WO2024057891A1 - Composition de résine thermoplastique et article moulé associé - Google Patents

Composition de résine thermoplastique et article moulé associé Download PDF

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Publication number
WO2024057891A1
WO2024057891A1 PCT/JP2023/030921 JP2023030921W WO2024057891A1 WO 2024057891 A1 WO2024057891 A1 WO 2024057891A1 JP 2023030921 W JP2023030921 W JP 2023030921W WO 2024057891 A1 WO2024057891 A1 WO 2024057891A1
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vinyl
mass
copolymer
monomer
parts
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PCT/JP2023/030921
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English (en)
Japanese (ja)
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圭太郎 杉村
尚季 大橋
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テクノＵｍｇ株式会社
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Publication of WO2024057891A1 publication Critical patent/WO2024057891A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a thermoplastic resin composition containing a vinyl copolymer, a rubber-reinforced graft copolymer, and a polyamide elastomer. According to the thermoplastic resin composition of the present invention, it is possible to obtain a molded article with excellent sheet molding productivity and excellent chemical resistance, transparency, and rigidity. The present invention also relates to a molded article formed by molding this thermoplastic resin composition.
  • Rubber-reinforced styrene obtained by graft copolymerizing a rubbery polymer such as diene rubber with an aromatic vinyl compound such as styrene or ⁇ -methylstyrene and a vinyl cyanide compound such as acrylonitrile or methacrylonitrile.
  • the resin has excellent impact resistance, mechanical strength such as rigidity, moldability, and cost performance. For this reason, rubber-reinforced styrene resins are widely used in fields such as home appliances, communication-related equipment, transportation containers, general goods, and medical-related equipment.
  • rubber-reinforced styrene resins are sometimes used as films and sheets.
  • sheet molding a resin with relatively low fluidity in sheet or film molding (hereinafter collectively referred to as "sheet molding"). Therefore, in order to reduce fluidity, the ratio of the rubbery polymer in the rubber-reinforced styrenic resin is designed to be high.
  • rubber-reinforced styrene resins are generally opaque, but depending on the product, transparency like polymethyl methacrylate or polycarbonate resins may be required.
  • transparency like polymethyl methacrylate or polycarbonate resins may be required.
  • Patent Document 1 it is possible to obtain transparency even in rubber-reinforced styrene resin by adjusting the composition ratio of each constituent component of the resin. It has been known.
  • Examples of uses for transparent sheet materials include transportation equipment and transportation containers for precision parts. In such applications, there is a risk that the resin will deteriorate due to the adhesion of cleaning agents used for precision parts, resulting in a decrease in transparency and the occurrence of cracks and cracks. Therefore, from the viewpoint of preventing such problems, chemical resistance is also required.
  • Patent Document 2 and Patent Document 3 conventionally provided transparent materials made of rubber-reinforced styrene resins can be made transparent by increasing the ratio of (meth)acrylic acid ester in the composition. is improving. For this reason, as a result of increasing the (meth)acrylic acid ester ratio, chemical resistance to cleaning agents such as isopropyl alcohol was insufficient.
  • Patent Document 3 proposes the following thermoplastic resin composition, aiming not at sheet moldability or chemical resistance but at improving adhesiveness with organic solvents, impact resistance, antistatic property, and color tone. At least 5 to 40% by mass of aromatic vinyl monomer (a1), 30 to 80% by mass of (meth)acrylic acid ester monomer (a2), and 10 to 50% by mass of vinyl cyanide monomer (a3) %, a vinyl copolymer (A) obtained by copolymerizing a vinyl monomer mixture (a) containing at least an aromatic vinyl monomer (b1) in the presence of a rubbery polymer (r).
  • a vinyl monomer mixture ( A thermoplastic resin composition comprising a graft copolymer (B) obtained by graft copolymerizing mb) and a polyamide elastomer (C), the thermoplastic resin composition comprising a vinyl copolymer (A) and a graft copolymer.
  • a thermoplastic resin composition containing 1 part or more.
  • Patent Document 3 does not have the problem of improving sheet molding productivity and chemical resistance.
  • the vinyl copolymer (A) has a small molecular weight and the proportion of the rubber-reinforced graft copolymer (B) in the resin component is also small, which is an issue in the present invention. It is not possible to obtain the sheet formability that is desired.
  • Patent Document 4 discloses a technique for regulating the acrylonitrile content in the acetone soluble content of a thermoplastic resin composition.
