acrylic-styrene (AAS) resin, acrylonitrile-ethylene, Examples include propylene / diene-styrene (AES) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and methyl methacrylate-butadiene-styrene (MBS) resin.

  The polyester-based resin (II) in the present invention refers to a resin having an ester bond in the main chain, a polymer of dicarboxylic acid or its ester-forming derivative and glycol, and a single monomer having a carboxyl group and a hydroxyl group in the molecule. And the like. Examples thereof include polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polylactic acid (PLA) resin, and the like. From the viewpoint of improving the chemical resistance of the molded product, a polyethylene terephthalate resin is preferable. By including the polyester resin (II) in the thermoplastic resin composition of the present invention, mechanical strength such as tensile strength of the molded article and chemical resistance can be improved.

  The polyethylene terephthalate resin in the present invention refers to a polymer of terephthalic acid or an ester-forming derivative thereof and ethylene glycol. Along with terephthalic acid, isophthalic acid, adipic acid, oxalic acid, etc. may be used, and together with ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexane. Long chain glycols such as diol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, polyethylene glycol having a molecular weight of 400 to 6000, poly-1,3-propylene glycol, and polytetramethylene glycol may be used. It is preferable to use 80 mol% or more of terephthalic acid or its ester-forming derivative in a total of 100 mol% of dicarboxylic acid or its ester-forming derivative, and to use 80 mol% or more of ethylene glycol in a total of 100 mol% of diol. Is preferred.

  The polyethylene terephthalate resin preferably has an IV value of 0.5 to 1.0 as measured in accordance with JIS K 7367 (2002). If the IV value is 0.5 or more, the impact resistance of the molded product can be further improved. On the other hand, if IV value is 1.0 or less, the fluidity | liquidity of a thermoplastic resin composition can be improved more.

  The polyester-based resin (II) may be a virgin material that has not been subjected to a thermal history such as molding, and is a recycled material (hereinafter abbreviated as a recycled material) of a polyester-based resin (II) molded product. However, from the viewpoint of resource protection, it is preferable that at least a part of the polyester-based resin (II) is a recycled material. Examples of the recycled material include waste materials obtained by collecting a molded product molded into a plastic bottle or the like at least once, and scrap materials generated in a trimming process at the time of molding a sheet-shaped article. Examples of the shape of the recycled material include a flake shape, a powder shape, and a pellet shape repelletized for removing foreign substances. It is preferable that the recycled material is not mixed with a reinforcing material such as glass fiber.

  In addition, polyester-type resin (II) can select and use arbitrary things from the commercially available thing which has various compositions and IV value.

  The compounding amount of the epoxy group-containing vinyl copolymer in the thermoplastic resin composition of the present invention is 0.01 to 2 parts by weight with respect to a total of 100 parts by weight of the styrene resin (I) and the polyester resin (II). preferable. By setting the compounding amount of the epoxy group-containing vinyl copolymer to 0.01 parts by weight or more, the compatibility of the styrene resin (I) and the polyester resin (II) is further improved, and the impact resistance of the molded product. Can be improved. The amount of the epoxy group-containing vinyl copolymer is preferably 0.03 parts by weight or more, and more preferably 0.05 parts by weight or more. On the other hand, when the amount of the epoxy group-containing vinyl copolymer is 2 parts by weight or less, the fluidity of the thermoplastic resin composition and the surface gloss of the molded product can be further improved. The amount of the epoxy group-containing vinyl copolymer is preferably 1.0 part by weight or less, and more preferably 0.7 part by weight or less.

