JP2009227931A - Thermoplastic resin composition, and molding comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having both excellent heat resistance and excellent dimensional stability, and obtaining a molding excellent in molding workability and cost performance, and the molding comprising the same. <P>SOLUTION: This thermoplastic resin composition is blended with 3-10 pts.wt. fats and oils D having 50-200°C of melting point, with respect to 100 pts.wt. thermoplastic resin mixture mixed with 10-30 pts.wt. rubber-containing graft copolymer A, 45-50 pts.wt. vinyl copolymer B, and 5-40 pts.wt. maleimide copolymer C containing a maleimide monomer moiety within a range of 20-50 wt.%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition comprising a maleimide copolymer and a styrene thermoplastic resin containing fats and oils, having excellent heat resistance and dimensional stability, and excellent in moldability, and a molded article comprising the same. Is.

  Styrenic resins (ABS resins are included in styrene resins) are widely used in applications such as OA equipment and home appliances because they are excellent in mechanical strength and moldability.

  In recent years, with the downsizing, lightening, and integration of home appliances, resin parts are also required to be downsized and thinned. Naturally, such as polycarbonate, polyacetal, and polyamide that have high strength, excellent heat resistance and dimensional stability. Engineering plastics, and super engineering plastics such as polyetheretherketone and polyimide are increasingly used. These engineering plastics and super engineering plastics certainly have excellent characteristics, but there are many cases where the heat resistance and strength properties are too high and the performance is excessive, and there is a problem of high cost. Therefore, there is still a demand for higher functionality of inexpensive semi-engineering plastics such as styrene resins.

  As a technology for enhancing the functionality of styrene-based resins, a method of increasing strength, heat resistance and dimensional stability by adding glass fibers and inorganic fillers to styrene-based resins (see Patent Document 1), styrene-based resins. A method of stabilizing the size by adding fats and oils such as triglyceride (see Patent Documents 2 and 6) and a method of improving the heat distortion temperature by adding a maleimide copolymer to a styrene resin (Patent Document) 3, 4, 5 and 6) are proposed.

  However, in the resin composition obtained by adding glass fiber or powdered calcium carbonate proposed in Patent Document 1, problems such as high specific gravity have been pointed out along with a decrease in molding processability and impact resistance. . In addition, many of these resin compositions have poor sliding performance, and there are concerns about problems due to generation of particles, such as generation of wear powder and dropping of inorganic fillers when used in sliding portions.

  In addition, with respect to the resin composition obtained by adding the triglyceride proposed in Patent Document 2, when using a low melting point triglyceride, there may be a problem in mold dirtiness at the time of molding processing. Since there is no regulation in the intrinsic viscosity of the polymer and the flow characteristics of the obtained resin composition, there is a problem that it cannot always be suitably used in applications requiring dimensional stability.

  In the resin composition obtained by adding the maleimide copolymer proposed in Patent Documents 3 and 5, although the heat distortion temperature is certainly improved, the amount of maleimide copolymer added is generally large. It is considered that the viscosity is considerably high in the general molding temperature range of styrenic resins, and the relationship between the amount of maleimide copolymer added and flow characteristics and the effect on molding processability and dimensional stability are not specified and are unknown For example, there is a concern that warping due to molding distortion may be concerned, and that it cannot always be used appropriately in applications that require heat resistance, good molding processability and dimensional stability at the same time. .

  The resin composition proposed in Patent Document 4 is merely an expression that the maleimide copolymer can be compatible with the styrene resin, and the styrene thermoplasticity by containing the maleimide copolymer. No proposal has been made regarding the properties and functions of the resin.

In the resin composition obtained by adding animal oil and / or vegetable oil having a melting point of 50 ° C. or higher as proposed in Patent Document 6, maleimide monomer is used as a constituent of rubber-containing graft copolymer or vinyl cyanide copolymer. Although it is described that the monomer can be selected, as in the proposal of Patent Document 4, there is no proposal regarding the properties and functions of the styrene-based thermoplastic resin containing the maleimide-based copolymer.
Japanese Examined Patent Publication No. 44-7532 Japanese Patent Publication No.52-9699 JP 63-9544 A JP 04-38776 A JP 05-86105 A JP 2004-277467 A

  An object of the present invention is to solve the above-described conventional technical problems, and to provide a thermoplastic resin composition having excellent heat resistance and dimensional stability and excellent moldability, and a molded article comprising the same. It is to provide.

  As a result of intensive studies on the achievement of the above-mentioned object, the present inventors have found that a thermoplastic resin composition comprising a rubber-containing graft copolymer, a vinyl cyanide-based copolymer, a maleimide-based copolymer, and an oil and fat has a “heat resistance”. The present inventors have found that the above problems can be effectively solved by establishing a formulation and a manufacturing method that take into consideration the balance between `` dimensional stability, mechanical properties '' and `` flow characteristics, moldability ''. .

  The thermoplastic resin composition of the present invention comprises 10% to 90% by weight of an aromatic vinyl monomer (b) and 0% to 50% by weight of a vinyl cyanide monomer (c). And 10 to 30 parts by weight of a rubber-containing graft copolymer (A) obtained by graft copolymerization of 0 to 90% by weight of a copolymerizable vinyl monomer (d), an aromatic vinyl monomer (b 10 to 90% by weight, vinyl cyanide monomer (c) 0 to 50% by weight, and other copolymerizable vinyl monomers (f) except maleimide monomer (e) (0) to 90% by weight % Of vinyl copolymer (B) obtained by copolymerization of 45% by weight and maleimide copolymer (C) containing maleimide monomer (e) residues in the range of 20 to 50% by weight (C) ) To 100 parts by weight of a thermoplastic resin mixture obtained by mixing 5 to 40 parts by weight of Oil is to 200 DEG ° C. (D) a thermoplastic resin composition obtained by blending 3-10 parts by weight.