  • this technique is used to improve chemical resistance or impart antistatic properties by blending polyamide elastomer, there is a problem in that transparency is significantly impaired.
  • An object of the present invention is to provide a thermoplastic resin composition that has excellent sheet molding productivity and can yield molded products with excellent chemical resistance, transparency, rigidity, and heat resistance.
  • thermoplastic resin composition containing a specific vinyl copolymer, a rubber-reinforced graft copolymer, and a polyamide elastomer in a predetermined ratio can solve the above problems. That is, the gist of the present invention is as follows.
  • the vinyl copolymer (A) is a vinyl copolymer containing an aromatic vinyl monomer (a1), a (meth)acrylic acid ester monomer (a2), and a vinyl cyanide monomer (a3).
  • the vinyl copolymer (A) is a vinyl copolymer containing an aromatic vinyl monomer (a1), a (meth)acrylic acid ester monomer (a2), and a vinyl cyanide monomer (a3).
  • the vinyl copolymer (A) further contains an aromatic vinyl monomer (a1), a (meth)acrylic acid ester monomer (a2), and a maleimide monomer (a4).
  • a vinyl copolymer (A2) obtained by copolymerizing a vinyl monomer mixture (ma2) containing a vinyl monomer mixture (ma2) and having a weight average molecular weight of 100,000 to 250,000, [ The thermoplastic resin composition according to any one of [1] to [3].
  • the refractive index of the vinyl copolymer (A), the acetone-soluble content of the rubber-reinforced graft copolymer (B), and the polyamide elastomer (C) is in the range of 1.505 to 1.520,
  • thermoplastic resin composition Any of [1] to [5], wherein the content of the vinyl cyanide monomer component in 100% by mass of the acetone soluble content of the thermoplastic resin composition is 0.5 to 10% by mass.
  • thermoplastic resin composition A molded article made of the thermoplastic resin composition according to any one of [1] to [6].
  • thermoplastic resin composition of the present invention it is possible to provide a molded article, especially a sheet-like molded article, which has excellent productivity in sheet molding and has excellent chemical resistance, transparency, rigidity, and heat resistance.
  • molded article refers to an article formed by molding a thermoplastic resin composition.
  • (co)polymerization” and “(co)polymer” refer to “homopolymerization” and/or “copolymerization” and “homopolymer” and/or “copolymer”, respectively.
  • (Meth)acrylic” and “(meth)acrylate” mean “acrylic” and/or “methacrylic” and “acrylate” and/or “methacrylate”, respectively.
  • sheet molding productivity may be simply referred to as "sheet moldability”.
  • the thermoplastic resin composition of the present invention includes: Vinyl copolymer (A) obtained by copolymerizing a vinyl monomer mixture (ma) containing an aromatic vinyl monomer (a1) and a (meth)acrylic acid ester monomer (a2) and, Contains at least an aromatic vinyl monomer (b1), a (meth)acrylic acid ester monomer (b2), and a cyanide vinyl monomer (b3) in the presence of a rubbery polymer (r).
  • Vinyl copolymer (A) obtained by copolymerizing a vinyl monomer mixture (ma) containing an aromatic vinyl monomer (a1) and a (meth)acrylic acid ester monomer (a2) and, Contains at least an aromatic vinyl monomer (b1), a (meth)acrylic acid ester monomer (b2), and a cyanide vinyl monomer (b3) in the presence of a rubbery polymer (r).
  • the vinyl copolymer (A) is a vinyl copolymer containing an aromatic vinyl monomer (a1), a (meth)acrylic acid ester monomer (a2), and a vinyl cyanide monomer (a3).
  • the rubber-reinforced graft copolymer (B) may be simply referred to as "graft copolymer (B)".
  • the thermoplastic resin composition of the present invention comprises a vinyl copolymer (A) containing the vinyl copolymer (A1), a rubber-reinforced graft copolymer (B), and a polyamide elastomer (C) in a predetermined ratio. and the vinyl copolymer (A1) has a weight average molecular weight of 50,000 to 300,000, thereby improving the transparency, rigidity, and heat resistance of the resulting molded product. Moreover, by containing the rubber-reinforced graft copolymer (B), the chemical resistance of the molded article and the fluidity suitable for sheet molding can be improved. Furthermore, by containing the polyamide elastomer (C), the chemical resistance of the molded article can be improved.