  The blending amount of the styrene resin (I) and the polyester resin (II) in the thermoplastic resin composition of the present invention is styrene based on a total of 100 parts by weight of the styrene resin (I) and the polyester resin (II). 50 to 99 parts by weight of the resin (I) and 1 to 50 parts by weight of the polyester resin (II) are preferable. By blending 50 parts by weight or more of styrene resin (I) and 50 parts by weight or less of polyester resin (II) with respect to a total of 100 parts by weight of styrene resin (I) and polyethylene terephthalate resin, Impact properties can be further improved. More preferably, 55 parts by weight or more of styrene resin (I) and 45 parts by weight or less of polyester resin (II) are blended, 60 parts by weight or more of styrene resin (I), and 40 of polyester resin (II). More preferably, the amount is not more than parts by weight. On the other hand, by blending 99 parts by weight or less of styrene resin (I) and 1 part by weight or more of polyethylene terephthalate resin with respect to 100 parts by weight of the total of styrene resin (I) and polyester resin (II), a molded product is obtained. The chemical resistance of can be further improved. More preferably, 95 parts by weight or less of styrene resin (I) and 5 parts by weight or more of polyester resin (II) are blended, 90 parts by weight or less of styrene resin (I), and 10 of polyester resin (II). More preferably, it is blended in an amount of at least parts by weight.

  The thermoplastic resin composition of the present invention is a fluorine-based material such as polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyamides such as nylon 6 and nylon 66, polycarbonate, and polytetrafluoroethylene, as long as the object of the present invention is not impaired. You may contain resin and various elastomers.

  In addition, the thermoplastic resin composition of the present invention is, as necessary, glass fiber, glass powder, glass beads, glass flakes, alumina, alumina fibers, carbon fibers, graphite fibers as long as the object of the present invention is not impaired. Inorganic fillers such as stainless steel fibers, silicon carbide whiskers, potassium titanate fibers, wollastonite, asbestos, hard clay, calcined clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, aluminum oxide and minerals, and hinders Antioxidants such as dophenols, sulfur-containing compounds, and phosphorus-containing organic compounds, heat stabilizers such as phenols and acrylates, UV absorbers such as benzotriazoles, benzophenones, and salicylates, hindered amines Agent, higher fatty acid, acid ester, acid Lubricants, plasticizers such as higher alcohols, montanic acid and salts thereof, esters thereof, half esters thereof, release agents such as stearyl alcohol, stearamide and ethylene wax, flame retardant aids, phosphites, hypoxia Anti-coloring agents such as phosphates, neutralizing agents such as phosphoric acid, monosodium phosphate, maleic anhydride, succinic anhydride, nucleating agents, amine-based, sulfonic acid-based, polyether-based antistatic agents, carbon You may contain 1 or more types of additives, such as colorants, such as black, a pigment, and dye.

  Next, the manufacturing method of the thermoplastic resin composition of this invention is demonstrated. The thermoplastic resin composition of the present invention is prepared by mixing, for example, an epoxy group-containing vinyl copolymer, a styrene resin (I), a polyester resin (II) and other components as required using a mixer. And a melt kneading method using a melt kneader. Examples of the mixer include a V-type blender, a super mixer, a super floater, and a Henschel mixer. Examples of the melt kneader include a kneader, a single screw extruder and a twin screw extruder. In general, a method of premixing each component using a mixer and uniformly melt kneading the premix using a melt kneader is preferably used. The melt kneading temperature is preferably about 230 to 300 ° C, more preferably about 250 to 285 ° C. A method of pelletizing with a pelletizer after melt-kneading is common.

  The thermoplastic resin composition of the present invention can be molded by any molding method used for molding a thermoplastic resin composition and used as a molded product having an arbitrary shape. Examples of the molding method include injection molding, extrusion molding, blow molding, vacuum molding, compression molding, and gas assist molding. Examples of the shape of the molded product include injection molded products such as films, sheets, television frames, pedestals, and cosmetic containers.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this does not restrict | limit this invention with this. First, a method for measuring and evaluating various characteristics in Examples and Comparative Examples will be described.

(1) Weight average molecular weight About 0.03 g of each epoxy group-containing vinyl copolymer sample obtained in each Example and Comparative Example 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, polystyrene was calculated when styrene was the main component, and polymethyl methacrylate was converted as a standard material when methyl methacrylate was the main component, and the weight average molecular weight 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).