  According to a preferred embodiment of the thermoplastic resin composition of the present invention, the rubbery polymer (a) has a weight average particle diameter of 0.1 to 0.5 μm, and a rubber-containing graft copolymer (A The content of the rubbery polymer (a) is 20 to 80% by weight.

  According to a preferred embodiment of the thermoplastic resin composition of the present invention, the intrinsic viscosity [η] measured at a temperature of 30 ° C. of the methyl ethyl ketone soluble portion of the vinyl copolymer (B) is 0.25 to 0. In the range of .60 dl / g.

  According to a preferred embodiment of the thermoplastic resin composition of the present invention, the aromatic vinyl monomer (b) residue constituting the maleimide copolymer (C) is 10 to 60% by weight, vinyl cyanide. The monomer (c) residue is 0 to 20% by weight and the other vinyl monomer (d) residue is 0 to 20% by weight. N, N of the maleimide copolymer (C) The reduced viscosity ηsp / c measured at a temperature of 30 ° C. of the soluble part of dimethylformamide is in the range of 0.40 to 0.65 dl / g.

  The thermoplastic resin composition of the present invention can be molded into a molded product having an arbitrary shape by various molding methods.

  According to the present invention, excellent heat resistance (high load deflection temperature and high heat deformability) can be imparted to the styrene resin without using an inorganic filler due to the effect of the maleimide copolymer. In conventional methods, moldability is increased by increasing the amount of maleimide copolymer added or increasing the amount of maleimide monomer residues in the maleimide copolymer, resulting in increased viscosity of the thermoplastic resin composition. Dimensional stability is deteriorated, for example, the molding distortion caused by the deterioration is accelerated and warpage is caused. Therefore, in order to satisfy the heat resistance, dimensional stability and molding processability at the same time, the viscosity of the resulting thermoplastic resin can be controlled by using a low-viscosity vinyl cyanide copolymer in combination. Thereby, molding distortion due to viscosity is suppressed, and moldability and dimensional stability are improved. In addition, by using high melting point oils and fats, a thermoplastic resin composition having superior dimensional stability (low warpage and low molding shrinkage) can be obtained. The reason why the high melting point fat is used in a limited manner is that it is indispensable for suppressing volatilization during melt-kneading and for preventing mold contamination during injection molding.

  The thermoplastic resin composition obtained by the present invention is not only excellent in dimensional stability immediately after molding, but also can maintain sufficient heat resistance and dimensional stability in a heat generation environment of less than 100 ° C., It can also be used for applications that are difficult to use with conventional styrenic thermoplastic resins. For example, it can be suitably used as an interior / exterior resin component for home appliances that are becoming smaller, lighter and more integrated.

  In the thermoplastic resin composition of the present invention, the rubbery polymer (a) is added to the aromatic vinyl monomer (b), the vinyl cyanide monomer (c) and other copolymerizable vinyl monomers. Rubber-containing graft copolymer (A) obtained by graft copolymerization of monomer (d), aromatic vinyl monomer (b), vinyl cyanide monomer (c) and maleimide monomer ( Vinyl copolymer (B) obtained by copolymerizing other copolymerizable vinyl monomers (f) except e), maleimide monomer (e) residue and aromatic vinyl monomer (B) a maleimide copolymer (C) composed of a residue, a vinyl cyanide monomer (c) residue and another vinyl monomer (d) residue, and a melting point of 50 to 200 Use fats and oils (D) which is ° C.

  As the rubbery polymer (a) used in the rubber-containing graft copolymer (A), diene rubber, acrylic rubber, ethylene rubber, and the like can be preferably used.

  Specific examples of the rubbery polymer (a) include polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene-methyl methacrylate), Examples include poly (butyl acrylate-methyl methacrylate), poly (butadiene-ethyl acrylate), ethylene-propylene rubber, ethylene-propylene-diene rubber, poly (ethylene-isoprene), and poly (ethylene-methyl acrylate). . These rubbery polymers (a) can be used alone or in a mixture of two or more. Among these rubbery polymers (a), polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile) and ethylene-propylene rubber are particularly preferably used in terms of impact resistance.

  Specific examples of the aromatic vinyl monomer (b) used in the rubber-containing graft copolymer (A), vinyl copolymer (B) and maleimide copolymer (C) in the present invention include styrene. , Α-methylstyrene, o-methylstyrene, pt-butylstyrene, halogenated styrene and the like. These aromatic vinyl monomers (b) can be used alone or in combination of two or more. Among these aromatic vinyl monomers (b), styrene and α-methylstyrene are preferable, and styrene is more preferable.

  Specific examples of the vinyl cyanide monomer (c) used in the rubber-containing graft copolymer (A), vinyl copolymer (B) and maleimide copolymer (C) in the present invention include acrylonitrile and Examples include methacrylonitrile. These vinyl cyanide monomers (c) can be used alone or in combination of two or more. Among these vinyl cyanide monomers (c), acrylonitrile is particularly preferably used from the viewpoint of impact resistance.

  Specific examples of the other copolymerizable vinyl monomer (d) used in the rubber-containing graft copolymer (A) and the maleimide copolymer (C) in the present invention include methyl (meth) acrylate, ( (Meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate n-butyl, (meth) acrylate t-butyl, (meth) acrylate n-hexyl, (meth) acrylate cyclohexyl, ( Maleimide compounds such as (meth) acrylic acid ester compounds having 1 to 6 carbon atoms or substituted alkyl groups such as 2-chloroethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide and N-methylmaleimide , Unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic anhydrides such as maleic anhydride, and acrylamide Etc. can be mentioned unsaturated amide compounds. These other copolymerizable vinyl monomers (d) can be used alone or in combination of two or more.

