JP5505587B2 - Resin composition, matting agent, thermoplastic resin composition containing the same, and resin molded article formed by molding the same - Google Patents

Description

  The present invention relates to a resin composition that gives a resin molded article having high matteness, weather resistance, and light color, a matting agent comprising the resin composition, a thermoplastic resin composition containing the resin composition, and molding the same. It is related with the resin molding which becomes.

  AS resin, ABS resin, polycarbonate resin, and polyester resin are used as raw materials for OA equipment, home appliances, camera housings, automobile interior materials, and the like because of their excellent mechanical properties. These resin moldings often need to have a matte appearance to provide an elegant and soothing visual effect. Conventionally, in order to meet this requirement, a resin composition having excellent matting properties has been used as a raw material for molded articles. As a resin composition excellent in matting properties, it comprises (1) a rubber component containing an acrylonitrile-styrene resin and (2) an unsaturated nitrile-conjugated diene polymer rubber, and the (2) rubber component is formed by a crosslinking agent. A cross-linked resin composition has been studied (for example, see Patent Document 1). (1) an acrylonitrile-styrene resin, (2) an unsaturated nitrile-conjugated diene polymer rubber and / or a rubber component containing a rubber in which a carbon-carbon double bond portion of the rubber is hydrogenated, A resin composition comprising a resin in which a rubber component is cross-linked and (3) a resin that can be mixed with the acrylonitrile-styrene resin has also been studied (see, for example, Patent Document 2). Further, (1) a resin, (2) a polymer component comprising an epoxy group or carboxyl group-containing acrylic rubber, and (3) a resin composition comprising a crosslinking agent are heat-kneaded, and (2) the component is dynamically vulcanized. The resin which becomes is examined (for example, refer to Patent Document 3).

In recent years, there has been a demand for a resin composition that provides a resin molded article having weather resistance for making it difficult to discolor for a long period of time, and light-coloring properties for facilitating easy toning, in addition to a highly matte appearance. However, such a resin composition has not been found.
JP-A-62-221148 Japanese Patent Laid-Open No. 3-12440 Japanese Patent Laid-Open No. 8-151502

  The problem to be solved by the present invention is to provide a resin composition that gives a resin molded article having high matteness, weather resistance and light color, a matting agent comprising the resin composition, and a thermoplastic resin composition containing the same. And a resin molded body obtained by molding the same.

The inventor of the present invention has intensively studied to solve the above problems, and as a result, the ethylenically unsaturated nitrile-aromatic vinyl copolymer, the aromatic vinyl-conjugated diene copolymer, and the alkyl group is at least one of the aromatic rings. A resin composition obtained by dynamically vulcanizing a polymer composition containing a hydrogenated aromatic vinyl-conjugated diene copolymer bonded to a part and an organic peroxide crosslinking agent solves the above problem. The headline and the present invention have been completed.

According to the present invention, (a) ethylenically unsaturated nitrile-aromatic vinyl copolymer 40-70% by mass, (b) aromatic vinyl-conjugated diene copolymer 10-40% by mass and (c) alkyl group 100 parts by mass of a polymer component comprising 5 to 50% by mass of a hydride of an aromatic vinyl-conjugated diene copolymer in which is bonded to at least a part of the aromatic ring, and 0.05 to 5% by mass of an organic peroxide crosslinking agent A resin composition obtained by dynamically vulcanizing a polymer composition containing parts is provided. Moreover, it is preferable that the said polymer composition contains the crosslinking agent which has more than 0.5-10 mass parts carbon-carbon double bond in 1 molecule with respect to 100 mass parts of polymer components further.
Moreover, according to this invention, the matting agent which consists of the said resin composition is provided.
Furthermore, according to this invention, the thermoplastic resin composition which comprises 2-10 mass parts of said matting agents with respect to 100 mass parts of thermoplastic resins is provided.
Furthermore, according to this invention, the resin molding formed by shape | molding the said thermoplastic resin composition is provided.