(2) Sulfur content About the sample of the epoxy-group containing vinyl copolymer obtained by each Example and the comparative example, sulfur content was calculated | required by the fluorescent X ray analysis measured on condition of the following.
Equipment: Shimadzu EDX-72
X-ray tube: Rh target tube voltage: 50 kV
Tube current: Automatic collimator: 10 mm diameter detector: Si (Li) detector Integration time: 100 seconds Dead time: 39%
Atmosphere: Vacuum quantitative method: Bulk FP method.

(3) Compatibility of epoxy group-containing vinyl copolymer 0.5 parts by weight of the epoxy group-containing vinyl copolymer obtained in each Example and Comparative Example, graft copolymer described in Reference Example 1 described later (A) 25 parts by weight, 45 parts by weight of the vinyl copolymer (B) described in Reference Example 2 to be described later and 30 parts by weight of a polyethylene terephthalate resin described in Reference Example 3 to be described later are mixed, and 30 mm biaxial with a vent Using an extruder, the mixture was melt-kneaded at a cylinder set temperature of 260 ° C. to obtain pellets. The obtained pellets were pre-dried in a hot air drier at 105 ° C. for 5 hours, and the cylinder temperature was 260 ° C. and the mold temperature was 60 ° C. using an electric injection molding machine SE50 manufactured by Sumitomo Heavy Industries, Ltd. Then, a multi-purpose test piece A type (total length 150 mm, test section width 10 mm, thickness 4 mm) defined in ISO 3167 (2002) was injection molded. The obtained multipurpose test piece A type was cut out in the direction perpendicular to the flow direction of the thermoplastic resin composition to obtain a sample for SEM observation. About the sample for SEM observation, the area | region of 64 micrometers x 60 micrometers was observed by SEM on the following conditions with the magnification of 2000 times. In the SEM photograph, the white portion is the polyethylene terephthalate resin phase, and the compatibility of the epoxy group-containing vinyl copolymer was evaluated from the size of the dispersion diameter of the polyethylene terephthalate resin phase. When the polyethylene terephthalate resin phase is small and dispersed, the compatibility is high (◯), and when the polyethylene terephthalate resin phase is large, the compatibility is low (x).
(I) Cross sectional surface cutting device: Ultra microtome cutting blade: Glass knife cutting angle: 6 degrees Cutting amount: 30 μm
(Ii) SEM observation condition observation device: S-3000N (Hitachi High-Technologies Corporation)
Acceleration voltage: 15 kV
Working distance: 15mm
Observation angle: 0 degree (cross section 90 degrees)
Observation magnification: 2000 times.

(4) Weight average particle diameter of rubbery polymer (R) The polybutadiene latex used in the production of the graft copolymer (A) described in Reference Example 1 described later is diluted and dispersed in an aqueous medium, and laser scattering diffraction method is used. The particle size distribution was measured with a particle size distribution measuring device LS 13 320 (manufactured by Beckman Coulter, Inc.). From the particle size distribution, the weight average particle size of the rubber polymer (R) was calculated.

(5) Graft ratio of graft copolymer (A) Acetone was added to about 1 g (m: sample weight) of the graft copolymer (A) obtained by the method described in Reference Example 1 described later, and the mixture was refluxed for 3 hours. The solution was centrifuged at 8800 rpm (10000 G) for 40 minutes, and the insoluble matter was collected by filtration. This insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and its weight (n) was measured. The graft ratio was calculated from the following formula. In the following formula, L represents the rubbery polymer content (% by weight) of the graft copolymer.
Graft ratio (%) = {[(n) − [(m) × L / 100]] / [(m) × L / 100]} × 100.