  • the vinyl copolymer (A) is obtained by copolymerizing a vinyl monomer mixture (ma) containing an aromatic vinyl monomer (a1) and a (meth)acrylic acid ester monomer (a2). That's what happens.
  • the vinyl copolymer (A) is a vinyl copolymer containing an aromatic vinyl monomer (a1), a (meth)acrylic acid ester monomer (a2), and a vinyl cyanide monomer (a3). It contains a vinyl copolymer (A1) formed by copolymerizing a monomer mixture (ma1) and having a weight average molecular weight of 50,000 to 300,000.
  • the vinyl copolymer (A) preferably includes a vinyl copolymer (A1), Copolymerizing a vinyl monomer mixture (ma2) containing an aromatic vinyl monomer (a1), a (meth)acrylic acid ester monomer (a2), and a maleimide monomer (a4) It contains a vinyl copolymer (A2) having a weight average molecular weight of 100,000 to 250,000 in a suitable content as described below.
  • the vinyl copolymer (A) may consist only of the vinyl copolymer (A1) and may not contain the vinyl copolymer (A2), or may be composed of the vinyl copolymer (A1) and the vinyl copolymer (A1). It may also contain a vinyl copolymer (A2).
  • a vinyl copolymer (A2) only one type of vinyl copolymer (A1) may be used, or two or more types having different monomer compositions, physical properties, etc. may be used as a mixture.
  • the vinyl copolymer (A2) only one type may be used, or two or more types having different monomer compositions, physical properties, etc. may be used in combination.
  • the vinyl copolymer (A1) is a vinyl copolymer containing an aromatic vinyl monomer (a1), a (meth)acrylic acid ester monomer (a2), and a vinyl cyanide monomer (a3). It is obtained by copolymerizing a monomer mixture (ma1).
  • the vinyl copolymer (A1) contains 5 to 40% by mass of an aromatic vinyl monomer (a1), 30 to 85% by mass of a (meth)acrylic acid ester monomer (a2), and a vinyl cyanide monomer.
  • it is obtained by copolymerizing a vinyl monomer mixture (ma1) containing 2 to 30% by mass of monomer (a3) according to a conventional method.
  • the vinyl monomer mixture (ma1) is copolymerized with an aromatic vinyl monomer (a1), a (meth)acrylate monomer (a2), and a vinyl cyanide monomer (a3). It may further contain other possible vinyl copolymers.
  • aromatic vinyl monomer (a1) examples include styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, vinyltoluene, t-butylstyrene, and the like. These may be used alone or in combination of two or more. Among these, styrene is preferred from the viewpoint of improving the moldability of the thermoplastic resin composition and the rigidity of the resulting molded product.
  • the content of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (ma1) is preferably 5% by mass or more based on the total 100% by mass of the vinyl monomer mixture (ma1). , more preferably 10% by mass or more, still more preferably 19% by mass or more. If the content of the aromatic vinyl monomer (a1) is at least the above-mentioned lower limit, the moldability of the thermoplastic resin composition (A1) and the rigidity of the resulting molded product can be further improved.
  • the content of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (ma1) is preferably 40% by mass or less based on the total 100% by mass of the vinyl monomer mixture (ma1). , more preferably 30% by mass or less, still more preferably 27% by mass or less. If the content of the aromatic vinyl monomer (a1) is below the above upper limit, the impact resistance and transparency of the resulting molded product can be further improved.
  • the (meth)acrylic acid ester monomer (a2) is not particularly limited, but esters of alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid are preferred.
  • the ester of an alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid may further have a substituent such as a hydroxyl group or a halogen group.
  • Examples of esters of alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-(meth)acrylate.
  • the content of the (meth)acrylic acid ester monomer (a2) in the vinyl monomer mixture (ma1) is preferably 30% by mass out of the total 100% by mass of the vinyl monomer mixture (ma1). or more, more preferably 50% by mass or more, still more preferably 65% by mass or more.
  • the content of the (meth)acrylic acid ester monomer (a2) in the vinyl monomer mixture (ma1) is preferably 85% by mass out of the total 100% by mass of the vinyl monomer mixture (ma1). or less, more preferably 80% by mass or less, still more preferably 75% by mass or less. If the content of the (meth)acrylic acid ester monomer (a2) is below the above upper limit, the chemical resistance and transparency of the resulting molded product can be further improved.