  As the other copolymerizable vinyl monomer (f) used for the vinyl copolymer (B), a vinyl monomer other than the maleimide monomer can be used. Other specific examples of copolymerizable vinyl monomer (f) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, It has an alkyl group having 1 to 6 carbon atoms or a substituted alkyl group such as t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, etc. Examples thereof include (meth) acrylic acid ester compounds, unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic acid anhydrides such as maleic anhydride, and unsaturated amide compounds such as acrylamide. These other copolymerizable vinyl monomers (f) can be used alone or in combination of two or more.

  The maleimide copolymer (C) in the present invention includes a maleimide monomer (e), an aromatic vinyl monomer (b), a vinyl cyanide monomer (c), and other copolymerizable vinyls. Obtained by copolymerization of a monomer (f), or maleic anhydride, an aromatic vinyl monomer (b), a vinyl cyanide monomer (c) and other copolymerizable vinyl monomers It can be obtained by imidizing the copolymer of the body (d) with the primary amine (h).

  Specific examples of the maleimide monomer (e) used here include N-phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide. These maleimide monomers (e) can be used alone or in combination of two or more. Among these maleimide monomers (e), N-phenylmaleimide is particularly preferably used in terms of performance balance and productivity.

  Further, when imidizing a copolymer of maleic anhydride, aromatic vinyl monomer (b), vinyl cyanide monomer (c) and other copolymerizable vinyl monomer (d). Specific examples of the primary amine (h) used in the above include aniline, cyclohexylamine, methylamine and the like. At least one of these primary amines (h) can be used. Among these primary amines, aniline is particularly preferably used in terms of performance balance and productivity.

  The preferred composition of the thermoplastic resin mixture comprising the rubber-containing graft copolymer (A), vinyl copolymer (B) and maleimide copolymer (C) in the present invention is the rubber-containing graft copolymer (A). Is 10 to 30% by weight, more preferably 15 to 25% by weight, and the vinyl copolymer (B) is 45 to 85% by weight, more preferably 50 to 75% by weight. Moreover, regarding maleimide-type copolymer (C), it is 5 to 40 weight%, More preferably, it is the range of 10 to 35 weight%.

  The proportion of the rubber-containing graft copolymer (A) is 10% by weight based on the total amount of the rubber-containing graft copolymer (A) + vinyl copolymer (B) + maleimide copolymer (C). Or the ratio of the total amount of the vinyl copolymer (B) and the maleimide copolymer (C) is a rubber-containing graft copolymer (A) + vinyl copolymer (B) + When it exceeds 90% by weight with respect to the total amount of the maleimide copolymer (C), the impact strength is lowered.

The ratio of the rubber-containing graft copolymer (A) is 30 with respect to the total amount of the rubber-containing graft copolymer (A) + vinyl copolymer (B) + maleimide copolymer (C). Or the proportion of maleimide copolymer (C) exceeds the total amount of rubber-containing graft copolymer (A) + vinyl copolymer (B) + maleimide copolymer (C). If it exceeds 40% by weight, the melt viscosity increases and the molding processability deteriorates. Furthermore, in the case of a compound that deteriorates the moldability, the internal distortion of the molded body is promoted and the dimensional stability is lowered.
The ratio of the maleimide copolymer (C) exceeds 40% by weight with respect to the total amount of the rubber-containing graft copolymer (A) + vinyl copolymer (B) + maleimide copolymer (C). In this case, the impact performance of the obtained molded product is also lowered.

  The weight average particle diameter of the rubbery polymer (a) constituting the rubber-containing graft copolymer (A) used in the present invention is preferably in the range of 0.1 to 0.5 μm, more preferably 0. In the range of 2 to 0.4 μm. When the weight average particle diameter is in the above preferred range, the balance between impact resistance and moldability is good.

  The content of the rubbery polymer (a) in the rubber-containing graft copolymer (A) is preferably in the range of 20 to 80% by weight, more preferably in the range of 35 to 60% by weight. When the content of the rubber polymer (a) is within this range, the impact strength of the resulting thermoplastic resin composition does not decrease.

  The rubber-containing graft copolymer (A) used in the present invention contains 10 to 90% by weight of the aromatic vinyl monomer (b) as a composition ratio, and the preferred content is 20 to 80% by weight. is there. The rubber-containing graft copolymer (A) can contain a vinyl cyanide monomer (c) as necessary, and its content is 0 to 50% by weight, preferably 0 to 40%. % By weight. Furthermore, the rubber-containing graft copolymer (A) can contain other copolymerizable vinyl monomers (d) as required, and the content thereof is in the range of 0 to 90% by weight. , Preferably 0 to 80% by weight. In such a composition, the balance between impact resistance and moldability is good.

  The monomer mixture blended with the rubber-containing graft copolymer (A) does not have to be all grafted onto the rubbery polymer (a), and the monomers in the monomer mixture are bonded together. In addition, an ungrafted polymer may be contained. A preferable graft ratio is in the range of 10 to 100%, and more preferably in the range of 20 to 80%.

  Other than the aromatic vinyl monomer (b), vinyl cyanide monomer (c) and maleimide monomer (e) constituting the vinyl copolymer (B) used in the present invention. The composition ratio of the polymerizable vinyl monomer (f) includes 10 to 90% by weight of the aromatic vinyl monomer (b) in terms of balancing impact resistance and moldability. The preferred content is 20 to 80% by weight.

  Further, the vinyl copolymer (B) can contain a vinyl cyanide monomer (c) as required, and its content is 0 to 50% by weight, preferably 0 to 40%. % By weight. Furthermore, the vinyl copolymer (B) can contain other copolymerizable vinyl monomers (f) excluding the maleimide monomer (e), if necessary, It is 0 to 90% by weight, preferably 0 to 80% by weight. In such a preferred composition, the balance between impact resistance and moldability is good.