(6) Reduced viscosity [η _sp / c] of graft copolymer (A) and vinyl copolymer (B)
For a graft copolymer (A) obtained by the method described in Reference Example 1 described later and a vinyl copolymer (B) obtained by the method described in Reference Example 2 described later, 200 ml of acetone was added to 1 g of a sample. In addition, the solution refluxed for 3 hours was centrifuged at 8800 rpm (10000 G) for 40 minutes, and the insoluble matter was filtered. The filtrate was concentrated using a rotary evaporator, and the precipitate (acetone soluble component) was dried under reduced pressure at 60 ° C. for 5 hours. Then, a methyl ethyl ketone solution (30 ° C.) having a concentration of 0.4 g / 100 ml was prepared, and an Ubbelohde viscometer was used. [eta] _sp / c] was measured.

(7) Impact resistance (Charpy impact strength)
The pellets obtained in Examples 7 to 20 and Comparative Examples 10 to 24 were pre-dried in a hot air drier at 105 ° C. for 5 hours, and cylinder temperature was measured using an electric injection molding machine SE50 manufactured by Sumitomo Heavy Industries, Ltd. : A multipurpose test piece A type (full length 150 mm, test section width 10 mm, thickness 4 mm) defined in ISO 3167 (2002) was injection molded under the conditions of 260 ° C. and mold temperature: 60 ° C. Using the obtained multipurpose specimen A type, the impact strength was measured under the conditions of V notch (remaining width 8.0 mm), 23 ° C., and 50% RH in accordance with the provisions of ISO 179 (2000). The Charpy impact strength was measured for each of 10 test pieces, and the number average value was calculated.

(8) Impact resistance (DuPont impact strength)
The pellets obtained in Examples 7 to 20 and Comparative Examples 10 to 24 were pre-dried in a hot air drier at 105 ° C. for 5 hours, and cylinder temperature was measured using an electric injection molding machine SE50 manufactured by Sumitomo Heavy Industries, Ltd. A square plate specimen having a thickness of 2 mm was injection molded under the conditions of: 260 ° C. and mold temperature: 60 ° C. Using the obtained square plate molded article, the DuPont impact value E (J) was measured under the conditions of temperature: 23 ° C., humidity: 50% RH, weight weight: 2 kg, test piece thickness: 2 mm. The DuPont impact strength was calculated by the following formula.
DuPont impact strength E (J) = [{H−h ((N / G) − (1/2))} × W × 0.098]
H: Minimum level (cm) at which all specimens break
h: Difference between adjacent levels (5 cm)
N: Sum of the number of destruction at each level up to H (including H level)
G: Number of specimens at each level (5)
W: Weight of weight (2kg)

(9) Fluidity (melt flow rate)
The pellets of the thermoplastic resin compositions obtained in Examples 7 to 20 and Comparative Examples 10 to 24 were pre-dried in a hot air dryer at 105 ° C. for 5 hours, in accordance with the provisions of ISO 1133 (2005), 260 ° C. , 49N, the melt flow rate was measured.

(10) Surface glossiness The pellets obtained in Examples 7 to 20 and Comparative Examples 10 to 24 were pre-dried in a hot air drier at 105 ° C. for 5 hours, and electric injection molding machine SE50 manufactured by Sumitomo Heavy Industries, Ltd. A square plate test piece having a thickness of 3 mm was injection molded under the conditions of cylinder temperature: 260 ° C. and mold temperature: 60 ° C. Using the obtained 3 mm thick square plate molded article, the specular glossiness (%) of the square plate molded article was determined in accordance with the provisions of JIS Z 8741 (1997) under the conditions of an incident angle and a reflection angle of 60 °. ) Was measured. The specular gloss was measured for each of five test pieces, and the number average value was calculated.

(11) Color tone The pellets obtained in Examples 7 to 20 and Comparative Examples 10 to 24 were pre-dried in a hot air dryer at 105 ° C. for 5 hours, and an electric injection molding machine SE50 manufactured by Sumitomo Heavy Industries, Ltd. was used. Then, a square plate test piece having a thickness of 3 mm was injection molded under the conditions of cylinder temperature: 260 ° C. and mold temperature: 60 ° C. Yellowness (YI) was measured using a square plate molded product having a thickness of 3 mm in accordance with JIS K 7105 (1981). The yellowness was measured for each of five test pieces, and the number average value was calculated.