  The resin composition of the present invention provides a resin molded article having high matteness, weather resistance and light color.

  Specific examples of the (a) ethylenically unsaturated nitrile-aromatic vinyl copolymer constituting the resin composition of the present invention are copolymer resins of acrylonitrile and styrene or α-methylstyrene called AS resin; Impact-resistant resin in which AS resin is grafted to dispersed polybutadiene rubber particles called ABS resin [For example, edited by Polymer Society, Polymer Data Handbook, ABS resin, pp. 39-44 (Showa 61) (May 30 May issue) ”(Note that“ ethylenically unsaturated nitrile-aromatic vinyl-conjugated diene copolymer ”refers to a broader concept copolymer including an ABS resin as defined above.) A weather-resistant / impact-resistant resin in which an acrylonitrile-styrene copolymer is partially grafted on an acrylic rubber called an AAS or ASA resin; called an AES resin , And the like; EPDM styrene copolymer grafted partially weatherability and impact resin (ethylene - propylene - - diene copolymer rubber) acrylonitrile. These may be used alone or in combination of two or more. The copolymerization ratio of the ethylenically unsaturated nitrile and the aromatic vinyl is ethylenically unsaturated nitrile / aromatic vinyl = 5 to 95/95 to 5 (mass ratio).

The (b) aromatic vinyl-conjugated diene copolymer constituting the resin composition of the present invention is an aromatic vinyl such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene. Obtained by random or block copolymerization of at least one compound and at least one conjugated diene such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, isoprene, and 1,3-pentadiene. Random copolymer or block copolymer. Specific examples of the random copolymer include styrene-butadiene copolymer rubber (SBR), styrene-isoprene copolymer rubber (SIR), and styrene-butadiene-isoprene copolymer rubber (SBIR). Specific examples of the block copolymer are ABA type linear and radial block copolymers (A is a polystyrene block, B is a polybutadiene block and / or a polyisoprene block).
(B) The copolymerization ratio of aromatic vinyl and conjugated diene in the aromatic vinyl-conjugated diene copolymer is usually aromatic vinyl / conjugated diene = 5 to 95/95 to 5 (mass ratio), preferably 15 to 35/85 to 65 (mass ratio). By setting it as the said preferable range, dynamic vulcanization advances effectively and the matting effect of the matting agent obtained becomes high.
(B) The Mooney viscosity (ML _{1 + 4} , 100 ° C.) in the aromatic vinyl-conjugated diene copolymer is preferably 30 to 70, more preferably 40 to 65. By setting it as the said preferable range, kneading | mixing is performed smoothly and dynamic vulcanization | cure becomes easy to advance effectively.

(C) a hydride of an aromatic vinyl-conjugated diene copolymer in which an alkyl group constituting the resin composition of the present invention is bonded to at least a part of an aromatic ring (hereinafter referred to as “alkyl-modified aromatic vinyl-conjugated diene”). The hydride of the copolymer ") has a structure in which hydrogen is bonded to a carbon atom bonded to at least a part of the aromatic ring. (C) The hydride of an alkyl-modified aromatic vinyl-conjugated diene copolymer preferably has a reactive group that undergoes a crosslinking reaction or a crosslinking reactive bond. Here, as a reactive group which performs a crosslinking reaction, for example, a group having a carbon-carbon double bond such as a vinyl group or an allyl group; a group having an epoxy such as a glycidyl group; a carboxyl group; a hydroxyl group; an isocyanur group; A tertiary alkyl group in which hydrogen is bonded to a tertiary carbon ; and the like. Examples of the crosslinking reactive bond include a carbon-carbon double bond; a carbon-oxygen double bond; a carbon-nitrogen double bond; a carbon-carbon triple bond; Among these, a tertiary alkyl group in which hydrogen is bonded to a tertiary carbon is particularly preferable.