  • Examples of the vinyl cyanide monomer (a3) include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. These may be used alone or in combination of two or more. Among these, acrylonitrile is preferred from the viewpoint of further improving the chemical resistance of the molded product obtained.
  • the content of the vinyl cyanide monomer (a3) in the vinyl monomer mixture (ma1) shall be 2 to 30% by mass based on the total 100% by mass of the vinyl monomer mixture (ma1). is preferred. If the content of the vinyl cyanide monomer (a3) is less than 2% by mass, chemical resistance tends to decrease. Therefore, the content of the vinyl cyanide monomer (a3) is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 6% by mass or more. On the other hand, if the content of the vinyl cyanide monomer (a3) exceeds 30% by mass, the yellowness (YI) of the obtained molded article tends to increase and the color tone tends to decrease.
  • the content of the vinyl cyanide monomer (a3) in the vinyl monomer mixture (ma1) is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass. % or less, particularly 9% by weight or less, most preferably 8% by weight or less.
  • Examples of unsaturated fatty acids include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid.
  • Examples of the acrylamide monomer include acrylamide, methacrylamide, and N-methylacrylamide.
  • Examples of maleimide monomers include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, Examples include N-phenylmaleimide.
  • the content of the other vinyl copolymers in 100% by mass of the vinyl monomer mixture (ma1) is It is preferably 10% by mass or less, more preferably 0 to 5% by mass. If the content of other vinyl copolymers is below the above upper limit, aromatic vinyl monomer (a1), (meth)acrylic acid ester monomer (a2) and vinyl cyanide monomer The effect of using (a3) at a predetermined ratio can be effectively obtained.
  • the vinyl copolymer (A2) is a vinyl monomer containing an aromatic vinyl monomer (a1), a (meth)acrylic acid ester monomer (a2), and a maleimide monomer (a4). It is obtained by copolymerizing a mixture of substances (ma2).
  • the vinyl copolymer (A2) contains 2 to 30% by mass of aromatic vinyl monomer (a1), 30 to 80% by mass of (meth)acrylic acid ester monomer (a2), and maleimide monomer.
  • (a4) Preferably, it is obtained by copolymerizing a vinyl monomer mixture (ma2) containing 10 to 50% by mass according to a conventional method.
  • the vinyl monomer mixture (ma2) is copolymerizable with the aromatic vinyl monomer (a1), the (meth)acrylic acid ester monomer (a2), and the maleimide monomer (a4). It may further contain other monomers.
  • aromatic vinyl monomer (a1) examples include those exemplified as the aromatic vinyl monomer (a1) used in the vinyl copolymer (A1). Styrene is preferred as the aromatic vinyl monomer (a1).
  • the content of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (ma2) is preferably 2% by mass or more based on the total 100% by mass of the vinyl monomer mixture (ma2). , more preferably 5% by mass or more.
  • the content of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (ma2) is preferably 30% by mass or less based on the total 100% by mass of the vinyl monomer mixture (ma2). , more preferably 20% by mass or less, still more preferably 15% by mass or less. If the content of the aromatic vinyl monomer (a1) is below the above upper limit, the impact resistance and transparency of the resulting molded product can be further improved.
  • Examples of the (meth)acrylic ester monomer (a2) include those exemplified as the (meth)acrylic ester monomer (a2) used in the vinyl copolymer (A1).
  • As the (meth)acrylic acid ester monomer (a2) methyl (meth)acrylate is preferable.
  • the content of the (meth)acrylic acid ester monomer (a2) in the vinyl monomer mixture (ma2) is preferably 30% by mass out of the total 100% by mass of the vinyl monomer mixture (ma2).
  • the content is preferably at least 50% by mass, and even more preferably at least 55% by mass.
  • the transparency of the resulting molded product can be further improved.
  • the content of the (meth)acrylic acid ester monomer (a2) in the vinyl monomer mixture (ma2) is preferably 80% by mass out of the total 100% by mass of the vinyl monomer mixture (ma2).
  • the content is not more than 75% by mass, more preferably not more than 70% by mass. If the content of the (meth)acrylic acid ester monomer (a2) is below the above upper limit, the chemical resistance of the resulting molded product can be further improved.
  • maleimide monomer (a4) examples include those exemplified as maleimide monomers for other vinyl copolymers that may be used as needed in the vinyl copolymer (A1).
  • maleimide monomer (a4) N-phenylmaleimide is preferred.