Examples [Reference Example 1] Production of graft copolymer (A) In a reactor purged with nitrogen, 120 parts by weight of pure water, 0.5 parts by weight of glucose, 0.5 parts by weight of sodium pyrophosphate, ferrous sulfate 0 0.005 part by weight and 60 parts by weight (converted to solid content) of polybutadiene latex (weight average particle size 0.3 μm, gel content 85%) were charged, and the temperature in the reactor was raised to 65 ° C. while stirring. When the internal temperature reached 65 ° C., polymerization was started and a mixture comprising 30 parts by weight of styrene, 10 parts by weight of acrylonitrile and 0.3 parts by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours. At the same time, an aqueous solution consisting of 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously dropped over 7 hours to complete the reaction. The obtained styrene copolymer latex was coagulated in a dilute sulfuric acid aqueous solution at a temperature of 90 ° C., neutralized with an aqueous sodium hydroxide solution, washed, filtered and dried to obtain a graft copolymer (A). The graft ratio of this graft copolymer (A) was 35%, and the reduced viscosity η _sp / c of the acetone-soluble component was 0.35 dl / g.

[Reference Example 2] Method for producing vinyl copolymer (B) 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 ion-exchanged water are charged into the reactor. The gas phase in the vessel was replaced with nitrogen gas and kept at 70 ° C. with stirring. The reaction was continued until the monomer was completely converted to a polymer to obtain an aqueous solution of an acrylamide-methyl methacrylate copolymer. To the obtained aqueous solution, 20 parts by weight of sodium hydroxide and 2000 parts by weight of ion-exchanged water are added, stirred at 70 ° C. for 2 hours, and then cooled to room temperature, whereby methacrylic acid to be a suspension polymerization medium. A methyl-acrylamide copolymer aqueous solution was obtained.

A solution prepared by dissolving 0.05 parts by weight of the methyl methacrylate-acrylamide copolymer aqueous solution in 150 parts by weight of ion-exchanged water was placed in a stainless steel autoclave having a capacity of 20 L and equipped with a baffle and a foudra-type stirring blade at 400 rpm. The mixture was stirred and the system was replaced with nitrogen gas. Next, a monomer mixture of 28.9 parts by weight of acrylonitrile, 11.1 parts by weight of styrene, 0.32 parts by weight of 2,2′-azobisisobutyronitrile and 0.32 parts by weight of t-dodecyl mercaptan, The reaction system was initially added over 30 minutes with stirring, and the temperature was raised to 70 ° C. to initiate a copolymerization reaction. After 1 hour from the initial addition of the monomer mixture, 15 parts by weight of styrene was added using a feed pump. Thereafter, 15 parts by weight of styrene was added to the reaction system three times at 30-minute intervals. After the third addition of styrene, the temperature was raised to 100 ° C. over 60 minutes. After reaching 100 ° C., the mixture was kept at 100 ° C. for 30 minutes and then cooled, and the polymer was separated, washed and dried to obtain a bead-like vinyl copolymer (B). The reduced viscosity η _sp / c of the vinyl copolymer (B) was 0.43 dl / g.

[Reference Example 3] Polyethylene terephthalate resin A polyethylene terephthalate resin recycled pellet (manufactured by Kyoei Sangyo Co., Ltd.) having a measured IV value of 0.76 was prepared in accordance with JIS K 7367 (2002). .

[Reference Example 4] Epoxy group-containing vinyl resin An epoxy group-containing acrylic / styrene copolymer (trade name: “ARUFON” (registered trademark)) which is a copolymer of glycidyl methacrylate, methyl (meth) acrylate and styrene. UG-4035, manufactured by Toagosei Co., Ltd.) was prepared. The weight average molecular weight in terms of polystyrene measured by the method described in (1) above was 11,000, the sulfur content measured by the method described in (2) above was 0.0% by weight, measured by the hydrochloric acid-dioxane method. The epoxy value was 1.8 meq / g.