  The intrinsic viscosity [η] of the methyl ethyl ketone soluble component at 30 ° C. of the vinyl copolymer (B) used in the present invention is preferably in the range of 0.25 to 0.60 dl / g, more preferably. Is in the range of 0.30 to 0.45 dl / g. When the intrinsic viscosity [η] is within this range, the resulting thermoplastic resin composition has a good balance between the impact strength and the moldability. When the intrinsic viscosity [η] exceeds 0.60, the fluidity of the obtained thermoplastic resin is deteriorated, and the moldability and dimensional stability tend to be deteriorated.

  Maleimide monomer (e) residue constituting maleimide copolymer (C) used in the present invention, or maleimide monomer (e) equivalent part (imidation part of maleic anhydride with primary amine) Is also equivalent to a maleimide monomer (e) residue), an aromatic vinyl monomer (b) residue, a vinyl cyanide monomer (c) residue, and other copolymerizable vinyl systems. A preferable composition ratio of the monomer (d) residue is a maleimide monomer (e) residue or a maleimide monomer (e) equivalent part (maleic anhydride (f It is preferable that the imidized portion of the residue by the primary amine also corresponds to the maleimide monomer (e) residue) in an amount of 20 to 50% by weight, and a more preferable content is 22 to 40% by weight. .

  Further, from the viewpoint of ensuring dispersibility and moldability, it is preferable to contain 0 to 80% by weight of the aromatic vinyl monomer (b) residue, more preferably 30 to 60% by weight of the aromatic vinyl type. It contains the monomer (b) residue. If necessary, the vinyl cyanide monomer (c) residue and other copolymerizable vinyl monomer (d) residues are preferably contained in the range of 0 to 20% by weight, respectively. More preferably, it is in the range of 0 to 10% by weight. However, when other copolymerizable vinyl monomer (d) residue is derived from maleimide monomer (e), maleimide monomer (e) in maleimide copolymer (C) The residue should not exceed the range of 20-50% by weight.

  The amount of maleimide monomer (e) residue or maleimide monomer (e) residue equivalent part constituting maleimide copolymer (C) is maleimide monomer (e) + aromatic vinyl. Exceeds 50% by weight based on the total amount of monomer (b) + vinyl cyanide monomer (c) + other copolymerizable vinyl monomer (d), or aromatic vinyl monomer The total amount of the monomer (b) residue, vinyl cyanide monomer (c) residue and other copolymerizable vinyl monomer (d) residue is the maleimide monomer (e) + If it is less than 50% by weight based on the total amount of aromatic vinyl monomer (b) + vinyl cyanide monomer (c) + other copolymerizable vinyl monomer (d), the melt viscosity As a result, the moldability deteriorates. Furthermore, the internal distortion of a molded object is accelerated | stimulated by the deterioration of a moldability, and dimensional stability deteriorates.

  Further, the amount of the maleimide monomer (e) residue or the maleimide monomer (e) residue equivalent part constituting the maleimide copolymer (C) is the maleimide monomer (e) + aromatic Or less than 20% by weight based on the total amount of vinyl monomer (b) + vinyl cyanide monomer (c) + other copolymerizable vinyl monomer (d) The total amount of vinyl monomer (b) residue, vinyl cyanide monomer (c) residue and other copolymerizable vinyl monomer (d) residue is the maleimide monomer ( e) When exceeding 80% by weight with respect to the total amount of the aromatic vinyl monomer (b) + vinyl cyanide monomer (c) + other copolymerizable vinyl monomer (d) The effect of addition as a maleimide copolymer is reduced, and the thermoplastic resin composition finally obtained and the molded product comprising the same Heat (high deflection temperature under load, high thermal deformation resistance) is lowered.

  The reduced viscosity ηsp / c of the N, N-dimethylformamide soluble component at a temperature of 30 ° C. of the maleimide copolymer (C) used in the present invention is in the range of 0.40 to 0.65 dl / g. Is more preferable, and the range of 0.50 to 0.60 dl / g is more preferable. If the reduced viscosity ηsp / c is less than 0.40 dl / g, there is a concern that the heat resistance of the obtained thermoplastic resin composition will be insufficient, and if the reduced viscosity exceeds 0.65 dl / g, the resulting thermoplastic resin The fluidity of the composition decreases and the maleimide copolymer (C) is poorly dispersed, and the moldability, dimensional stability, and impact strength tend to decrease.

  In the production of the rubber-containing graft copolymer (A), vinyl copolymer (B) and maleimide copolymer (C) in the present invention, for example, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. This method can be used. As the monomer charging, methods such as initial batch charging, continuous charging of a part or all of the monomer, or partial charging of part and all of the monomer can be used.

  The fats and oils (D) used in the present invention are at least one kind of fats and oils such as fats and oils collected from animals and plants, for example, palm extremely hardened oil, soybean extremely hardened oil, rapeseed extremely hardened oil, and beef fat extremely hardened. Oil etc. are mentioned. The amount of these fats and oils (D) is based on 100 parts by weight of the thermoplastic resin mixture comprising the rubber-containing graft copolymer (A), the vinyl copolymer (B) and the maleimide copolymer (C). 3 to 10 parts by weight, preferably 6 to 8 parts by weight. When the blending amount of the oil (D) is less than 3 parts by weight, the dimensional stability of the obtained molded product is inferior.

  The melting point of the oil (D) used in the present invention is in the range of 50 to 200 ° C, preferably in the range of 55 to 180 ° C. When the melting point of the oil (D) is less than 50 ° C., the effect of addition decreases due to volatilization during melt-kneading, and the mold soiling property during molding increases. When the melting point of the oil (D) exceeds 200 ° C., it becomes difficult to melt and blend with the thermoplastic resin mixture, which is not preferable in terms of dispersibility.