  • the content of the maleimide monomer (a4) in the vinyl monomer mixture (ma2) is preferably 10 to 50% by mass based on the total 100% by mass of the vinyl monomer mixture (ma2). preferable.
  • the content of the maleimide monomer (a4) is preferably 10% by mass or more, more preferably 15 parts by mass or more.
  • the content of the maleimide monomer (a4) exceeds 50% by mass, the fluidity of the thermoplastic resin composition tends to decrease. Therefore, the content of the maleimide monomer (a4) is preferably 50% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less.
  • aromatic vinyl monomer (a1) aromatic vinyl monomer (a1)
  • (meth)acrylic acid ester monomer (a2) vinyl monomer (a2)
  • maleimide monomer (a4) maleimide monomer
  • vinyl monomers other than those mentioned above as long as they do not impair the effects of the present invention.
  • Specific examples include vinyl cyanide monomers, unsaturated fatty acids, and acrylamide monomers.
  • Examples of the vinyl cyanide monomer include those exemplified as the vinyl cyanide monomer (a3) used in the vinyl copolymer (A1).
  • Examples of the unsaturated fatty acid and acrylamide monomer include those exemplified as other vinyl copolymers used in the vinyl copolymer (A1).
  • the content of the other vinyl copolymers in 100% by mass of the vinyl monomer mixture (ma2) is It is preferably 10% by mass or less, more preferably 0 to 5% by mass. If the content of other vinyl copolymers is below the above upper limit, aromatic vinyl monomer (a1), (meth)acrylic acid ester monomer (a2) and maleimide monomer (a4) ) in a predetermined ratio can be effectively obtained.
  • the weight average molecular weight (Mw) of the vinyl copolymer (A1) is 50,000 to 300,000, preferably 100,000 to 250,000.
  • the weight average molecular weight (Mw) of the vinyl copolymer (A2) is preferably 100,000 to 250,000. If the weight average molecular weight of each of the vinyl copolymer (A1) and the vinyl copolymer (A2) is at least the above lower limit, the resulting thermoplastic resin composition will have low fluidity and will have excellent sheet formability.
  • the vinyl copolymer (A1) having a weight average molecular weight (Mw) of 50,000 to 300,000 and the vinyl copolymer (A2) having a weight average molecular weight (Mw) of 100,000 to 250,000 are, for example, can be easily produced by using an initiator and a chain transfer agent, which will be described later, and by adjusting the polymerization temperature to a preferable range, which will be described later.
  • the refractive index of the vinyl copolymer (A) is preferably 1.505 to 1.520, more preferably 1.509 to 1.519, and preferably 1.510 to 1.517. More preferred. If the refractive index of the vinyl copolymer (A) is within the above range, the difference in refractive index with the rubber-reinforced graft copolymer (B) described below can be reduced, and the resulting molded product will have excellent transparency. It can be done.
  • the difference between the refractive index of the vinyl copolymer (A) and the refractive index of the acetone-soluble portion of the rubber-reinforced graft copolymer (B) and the refractive index of the polyamide elastomer (C), which will be described later, is 0.03 or less, especially It is preferable that it is 0.01 or less from the viewpoint of transparency of the molded product obtained.
  • the refractive index of the vinyl copolymer (A) mainly depends on the composition of the raw material vinyl monomer, so the refractive index can be adjusted by appropriately selecting the type and composition ratio of the vinyl monomer. It can be within any desired range.
  • the weight average molecular weight (Mw) and refractive index of the vinyl copolymer (A) are measured by the method described in the Examples section below.
  • the method for producing the vinyl copolymer (A) is not particularly limited, and the aforementioned vinyl monomer mixture (ma) (vinyl monomer mixture (ma1) or vinyl monomer mixture (ma2)) is used.
  • a raw material it can be produced by a known polymerization method. From the viewpoint of improving the moldability, transparency, and color stability of the resulting thermoplastic resin composition, continuous bulk polymerization or continuous solution polymerization is preferably used.
  • Any method can be used to produce the vinyl copolymer (A) by continuous bulk polymerization or continuous solution polymerization.
  • a method can be mentioned in which the vinyl monomer mixture (ma) is polymerized in a polymerization tank and then the monomer is removed (solvent removal/devolatilization).