Example 1
In a stainless steel autoclave having a capacity of 20 L and equipped with a baffle and a foudra-type stirring blade, 0.05 part by weight of an aqueous methyl methacrylate-acrylamide copolymer solution obtained by the method described in Reference Example 2 was added to 150 parts by weight of ion-exchanged water. The solution dissolved in the part was added and stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, 100 parts by weight of a vinyl monomer comprising 72.2 parts by weight of styrene, 22.8 parts by weight of acrylonitrile, 5.0 parts by weight of glycidyl methacrylate, 3.5 parts by weight of t-dodecyl mercaptan, 2,2′- 0.32 parts by weight of azobisisobutyronitrile was added, and the dissolved mixture was added over 30 minutes while stirring the reaction system, and the temperature was raised to 70 ° C. to initiate the copolymerization reaction. The temperature was raised to 100 ° C. over 50 minutes after 2 hours from the start of the copolymerization reaction. After reaching 100 ° C., the mixture was kept at 100 ° C. for 5 minutes, then cooled, and the polymer was separated, washed, and dried to obtain a bead-like epoxy group-containing vinyl copolymer 1. The resulting epoxy group-containing vinyl copolymer 1 had a weight average molecular weight of 14,000 and a sulfur content of 0.58% by weight.

(Examples 2-6, Comparative Examples 1-9)
Epoxy group-containing vinyl copolymers 2 to 15 were obtained in the same manner as in Example 1 except that the vinyl monomer composition and the type and blending amount of the chain transfer agent were changed as shown in Table 1.

  The compositions and evaluation results of Examples 1 to 6 and Comparative Examples 1 to 9 are shown in Table 1, and SEM observation photographs of Example 1 and Comparative Example 3 are shown in FIGS. 1 and 2, respectively. In Table 1, ST is styrene, AN is acrylonitrile, GMA is glycidyl methacrylate, MMA is methyl methacrylate, TDM is t-dodecyl mercaptan, NOM is n-octyl mercaptan, AMSD is α-methylstyrene dimer, AIBN is 2, Represents 2'-azobisisobutyronitrile.

(Examples 7 to 17 and Comparative Examples 10 to 20)
The graft copolymer (A) obtained in Reference Example 1, the vinyl copolymer (B) obtained in Reference Example 2, the polyethylene terephthalate resin obtained in Reference Example 3, and the epoxy groups shown in Tables 2 and 3 A pellet-shaped thermoplastic resin composition is prepared by mixing the vinyl-containing copolymer at a blending ratio shown in Tables 2 and 3 and melt-kneading at a cylinder set temperature of 260 ° C. using a vented 30 mm twin screw extruder. Manufactured. About the obtained thermoplastic resin composition, the result evaluated by the method as described in said (7)-(11) is shown to Tables 2-3.

  The thermoplastic resin compositions (Examples 7 to 17) of the present invention are all excellent in fluidity, and can provide molded articles excellent in impact resistance (Charpy impact strength and DuPont impact strength) and surface gloss. It was.

  In Comparative Example 10, no epoxy group-containing vinyl copolymer was added, and the impact resistance was inferior to Examples 7 to 17.

  Comparative Example 11 uses an epoxy group-containing vinyl copolymer having a weight average molecular weight of 60,000, but is inferior in impact resistance and surface gloss as compared with Examples 7-17. .

  In Comparative Example 12, an epoxy group-containing vinyl copolymer obtained by copolymerizing a vinyl monomer containing 40% by weight of a vinyl cyanide monomer was used. The impact and surface gloss were inferior and the yellowness was strong.

  Comparative Example 13 uses an epoxy group-containing vinyl copolymer obtained by copolymerizing a vinyl monomer containing 1% by weight of a vinyl monomer having an epoxy group, but is different from Examples 7-17. The impact resistance was inferior.

  Comparative Example 14 uses an epoxy group-containing vinyl copolymer obtained by copolymerizing a vinyl monomer containing 26% by weight of a vinyl monomer having an epoxy group, but is different from Examples 7 to 17. The fluidity, impact resistance and surface gloss were poor.