  It is preferable that the melt flow rate (temperature 220 degreeC, 98N) calculated | required by ISO1133 conformity of the thermoplastic resin composition of this invention is 10-55 g / 10min, More preferably, it is 15-40 g / 10min. When the melt flow rate is less than 10 g / 10 min, the flowability is poor and the molding processability is deteriorated, the internal distortion of the molded product is promoted, and the dimensional stability tends to be lowered. In the present invention, when the melt flow rate exceeds 55 g / 10 min, the addition amount of the maleimide copolymer (C) is too small or the addition amount of the rubber-containing graft copolymer (A) is too small. Can happen. In such a case, either the impact resistance or the heat resistance tends to decrease.

  The thermoplastic resin composition of the present invention comprises a thermoplastic resin mixture comprising a rubber-containing graft copolymer (A), a vinyl copolymer (B) and a maleimide copolymer (C), and an oil (D). For example, it can be produced by melt-kneading with a Banbury mixer, roll, extruder, kneader, etc. In order to more properly melt and disperse the maleimide copolymer (C), a twin screw extruder is used. It is preferable to use and knead and manufacture.

  The thermoplastic resin composition of the present invention can be colored in any color tone by adding various dyes and pigments. In addition, an antioxidant such as a hindered phenol, sulfur-containing compound, or phosphorus-containing organic compound, a thermal stabilizer such as a phenol or acrylate, and benzoate may be added as necessary without departing from the object of the present invention. UV absorbers such as triazole, benzophenone or succinate, light stabilizers such as organic nickel and hindered amines, higher fatty acid metal salts, higher fatty acid amides, lubricants such as silicone, phthalates and phosphates Add various plasticizers such as brominated compounds, various flame retardants such as phosphoric acid esters or red phosphorus, flame retardant aids such as antimony trioxide and antimony pentoxide, and metal salts of alkylcarboxylic acids and alkylsulfonic acids can do. Moreover, when each component is acidic or basic, one or more neutralizing agents can be added.

  The thermoplastic resin composition of the present invention and a molded product comprising the thermoplastic resin composition are characterized by not containing an inorganic filler. However, in the case of static use without generation of wear powder, or generation of wear powder. In the case where is not a problem, various reinforcing agents and inorganic fillers can be added.

  The thermoplastic resin composition of the present invention obtained as described above is produced by known molding methods currently used for molding thermoplastic resins, such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding and gas assist molding. Can be molded.

  In order to describe the present invention more specifically, the present invention will be described below with reference to examples, but the present invention is not limited thereby.

(1) Weight average particle diameter (μm)
The weight average particle diameter of the rubber polymer (a) was determined by the sodium alginate method described in “Rubber Age Vol. 88 p484-490 (1990) by E. Schmidt, P.H. Biddison”. That is, using the fact that the diameter of the polybutadiene particles to be creamed differs depending on the concentration of sodium alginate, the particle size of 50% cumulative weight fraction was determined from the weight proportion of cream and the cumulative weight fraction of sodium alginate concentration.

(2) Graft rate (%)
Acetone is added to a predetermined amount [m] of the rubber-containing graft copolymer (A) and refluxed for 3 hours. The solution is centrifuged at 8800 rpm (10000 G) for 40 minutes, and the insoluble matter is collected by filtration. Was dried under reduced pressure for 5 hours at a temperature of 60 ° C., and the weight [n] was measured. The graft ratio was calculated by the following formula.
Graft rate = {[n− (m × L)] / m × L} × 100
(Wherein L is the rubber content of the graft copolymer).

(3) Reduced viscosity ηsp / c (dL / g) of maleimide copolymer (C)
A 0.4 g sample was dissolved and adjusted with a 100 ml solvent (N, N-dimethylformamide), and the reduced viscosity was determined using an Ubbelohde viscometer.

(4) Intrinsic viscosity [η] (dL / g) of vinyl polymer (B)
Samples were dissolved in a solvent (methyl ethyl ketone), solutions having different concentrations were prepared, reduced viscosity ηsp / c was determined using an Ubbelohde viscometer, and the concentration was extrapolated to 0 to determine intrinsic viscosity [η].

(5) Charpy impact strength (kJ / m ² )
Measurement was performed in accordance with ISO 179 standards (2000) (temperature 23 ° C., with V notch).

(6) Bending strength / elastic modulus (MPa)
Measurement was performed in accordance with ISO 178 regulations (2000).

(7) Deflection temperature under load (℃)
It was measured (load: 1.8 MPa) in conformity with ISO75 standard (2000).

(8) Melt flow rate (g / 10 min)
Measurement was performed in accordance with ISO 1133 regulations (2000) (temperature 220 ° C., load 98 N).

(9) Mold fouling (mg / 15g)
After drying the pellets of the thermoplastic resin composition to an equilibrium moisture content (temperature 90 ° C., 3 hours or more), a flat mold (lower mold) is placed on a heating plate set at a temperature of 270 ° C. 15 g of sample pellets are weighed, and the sample pellets are laid flat on the lower mold. An upper mold is placed on the pellet on the lower mold (a spacer is inserted so that the distance between the lower mold and the upper mold is 4 mm), and then heated at a temperature of 270 ° C. for 10 minutes. After the heat treatment for 10 minutes, the bleedout material captured by the upper mold is collected and weighed to obtain the bleedout amount. The greater the bleed-out amount, the greater the mold dirtiness.

(10) Mold shrinkage (%)
The mold shrinkage rate measurement square plate shown in FIG. 1 is molded with a mold having a fan gate measuring 240 mm in length, 70 mm in width and 3 mm in thickness at a cylinder set temperature of 250 ° C. and a mold temperature of 60 ° C. Then, the dimension in the direction perpendicular to the flow direction of the resin was measured with calipers, and the molding shrinkage was calculated.