  • the graft copolymer (B) contains at least an aromatic vinyl monomer (b1), a (meth)acrylic acid ester monomer (b2), and a vinyl cyanide monomer in the presence of a rubbery polymer (r). It is obtained by graft copolymerizing a vinyl monomer mixture (mb) containing monomer (b3).
  • the graft copolymer (B) contains 5 to 40% by mass of an aromatic vinyl monomer (b1) and a (meth)acrylic acid ester monomer (b2) in the presence of a rubbery polymer (r).
  • a vinyl monomer mixture (mb) containing 30 to 85% by mass and 2 to 30% by mass of vinyl cyanide monomer (b3).
  • the vinyl monomer mixture (mb) is copolymerized with an aromatic vinyl monomer (b1), a (meth)acrylic acid ester monomer (b2), and a vinyl cyanide monomer (b3). It may further contain other possible vinyl copolymers.
  • Examples of the rubbery polymer (r) include polybutadiene, polyisoprene, butyl rubber, styrene-butadiene copolymer (styrene content is preferably 5 to 60% by mass), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, Ethylene- ⁇ -olefin copolymer, ethylene- ⁇ -olefin-polyene copolymer, silicone rubber, acrylic rubber, butadiene-(meth)acrylate copolymer, polyisoprene, styrene-butadiene block copolymer, styrene Examples include -isoprene block copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated butadiene polymers, and ethylene ionomers.
  • the styrene-butadiene block copolymer and styrene-isoprene block copolymer include those having an AB type, ABA type, tapered type, or radial teleblock type structure.
  • Hydrogenated butadiene-based polymers include hydrogenated products of polystyrene blocks and styrene-butadiene random copolymer blocks in addition to hydrogenated products of the block copolymer; 1,2-vinyl bond content in polybutadiene 20% by mass or less and a polybutadiene block having a 1,2-vinyl bond content of more than 20% by mass.
  • the amount of rubbery polymer (r) used per 100 parts by mass of the rubbery polymer (r) constituting the rubber reinforced graft copolymer (B) and the vinyl monomer mixture (mb) described below. is preferably 20 to 80 parts by mass. If the amount of the rubbery polymer (r) used is 20 parts by mass or more, the impact resistance of the resulting molded product can be further improved.
  • the content of the rubbery polymer (r) is more preferably 35 parts by mass or more. If the content of the rubbery polymer (r) is 80 parts by mass or less, the moldability of the thermoplastic resin composition can be further improved.
  • the content of the rubbery polymer (r) is more preferably 60 parts by mass or less.
  • the volume average particle diameter of the rubbery polymer (r) is not particularly limited, but from the viewpoint of further improving the impact resistance of the molded product obtained, it is preferably 80 nm or more, and more preferably 150 nm or more. From the viewpoint of improving the transparency of the resulting molded product, the volume average particle diameter of the rubbery polymer (r) is preferably 500 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less.
  • the volume average particle diameters of the rubbery polymer (r) and the rubber-reinforced graft copolymer (B) described below are measured by the method described in the Examples section below.
  • aromatic vinyl monomer (b1) examples include those exemplified as the aromatic vinyl monomer (a1). Styrene is preferred as the aromatic vinyl monomer (b1).
  • the content of the aromatic vinyl monomer (b1) in the vinyl monomer mixture (mb) is preferably 5% by mass or more based on the total 100% by mass of the vinyl monomer mixture (mb). , more preferably 10% by mass or more. If the content of the aromatic vinyl monomer (b1) is at least the above lower limit, the moldability of the thermoplastic resin composition and the rigidity of the resulting molded product can be further improved.
  • the content of the aromatic vinyl monomer (b1) in the vinyl monomer mixture (mb) is preferably 40% by mass or less based on the total 100% by mass of the vinyl monomer mixture (mb). , more preferably 30% by mass or less. If the content of the aromatic vinyl monomer (b1) is below the above upper limit, the impact resistance and transparency of the resulting molded product can be further improved.
  • Examples of the (meth)acrylic ester monomer (b2) include those exemplified as the (meth)acrylic ester monomer (a2).
  • As the (meth)acrylic acid ester monomer (b2) methyl (meth)acrylate is preferable.
  • the content of the (meth)acrylic acid ester monomer (b2) in the vinyl monomer mixture (mb) is preferably 30% by mass out of the total 100% by mass of the vinyl monomer mixture (mb). or more, and more preferably 50% by mass or more.