  The aromatic block in the aromatic vinyl-conjugated diene block copolymer which is a preferred embodiment of the aromatic vinyl-conjugated diene copolymer is alkyl-modified by adding a styrene unit and an alkyl group having 1 to 8 carbon atoms. And styrene units. In addition, among said C1-C8 alkyl groups, a C1-C4 alkyl group is more preferable, a methyl group and an ethyl group are still more preferable, and a methyl group is especially preferable. The aromatic block is most preferably one obtained by copolymerizing styrene and p-methylstyrene.

  (C) Examples of hydrides of alkyl-modified aromatic vinyl-conjugated diene copolymers include styrene-ethylene-butene-styrene block copolymers (alkyl-modified SEBS) in which at least a part of styrene units is alkyl-modified. ); A styrene-ethylene-propylene-styrene block copolymer (alkyl-modified SEPS) in which at least a part of the styrene unit is alkyl-modified; (S: styrene, E: ethylene, B: butene, P: propylene, respectively) Abbreviations). The hydride of the above-mentioned (c) alkyl-modified aromatic vinyl-conjugated diene copolymer is preferably 80 to 99.9 mol% of unsaturated double bonds in the polymer chain, more preferably 90 to 99.9. The mol%, more preferably 95-99.9 mol% is hydrogenated.

  Hydrogenated alkyl-modified aromatic vinyl-conjugated diene copolymers are commercially available, and specific examples thereof include Kuraray Septon V9461.

A preferable mixing ratio of (a) to (c) constituting the resin composition of the present invention is (a) / (b) / (c) = 40 to 70/10 to 40/5 to 50 (mass ratio). is there. (A) a matting agent obtained by dynamically vulcanizing a mixture of (a), (b) and (c) when the amount of the ethylenically unsaturated nitrile-aromatic vinyl copolymer is too small; When mixing with a thermoplastic resin, a matting agent becomes difficult to mix uniformly and possibility that a matting effect may become small arises. On the other hand, even if the amount of the (a) ethylenically unsaturated nitrile-aromatic vinyl copolymer is excessive, the matting effect of the matting agent obtained is reduced.
In addition, when the amount of the (b) aromatic vinyl-conjugated diene copolymer is too small, the dynamic vulcanization is difficult to proceed when producing the matting agent, and the matting effect of the matting agent obtained is It gets smaller. On the other hand, if the amount of the (b) aromatic vinyl-conjugated diene copolymer is excessive, the resulting matting agent is inferior in heat resistance, and the resulting resin molded product has a large color difference after heat treatment.
Furthermore, when the amount of the hydride of the (c) alkyl-modified aromatic vinyl-conjugated diene copolymer is too small, the color difference of the resulting resin molded product tends to increase. On the other hand, when the amount of the hydride of (c) alkyl-modified aromatic vinyl-conjugated diene copolymer is excessive, dynamic vulcanization tends to be difficult to proceed when producing a matting agent.

  The resin composition of the present invention is obtained by dynamically vulcanizing a polymer composition containing 100 parts by mass of the polymer components (a) to (c) and 0.05 to 5 parts by mass of an organic peroxide crosslinking agent. Obtained. Specific examples of the organic peroxide crosslinking agent include dicumyl peroxide, bis (t-butyldioxyisopropyl) benzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane, 2 , 5-dimethyl-2,5-di- (t-butylperoxy) -hexyne-3. When the addition amount of the organic peroxide crosslinking agent is too small, dynamic vulcanization cannot be performed sufficiently. If the addition amount of the organic peroxide crosslinking agent is excessive, the impact resistance of the resin molded product formed by molding the thermoplastic resin composition is lowered. The preferable addition amount with respect to 100 parts by mass of the polymer component of the organic peroxide crosslinking agent is 0.1 to 2 parts by mass, and the more preferable addition amount is 0.2 to 1 part by mass.