(11) Warpage (mm)
A tray-shaped molded product is molded at a cylinder set temperature of 250 ° C. and a mold temperature of 60 ° C. with an injection molding machine, and the molded product is conditioned at a temperature of 23 ° C. and a humidity of 50% for 24 hours in an atmosphere. After adjusting the state, place a tray-shaped molded product on the surface plate, fix the points A and B shown in FIG. 2 in close contact with the surface plate, and use a three-dimensional measuring machine (manufactured by Mitutoyo Corporation) Warpage was evaluated by measuring the vertical dimension from the surface plate to point C. The smaller the gap from the surface plate to point C, the better the low warpage.

(12) Thermal deformation (mm)
A tray-shaped molded article with a clear warpage amount used in the evaluation of warpage is allowed to stand in a hot air oven maintained at a temperature of 65 ° C. for 24 hours, allowed to cool to 23 ° C., and then points A and B shown in FIG. Fix the point in close contact with the surface plate, and use a 3D measuring machine (Mitutoyo Co., Ltd.) to measure the vertical dimension from the surface plate to the point C, that is, to some extent after forming to condition adjustment. By measuring the movement of further dimensions in the vertical direction from the running state, the thermal deformability was evaluated.

  Even if it is not a tray-shaped molded product, it is possible to evaluate thermal deformation. A strip-shaped test piece (length 170 mm × width 10 mm × thickness 4 mm) or an ISO tensile test piece is molded at a cylinder set temperature of 250 ° C. and a mold temperature of 60 ° C. with an injection molding machine. Condition for 24 hours in a 50% atmosphere. After the condition adjustment, the cantilever shown in FIG. 3 was created, and the multistage system was maintained at a temperature of 65 ° C. in a no-load state and with a concentrated load of 31.5 g at a position 135 mm from the fixed end. After leaving still in a hot air oven for 24 hours and allowing to cool to a temperature of 23 ° C., the warp amount of the test piece is measured to evaluate thermal deformability. The evaluation result when the concentrated load was applied was similar in tendency to the thermal deformation evaluation result of the tray-shaped molded product.

[Reference Example 1] Method for Producing Rubber-Containing Graft Copolymer (A) (1) Method for Producing Rubber-Containing Graft Copolymer (A-1) In a reactor purged with nitrogen, 120 parts by weight of pure water, 0. 5 parts by weight, sodium pyrophosphate 0.5 parts by weight, ferrous sulfate 0.005 parts by weight and polybutadiene latex (rubber particle diameter 0.3 μm, gel content 85%) 60 parts by weight (in terms of solid content) were charged. While stirring, the temperature in the reactor was raised to 65 ° C. When the temperature reached 65 ° C., a monomer mixture consisting of a monomer mixture (30 parts by weight of styrene and 10 parts by weight of acrylonitrile) and 0.3 part by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours. At the same time, a mixture of 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate and 25 parts of pure water was continuously added dropwise over 7 hours to complete the monomer reaction.

  The obtained styrene copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a rubber-containing graft copolymer (A-1). The graft ratio of this rubber-containing graft copolymer (A-1) was 35%.

[Reference Example 2] Method for Producing Vinyl Copolymer (B) (1) Method for Producing Vinyl Copolymer (B-1) A monomer mixture composed of 76% by weight of styrene and 24% by weight of acrylonitrile is suspended. Polymerization was performed to obtain a vinyl copolymer (B-1). The intrinsic viscosity [η] of methyl ethyl ketone-soluble matter at a temperature of 30 ° C. of the obtained vinyl copolymer (B-1) was 0.42 dl / g.

(2) Production Method of Vinyl Copolymer (B-2) A monomer mixture comprising 70% by weight of styrene and 30% by weight of acrylonitrile is continuously bulk polymerized to obtain a vinyl copolymer (B-2). It was. The intrinsic viscosity [η] of methyl ethyl ketone soluble matter at 30 ° C. of the obtained vinyl copolymer (B-2) was 0.45 dl / g.

(3) Method for producing vinyl copolymer (B-3) A monomer mixture comprising 72% by weight of styrene and 28% by weight of acrylonitrile is continuously bulk polymerized to obtain a vinyl copolymer (B-3). It was. The intrinsic viscosity [η] of the methyl ethyl ketone-soluble component at a temperature of 30 ° C. of the obtained vinyl copolymer (B-3) was 0.53 dl / g.

(4) Method for producing vinyl copolymer (B-4) A monomer mixture consisting of 72% by weight of styrene and 28% by weight of acrylonitrile is subjected to suspension polymerization to obtain a vinyl copolymer (B-4). It was. The intrinsic viscosity [η] of the methyl ethyl ketone-soluble matter at 30 ° C. of the obtained vinyl copolymer (B-4) was 0.85 dl / g.

[Reference Example 3] Method for Producing Maleimide Copolymer (C) (1) Method for Producing Maleimide Copolymer (C-2) In a reactor purged with nitrogen, 160 parts pure water, 0.6 sodium lauryl sulfate, and 0.5 parts of potassium persulfate was charged, and the temperature in the reactor was raised to 70 ° C. while stirring. When the temperature of the reaction system reached 70 ° C., polymerization was started, and a mixed solution consisting of 30 parts of N-phenylmaleimide, 19 parts of acrylonitrile, 50 parts of styrene and 0.3 part of t-dodecyl mercaptan was continuously added dropwise over 9 hours. Thereafter, 1 part of acrylonitrile was continuously added dropwise over 1 hour. In parallel with this, 3 parts of sodium lauryl sulfate was continuously dropped in an aqueous solution over 12 hours from the start of polymerization. Further, 0.1 part of potassium persulfate was added 10 hours after the start of polymerization, and 0.01 part of potassium persulfate was added 11 hours later. The temperature of the reaction solution was maintained at 70 ° C. for 10 hours from the start of polymerization, then heated to 80 ° C. and maintained for 2 hours to complete the reaction.