  • the content of the (meth)acrylic acid ester monomer (b2) in the vinyl monomer mixture (mb) is preferably 85% by mass out of the total 100% by mass of the vinyl monomer mixture (mb). It is not more than 75% by mass, and more preferably not more than 75% by mass. If the content of the (meth)acrylic acid ester monomer (b2) is below the above upper limit, the chemical resistance of the resulting molded product can be further improved.
  • Examples of the vinyl cyanide monomer (b3) include those exemplified as the vinyl cyanide monomer (a3).
  • As the vinyl cyanide monomer (b3) acrylonitrile is preferred.
  • the content of the vinyl cyanide monomer (b3) in the vinyl monomer mixture (mb) shall be 2 to 30% by mass based on the total 100% by mass of the vinyl monomer mixture (mb). is preferred.
  • the content of the vinyl cyanide monomer (b3) is preferably 2% by mass or more, more preferably 5% by mass or more.
  • the content of the vinyl cyanide monomer (b3) exceeds 30% by mass, the yellowness (YI) of the obtained molded article tends to increase and the color tone tends to decrease. Therefore, the content of the vinyl cyanide monomer unit (b3) is preferably 30% by mass or less, more preferably 20% by mass or less.
  • the weight average molecular weight (Mw) of the acetone soluble portion of the rubber reinforced graft copolymer (B) is preferably 30,000 to 500,000, more preferably 40,000 to 250,000, 50,000 to 150, 000 is more preferred.
  • the rubber-reinforced graft copolymer (B) having a weight average molecular weight of 30,000 to 500,000 can be produced by, for example, using an initiator or a chain transfer agent as described below, or setting the polymerization temperature within the preferred range as described below. , can be easily manufactured.
  • the volume average particle diameter of the rubber-reinforced graft copolymer (B) is preferably 80 to 500 nm, particularly 100 to 300 nm, from the viewpoint of transparency.
  • the refractive index of the acetone-soluble portion of the rubber reinforced graft copolymer (B) is preferably 1.505 to 1.520, more preferably 1.509 to 1.519, and 1.510 to 1. More preferably, it is .517. If the refractive index of the acetone-soluble portion of the rubber-reinforced graft copolymer (B) is within the above range, a rubber-reinforced graft copolymer (B) with excellent transparency can be obtained.
  • the refractive index difference between the acetone-soluble portion of the vinyl copolymer (A) and the rubber-reinforced graft copolymer (B) and the polyamide elastomer (C) described below is 0.03 or less, particularly 0. It is preferable that it is .01 or less from the viewpoint of transparency of the molded product obtained.
  • the graft ratio of the graft copolymer (B) and the refractive index of the acetone soluble content are measured by the method described in the Examples section below.
  • the acetone soluble content which is the graft component of the rubber-reinforced graft copolymer (B)
  • To improve the transparency of the obtained molded product by reducing the difference between the refractive index of the rubber-reinforced graft copolymer (B) and the refractive index of the graft component and the rubbery polymer (r) to 0.03 or less. Can be done.
  • the refractive index of the graft component of the rubber-reinforced graft copolymer (B) mainly depends on the composition of the raw material vinyl monomer. Therefore, by appropriately selecting the type and composition ratio of the vinyl monomer mixture (mb), the refractive index can be set within a desired range. In particular, when the polymerization conversion rate is increased to 95% or more by emulsion polymerization, the composition of the graft component is approximately the same as the composition of the vinyl monomer mixture (mb).
  • the refractive index of the rubbery polymer (r) is shown in general literature. For example, in the case of polybutadiene rubber, it is 1.516.
  • the refractive index of the graft component of the graft copolymer (B) is determined by dissolving the graft copolymer (B) in acetone and drying the residue obtained by filtering the acetone-soluble content. It can be measured in the same manner as for polymer (A).
  • the method for producing the graft copolymer (B) is not particularly limited, and any method such as emulsion polymerization, suspension polymerization, continuous bulk polymerization, continuous solution polymerization, etc. can be used. Among these, emulsion polymerization method or bulk polymerization method is preferred, and emulsion polymerization method is more preferred. If the emulsion polymerization method is used, the particle size of the rubbery polymer (r) can be easily adjusted to a desired range, and the polymerization stability can be easily adjusted by removing heat during polymerization.