  The above polymer composition may be obtained by mixing the organic peroxide crosslinking agent and the polymer component comprising the above (a) to (c), and diluted rubber and / or resin such as acrylic rubber, lubricant, and organic peroxide. You may obtain the said polymer composition by mixing the polymer component which consists of a mixture containing an oxide crosslinking agent and said (a)-(c).

  In addition to the polymer component consisting of the above (a) to (c) and the organic peroxide cross-linking agent, the polymer composition contains 0.5 to 10 parts by mass of carbon-carbon two to 100 parts by mass of the polymer component. What comprises the crosslinking agent which has two or more heavy bonds in 1 molecule is preferable. Specific examples of the crosslinking agent having a plurality of carbon-carbon double bonds in one molecule include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate An unsaturated carboxylic acid diester of a polyalcohol such as polyethylene glycol di (meth) acrylate; a compound having three vinyl groups such as trimethylolpropane tri (meth) acrylate and ethylene oxide-modified trimethylolpropane tri (meth) acrylate; Compounds having four or more vinyl groups, such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexaacrylate; Among them, unsaturated carboxylic acid diesters of polyalcohols and compounds having four or more vinyl groups are preferred, polyethylene glycol di (meth) acrylate and pentaerythritol tetra (meth) acrylate are particularly preferred, and pentaerythritol tetra (meth) acrylate is preferred. Most preferred. By using the preferred cross-linking agent having a plurality of carbon-carbon double bonds in one molecule, the matting effect of the matting agent obtained is improved.

A polymer component comprising the above (a) to (c), a mixture containing a perorganic oxide crosslinker or an organic peroxide crosslinker, and a crosslink having a plurality of carbon-carbon double bonds in one molecule as necessary. So-called “dynamic vulcanization” in which a polymer composition containing an agent is kneaded at a temperature equal to or higher than the highest glass transition temperature of each of the above (a) to (c), and a vulcanization reaction is performed while kneading. By performing this, the resin composition of the present invention can be obtained. The temperature and time of dynamic vulcanization are variable depending on the composition of the polymer composition, but the preferred dynamic vulcanization temperature is 150 to 280 ° C., and the preferred dynamic vulcanization time is 5 to 30 minutes. By performing dynamic vulcanization at a dynamic vulcanization temperature and dynamic vulcanization time within a preferred range, the dynamic vulcanization effectively proceeds, and the heat resistance of the matting agent obtained and the resin molding The color difference can be prevented from deteriorating.
Specific examples of the kneader used for the dynamic vulcanization include a mixing roll and a screw type extruder.

  The resin composition of the present invention may contain various compounding agents such as a filler, a colorant, a plasticizer, a lubricant, a light stabilizer, and a heat stabilizer as necessary, as long as the effects of the present invention are not impaired. There is no particular limitation on the timing of addition of the compounding agent.

  The matting agent of the present invention comprises (a) an ethylenically unsaturated nitrile-aromatic vinyl copolymer 40 to 70% by mass, (b) an aromatic vinyl-conjugated diene copolymer 10 to 40% by mass, and (c). 100 parts by mass of a polymer component comprising 5 to 50% by mass of a hydride of an alkyl-modified aromatic vinyl-conjugated diene copolymer, 0.05 to 5 parts by mass of an organic peroxide crosslinking agent, and optionally carbon-carbon It consists of a resin composition obtained by dynamically vulcanizing a polymer composition containing 0.5 to 10 parts by mass of a crosslinking agent having a plurality of heavy bonds in one molecule.

  The thermoplastic resin composition of the present invention comprises 2 to 10 parts by mass of the matting agent with respect to 100 parts by mass of the thermoplastic resin.