  The obtained maleimide copolymer latex was coagulated with magnesium sulfate, washed with water, filtered and dried to obtain a powdery maleimide copolymer (C-2). The obtained maleimide copolymer (C-2) had an N-phenylmaleimide residue of 30% by weight and a reduced viscosity ηsp / c of 0.58 dl / g.

[Examples 1 to 13]
The following rubber-containing graft copolymers (A), vinyl copolymers (B), maleimide copolymers (C) and fats and oils (D) were blended at the blending ratios shown in Tables 1 and 2, respectively. Using a vented 30 mmφ twin screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.), melt-kneading was performed at a cylinder temperature of 250 ° C., and extrusion was performed to produce a pellet-shaped thermoplastic resin composition.
Rubber-containing graft copolymer (A-1): rubber-like polymer (a) having a weight average particle diameter of 0.3 μm, a content of 45% by weight, and a graft ratio of 35%
Vinyl copolymer (B-1): 76% by weight of styrene, 24% by weight of acrylonitrile, intrinsic viscosity [η] 0.42 dl / g
Vinyl copolymer (B-2): 70% by weight of styrene, 30% by weight of acrylonitrile, intrinsic viscosity [η] 0.45 dl / g
Vinyl copolymer (B-3): 72% by weight of styrene, 28% by weight of acrylonitrile, intrinsic viscosity [η] 0.53 dl / g
-Maleimide copolymer (C-1): "Polyimilex" (registered trademark) PAS1460, manufactured by Nippon Shokubai Co., Ltd., 38% by weight of N-phenylmaleimide residue, reduced viscosity ηsp / c: 0.56 dl / g
Maleimide copolymer (C-2): N-phenylmaleimide residue 30% by weight, reduced viscosity ηsp / c: 0.58 dl / g
・ Oil (D-1): Palm extremely hardened oil (melting point: 58 ° C.)
・ Oil (D-2): soybean hardened oil (melting point: 68 ° C.)
・ Oil (D-3): Rapeseed extremely hardened oil (melting point 61 ° C.)
・ Oil (D-4): Beef tallow extremely hardened oil (melting point 61 ° C)
・ Oil (D-5): Pork fat extremely hardened oil (melting point: 58 ° C)
Next, a test piece was molded from the thermoplastic resin composition obtained as described above at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine, and the characteristics were evaluated. The results are shown in Table 1 and Table 2 together.

[Comparative Examples 1 to 11]
The following rubber-containing graft copolymers (A), vinyl copolymers (B), maleimide copolymers (C) and fats and oils (D) were blended at the blending ratios shown in Tables 3 and 4, respectively. Using a vented 30 mmφ twin screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.), melt-kneading was performed at a cylinder temperature of 250 ° C., and extrusion was performed to produce a pellet-shaped thermoplastic resin composition.
Rubber-containing graft copolymer (A-1): rubber-like polymer (a) having a weight average particle diameter of 0.3 μm, a content of 45% by weight, and a graft ratio of 35%
Vinyl copolymer (B-1): 76% by weight of styrene, 24% by weight of acrylonitrile, intrinsic viscosity [η] 0.42 dl / g
Vinyl copolymer (B-2): 70% by weight of styrene, 30% by weight of acrylonitrile, intrinsic viscosity [η] 0.45 dl / g
Vinyl copolymer (B-4): 72% by weight of styrene, 28% by weight of acrylonitrile, intrinsic viscosity [η] 0.85 dl / g
-Maleimide copolymer (C-1): "Polyimilex" (registered trademark) PAS1460, manufactured by Nippon Shokubai Co., Ltd., 38% by weight of N-phenylmaleimide residue, reduced viscosity ηsp / c: 0.56 dl / g
・ Oil (D-1): Palm extremely hardened oil (melting point: 58 ° C.)
・ Oil (D-2): soybean hardened oil (melting point: 68 ° C.)
・ Oil (D-3): Rapeseed extremely hardened oil (melting point 61 ° C.)
・ Oil (D-6): Eggplant oil (melting point: 44 ° C.)
・ Oil (D-7): Linseed oil (melting point -10 ° C)
・ Oil (D-8): Tallow (melting point 35 ° C)
・ Oil (D-9): Pork fat (melting point 40 ° C)
Next, a test piece was molded from the thermoplastic resin composition obtained as described above using an injection molding machine at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and the characteristics were evaluated. The results are shown in Table 3 and Table 4 together.

[Comparative Example 12]
The following rubber-containing graft copolymer (A), maleimide copolymer (C), and fat (D) are blended at the blending ratio shown in Table 4, and a 30 mmφ twin screw extruder with a vent (Corporation) A pellet-shaped thermoplastic resin composition was manufactured by melt-kneading at a cylinder temperature of 280 ° C. and performing extrusion using Ikekai PCM-30).
Rubber-containing graft copolymer (A-1): rubber-like polymer (a) having a weight average particle diameter of 0.3 μm, a content of 45% by weight, and a graft ratio of 35%
-Maleimide copolymer (C-1): "Polyimilex" (registered trademark) PAS1460, manufactured by Nippon Shokubai Co., Ltd., 38% by weight of N-phenylmaleimide residue, reduced viscosity ηsp / c: 0.56 dl / g
・ Oil (D-2): soybean hardened oil (melting point: 68 ° C.)
Next, a test piece was molded from the thermoplastic resin composition obtained as described above using an injection molding machine at a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C., and the characteristics were evaluated. The results are also shown in Table 4.

  From the results of Tables 1 to 4, the following is clear. That is, all of the thermoplastic resin compositions of Examples 1 to 13 of the present invention have heat resistance (high load deflection temperature, high heat deformability), moldability and dimensional stability (low molding shrinkage, low warpage). It was excellent.