  Comparative Example 15 does not contain a vinyl cyanide monomer as a monomer component and uses the epoxy group-containing vinyl resin of Reference Example 4 which does not contain sulfur in the resin. Examples 7 to 17 Compared with, the DuPont impact strength was inferior.

  Comparative Examples 16 to 19 use an epoxy group-containing vinyl copolymer obtained by copolymerizing a vinyl monomer having a small content of an aromatic vinyl monomer and a vinyl cyanide monomer. Compared to Examples 7 to 17, the impact resistance was inferior.

  In Comparative Example 20, an epoxy group-containing vinyl copolymer containing no sulfur was used, but the DuPont impact strength and surface gloss were inferior to those of Examples 7-17.

(Examples 18-20, Comparative Examples 21-24)
Graft copolymer (A) obtained by Reference Example 1, vinyl copolymer (B) obtained by Reference Example 2, polyethylene terephthalate resin obtained by Reference Example 3, and epoxy group-containing vinyl shown in Table 4 The system copolymer was mixed at a blending ratio shown in Table 4 and melt-kneaded at a cylinder set temperature of 260 ° C. using a vented 30 mm twin screw extruder to produce a pellet-shaped thermoplastic resin composition. About the obtained thermoplastic resin composition, the result evaluated by the method as described in said (7)-(11) is shown in Table 4.

  The thermoplastic resin compositions (Examples 18 to 20) of the present invention are all excellent in fluidity, and can provide molded articles excellent in impact resistance (Charpy impact strength and Dupont impact strength) and surface gloss. It was.

  In Comparative Example 21, no epoxy group-containing vinyl copolymer was added, and the impact resistance was inferior to Examples 18-20.

  Comparative Example 22 uses an epoxy group-containing vinyl copolymer having a weight average molecular weight of 60000, but is inferior to Examples 18 to 20 in impact resistance and surface gloss. It was.

  Comparative Example 23 does not contain a vinyl cyanide monomer as a monomer component and uses the epoxy group-containing vinyl resin of Reference Example 4 which does not contain sulfur in the resin. Examples 18 to 20 Compared to the above, impact resistance and fluidity were inferior.

  Comparative Example 24 uses an epoxy group-containing vinyl copolymer obtained by copolymerizing a vinyl monomer having a small content of an aromatic vinyl monomer and a vinyl cyanide monomer. Compared with 18-20, the impact resistance was inferior.

Claims (7)

  At least aromatic vinyl monomer (a1) 55 to 88% by weight, vinyl cyanide monomer (a2) 10 to 35% by weight and epoxy group-containing vinyl monomer (a3) 2 to 25% by weight An epoxy group-containing vinyl copolymer having a weight average molecular weight of 11,000 to 50,000 and a sulfur content of more than 0.3% by weight. Polymer.   The method for producing an epoxy group-containing vinyl copolymer according to claim 1, wherein the vinyl monomer (a) is subjected to suspension polymerization.   A compatibilizing agent comprising the epoxy group-containing vinyl copolymer according to claim 1.   A thermoplastic resin composition comprising a styrenic resin (I), a polyester resin (II), and the epoxy group-containing vinyl copolymer according to claim 1, wherein the styrenic resin (I) and the polyester resin A thermoplastic resin composition comprising 0.01 to 2 parts by weight of the epoxy group-containing vinyl copolymer according to claim 1 with respect to a total of 100 parts by weight of (II).   50 to 99 parts by weight of styrene resin (I) and 1 to 55 parts by weight of polyester resin (II) with respect to a total of 100 parts by weight of styrene resin (I) and polyester resin (II), Item 5. The thermoplastic resin composition according to Item 4.   The thermoplastic resin composition according to claim 4 or 5, wherein the polyester resin (II) contains a polyethylene terephthalate resin.   The molded article which consists of a thermoplastic resin composition in any one of Claims 4-6.