  The matting agent can exhibit a matting effect by being mixed and contained in various thermoplastic resins. Examples of various thermoplastic resins include: polyolefins such as polyethylene, polypropylene and polybutene; polystyrenes; ethylenically unsaturated nitrile-aromatic vinyl copolymers such as acrylonitrile-styrene copolymers and AS resins; ABS resins, Ethylenically unsaturated nitrile-aromatic vinyl-conjugated diene copolymers; polyamides such as nylon-6,6, nylon-6,12; polyesters such as polyethylene terephthalate, polyethylene isophthalate, polyethylene adipate; polymethyl methacrylate And poly (meth) acrylates such as butyl acrylate-methyl methacrylate copolymer, polycarbonates, and polyvinyl chloride. Among these, an ethylenically unsaturated nitrile-aromatic vinyl-conjugated diene copolymer is preferable, and an ABS resin is particularly preferable. The matting effect of the matting agent on the ethylenically unsaturated nitrile-aromatic vinyl-conjugated diene copolymer is very excellent, and the matting effect of the matting agent on the ABS resin is particularly excellent.

  The resin molding of the present invention is formed by molding the thermoplastic resin composition.

  The molding conditions are not particularly limited, but the molding temperature is preferably equal to or higher than the temperature at which the thermoplastic resin composition is plasticized and lower than the temperature causing thermal degradation. Specifically, although it depends on the kind of the thermoplastic resin composition, 150 to 280 ° C. is preferable. The molding time is preferably 30 seconds to 1 hour.

  The molding machine for molding is not particularly limited, and examples thereof include a single screw extruder, a twin screw extruder, a press molding machine, and an injection molding machine.

  The resin molded product of the present invention obtained by the above molding can suppress the occurrence of gloss by the matting agent, and also suppress the color difference (change in color tone) due to heat to a small range.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the following examples, “parts” are based on mass unless otherwise specified. The measurement methods of (1) color difference and (2) gloss of the resin molded body are as follows.

(1) Color Difference of Resin Molded Body The initial color difference (YI ₀ ) of the resin molded body was measured by a sunshine carbon arc lamp type weather resistance tester based on JIS B 7753. After 700 hours of treatment, the color difference (YI ₁ ) of the resin molding was measured in the same manner. The smaller the color difference, the lighter the color.

(2) Gloss of resin molded body The gloss (60 degrees) of the resin molded body was measured with a gloss meter (Gloss Checker IG-331 manufactured by Horiba, Ltd.). The smaller the gloss value, the higher the matte properties.

Example 1
The polymer composition having the components shown in Table 1 was melt-mixed at 200 ° C. for 15 minutes using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd., Laboplastmill C model) to obtain pellets. Next, 5 parts of the obtained pellets and 95 parts of ABS resin (psychol EX114 manufactured by UMG ABS Co., Ltd.) were mixed, and a vertical injection molding machine (SAV-60-52 manufactured by Yamashiro Seiki Seisakusho Co., Ltd.) was used. Using the nozzle and barrel set temperature at 200 ° C., the resin composition was melted and injected into a strip-shaped molded product mold (die temperature 40 ° C.) having a width of 12.7 mm, a length of 170 mm, and a thickness of 3 mm. . Then, the thermoplastic resin composition injected and filled in the mold was cooled for 40 seconds to obtain a plate.
The color difference and gloss of the plate obtained by molding were measured. The results are shown in Table 2.

Examples 2-6 and Comparative Examples 1-3
The same operation as in Example 1 was performed except that the composition of the polymer composition was changed as shown in Table 1. The results are shown in Table 2.
The color difference and gloss of an ABS plate molded using only ABS resin were also measured. The results are shown in Table 2.