  On the other hand, Comparative Examples 1 and 2 in which the fat (D) and the maleimide copolymer (C) are not added are highly elastic due to the effect of the vinyl copolymer (B), and at first glance, they are excellent in heat resistance. Since the maleimide copolymer (C) was not contained, the heat deformability under load was inferior. In addition, when the oil (D) is not added, the molding shrinkage rate and warping amount are large, the dimensional stability is poor, and when the vinyl copolymer (B) reaches 85 parts (Comparative Example 1) Although the elasticization further progressed, the toughness was lowered correspondingly, and the impact performance was extremely deteriorated.

  In Comparative Example 3 in which the maleimide copolymer (C) is not added, a low molding shrinkage rate and low warpage are realized by the effect of addition of the fat (D), but the deflection temperature under load is low and thermal deformation is caused. The heat resistance was not good.

  In Comparative Example 4 in which the amount of oil (D) added was insufficient, the molding shrinkage ratio was increased and the dimensional stability was not good.

  In Comparative Example 5 in which the amount of oil (D) added was excessive, mold stains were remarkably generated and the moldability was poor.

  In Comparative Example 6 in which the amount of maleimide copolymer (C) added is insufficient, the tendency of defects is the same as in Comparative Example 3, and heat resistance is insufficient.

  In Comparative Example 7 in which the amount of maleimide copolymer (C) added is excessive, the melt flow rate is greatly reduced due to the influence of the high viscosity maleimide copolymer (C), and the molding processability is deteriorated. The warping property deteriorated and the molding shrinkage rate was not good. Moreover, the impact performance was reduced. This resulted in a small amount of cantilever deformation, but this was not released in a temperature environment of about 65 ° C. due to the heat resistance improved by the effect of the maleimide copolymer (C). Due to that.

  In Comparative Examples 8 to 11 in which the oil and fat (D) had a melting point of less than 50 ° C., mold stains were remarkably generated as in Comparative Example 6 without adding excessive amounts, and the moldability deteriorated. .

  Comparative Example 12 to which no vinyl copolymer (B) has been added is a thermoplastic resin described in Patent Document 6, but since this does not contain vinyl cyanide copolymer (B), the temperature is 220. Under the conditions of 98 ° C. and 98 N, it did not melt and flow, and the melt flow rate was not measurable. According to Patent Document 6, the thermoplastic resin having the composition should have a melt flow rate of 40 g / 10 min or more under the conditions of a temperature of 220 ° C. and 98 N, but this is clearly not satisfied. Further, Comparative Example 12 was difficult to mold unless the molding temperature was 265 ° C. or higher. Moreover, since the molding temperature was high, mold contamination due to volatilization of the added oil and fat was also confirmed. Regarding physical properties, although high elasticity and heat resistance were realized, the impact performance was extremely poor and fragile. Further, the warpage due to molding distortion was also large.

FIG. 1 is a schematic plan view and a schematic side view of a square plate for measuring molding shrinkage rate. FIG. 2 is a schematic plan view and a schematic side view of a tray-shaped molded product for measuring warpage and thermal deformability. FIG. 3 is a schematic plan view and a schematic side view for explaining a test apparatus using a cantilever for measuring thermal deformability.

Explanation of symbols

[Figure 1]
AA: Dimension measurement position in the resin flow direction of the molded body BB: Dimension measurement position in the direction perpendicular to the resin flow direction of the molded body (gate side)
CC: Dimension measurement position in the direction perpendicular to the resin flow direction of the molded body (on the opposite gate side)
[Figure 2]
Point A: Molded part end (gate side) to be in close contact with the surface plate during warpage measurement
Point B: End of the molded product that is in close contact with the surface plate when measuring warpage (on the opposite side of the gate)
Point C: When measuring warpage, measure the distance from the surface plate and use it as the amount of warpage

Claims (5)

  A rubbery polymer (a), aromatic vinyl monomer (b) 10 to 90% by weight, vinyl cyanide monomer (c) 0 to 50% by weight and other copolymerizable vinyl monomers 10 to 30 parts by weight of rubber-containing graft copolymer (A) obtained by graft copolymerization of 0 to 90% by weight of body (d), 10 to 90% by weight of aromatic vinyl monomer (b), vinyl cyanide A vinyl copolymer prepared by copolymerizing 0 to 50% by weight of the monomer (c) and other copolymerizable vinyl monomer (f) excluding the maleimide monomer (e) Heat in which 45 to 85 parts by weight of polymer (B) and 5 to 40 parts by weight of maleimide copolymer (C) containing maleimide monomer (e) residue in the range of 20 to 50% by weight were mixed. Oil and fat (D) having a melting point of 50 to 200 ° C. with respect to 100 parts by weight of the plastic resin mixture The thermoplastic resin composition obtained by 10 parts by weight.   The weight average particle diameter of the rubber polymer (a) is 0.1 to 0.5 μm, and the content of the rubber polymer (a) in the rubber-containing graft copolymer (A) is 20 to 80. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is in wt%.   The thermoplastic resin according to claim 1 or 2, wherein the intrinsic viscosity [η] measured at a temperature of 30 ° C of the methyl ethyl ketone soluble part of the vinyl copolymer (B) is in the range of 0.25 to 0.60 dl / g. Composition.   The aromatic vinyl monomer (b) residue constituting the maleimide copolymer (C) is 10 to 60% by weight, the vinyl cyanide monomer (c) residue is 0 to 20% by weight, and The other vinyl monomer (d) residue is 0 to 20% by weight, and the N, N-dimethylformamide soluble content of the maleimide copolymer (C) is measured at a temperature of 30 ° C. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the viscosity ηsp / c is in the range of 0.40 to 0.65 dl / g.   The molded article which consists of a thermoplastic resin composition in any one of Claims 1-4.

Images