1) Acrylonitrile-styrene resin (manufactured by UMG ABS Co., Ltd., UMGABS AP-10)
2) Styrene-butadiene copolymer rubber (hereinafter also referred to as “SBR”) (manufactured by Nippon Zeon Co., Ltd., Nipol NS210 (styrene content 25%, Mooney viscosity 56))
3) Acrylonitrile-butadiene copolymer rubber (hereinafter also referred to as “NBR”) (manufactured by Nippon Zeon Co., Ltd., Nipol DN3335 (acrylonitrile content 33%, Mooney viscosity 35))
4) Acrylonitrile-butadiene copolymer rubber (manufactured by Nippon Zeon Co., Ltd., Nipol DN2850 (acrylonitrile content 33%, Mooney viscosity 50))
5) Septon V9461 manufactured by Kuraray Co., Ltd.
6) Acrylic rubber (Nippon Zeon Co., Ltd., Nipol AR31) / stearic acid / organic peroxide (Kayaku Akzo Co., Ltd., Parkadox 14R-G) = 1.01 / 0.04 / 0.25 (Mass ratio) mixture 7) Ciba Specialty Chemicals, Irganox 1010
8) Kyoeisha Chemical Co., Ltd. product, light acrylate 14EG-A (polyethylene glycol (polymerization degree 600) diacrylate)
9) Light acrylate PE-4A (pentaerythritol tetraacrylate) manufactured by Kyoeisha Chemical Co., Ltd.

  Comparative Example 1 using a matting agent comprising a resin composition obtained by dynamically vulcanizing a polymer composition containing NBR and not containing a hydride of an alkyl-modified aromatic vinyl-conjugated diene copolymer The initial color of the resin molded product obtained by molding the thermoplastic resin composition of No. 2 and the color difference after 700 hours of treatment are the initial values of the resin molded products obtained by molding the thermoplastic resin compositions of Examples 1 to 6 and It is much larger than the color difference after 700 hours of processing. Therefore, the coloring degree of the resin molding obtained by molding the thermoplastic resin compositions of Comparative Examples 1 and 2 is high, and the coloring degree of the molding is further increased by light irradiation.

  Thermoplastic resin composition of Comparative Example 3 using a matting agent comprising a resin composition obtained by dynamically vulcanizing a polymer composition containing no hydride of an alkyl-modified aromatic vinyl-conjugated diene copolymer The initial color difference of the resin molded body obtained by molding the resin is comparable to the initial color difference of the resin molded bodies obtained by molding the thermoplastic resin compositions of Examples 1 to 6. However, the color difference after the 700-hour treatment of the resin molded body obtained by molding the thermoplastic resin composition of Comparative Example 3 is that of the resin molded body obtained by molding the thermoplastic resin compositions of Examples 1 to 6. It is much larger than the color difference after 700 hours of processing. Therefore, the weather resistance of the resin molding obtained by molding the thermoplastic resin composition of Comparative Example 3 is low, and the resin molding is easily colored by light irradiation.

  The resin composition of the present invention can be kneaded with a thermoplastic resin such as an AS resin, an ABS resin, a polycarbonate resin, or a polyester resin to give a resin molded article having high matteness, weather resistance, and lightness. Therefore, the resin composition of the present invention is useful as a raw material for OA equipment, home appliances, camera housings, automobile interior materials, and the like.

Claims (5)

(A) ethylenically unsaturated nitrile-aromatic vinyl copolymer 40-70% by mass, (b) aromatic vinyl-conjugated diene copolymer 10-40% by mass, and (c) the alkyl group is at least one aromatic ring. A polymer composition comprising 100 parts by mass of a polymer component consisting of 5 to 50% by mass of a hydride of an aromatic vinyl-conjugated diene copolymer bonded to a part and 0.05 to 5 parts by mass of an organic peroxide crosslinking agent A resin composition obtained by dynamically vulcanizing a product.   2. The polymer composition according to claim 1, further comprising a cross-linking agent having a plurality of carbon-carbon double bonds of 0.5 to 10 parts by mass in one molecule with respect to 100 parts by mass of the polymer component. Resin composition.   A matting agent comprising the resin composition according to claim 1 or 2.   A thermoplastic resin composition comprising 2 to 10 parts by mass of the matting agent according to claim 3 with respect to 100 parts by mass of the thermoplastic resin.   The resin molding formed by shape | molding the thermoplastic resin composition of Claim 4.