  • the method of charging the rubbery polymer (r) and the vinyl monomer mixture (mb) is not particularly limited. For example, all of these may be initially prepared at once. In addition, in order to adjust the distribution of the copolymer composition, a part of the vinyl monomer mixture (mb) may be continuously charged, or a part or all of the vinyl monomer mixture (mb) may be added. You can also divide it and prepare it.
  • “continuously charging a part of the vinyl monomer mixture (mb)” means that a part of the vinyl monomer mixture (mb) is initially charged and the rest is continuously charged over time. means. Feeding part or all of the vinyl monomer mixture (mb) in portions means feeding part or all of the vinyl monomer mixture (mb) at a later point in time than the initial feeding. .
  • rubber-reinforced graft copolymer (B) only one type of rubber-reinforced graft copolymer (B) may be used, or two or more types of rubber-reinforced graft copolymer (B) having different types, vinyl monomer compositions, physical properties, etc. may be mixed. It may also be used as
  • polyamide elastomer (C) constituting the thermoplastic resin composition of the present invention
  • examples of the polyamide elastomer (C) constituting the thermoplastic resin composition of the present invention include aminocarboxylic acids or lactams having 6 or more carbon atoms, or salts of diamines and dicarboxylic acids having 6 or more carbon atoms, and poly(alkylene oxide).
  • Graft copolymers or block copolymers with glycol are preferred.
  • poly(alkylene oxide) glycol polyethylene oxide glycol is preferably used.
  • aminocarboxylic acids or lactams having 6 or more carbon atoms, or salts of diamines and dicarboxylic acids having 6 or more carbon atoms include ⁇ -aminocaproic acid, ⁇ -aminoenantoic acid, ⁇ -aminocaprylic acid, ⁇ - Aminocarboxylic acids such as aminopergonic acid, ⁇ -aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid; Lactams such as caprolactam, enantlactam, capryllactam, laurolactam; Hexamethylenediamine-adipate, hexamethylene Examples include nylon salts such as diamine-sebacate and hexamethylenediamine-isophthalate. Two or more types of these may be used.
  • poly(alkylene oxide) glycol examples include polyethylene oxide glycol, poly(1,2-propylene oxide) glycol, poly(1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, and poly(hexamethylene oxide) glycol. ) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, and the like. Two or more types of these may be used. Furthermore, bisphenol A, alkylene oxide adducts of fatty acids, etc. may be copolymerized.
  • the number average molecular weight of the poly(alkylene oxide) glycol is preferably 200 or more, and more preferably 300 or more. From the viewpoint of further improving chemical resistance, the number average molecular weight of poly(alkylene oxide) glycol is preferably 6,000 or less, more preferably 4,000 or less.
  • Both ends of the poly(alkylene oxide) glycol may be aminated or carboxylated as necessary.
  • the bond between the aminocarboxylic acid or lactam having 6 or more carbon atoms, or the salt of diamine and dicarboxylic acid having 6 or more carbon atoms, and poly(alkylene oxide) glycol is usually an ester bond and an amide bond. However, it is not particularly limited to these.
  • a third component such as a dicarboxylic acid or diamine
  • a reaction component such as a dicarboxylic acid or diamine
  • terephthalic acid dicarboxylic acid
  • the dicarboxylic acid is preferably a dicarboxylic acid having 4 to 20 carbon atoms from the viewpoint of further improving polymerizability, color tone, and physical properties.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate; 1, Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid; succinic acid, oxalic acid, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, etc. aliphatic dicarboxylic acids; and the like.
  • diamine aromatic, alicyclic and aliphatic diamines are used.
  • hexamethylene diamine which is an aliphatic diamine, is preferably used.
  • the method for producing the polyamide elastomer (C) is not particularly limited, and any known production method can be used.
  • any known production method can be used.
  • methods (1) to (3) below may be used.
  • the melting point of the polyamide elastomer (C) is preferably 140°C or higher, more preferably 180°C or higher, and even more preferably 190°C or higher.
  • the upper limit of the melting point of the polyamide elastomer (C) is usually 220°C or lower.
  • the refractive index of the polyamide elastomer (C) is preferably 1.505 to 1.520, more preferably 1.509 to 1.519, and even more preferably 1.510 to 1.517. If the refractive index of the polyamide elastomer (C) is within the above range, the difference in refractive index between the polyamide elastomer (C) and the rubber-reinforced graft copolymer (B) can be reduced, which is preferable from the viewpoint of transparency of the resulting molded product.
  • the difference between the refractive index of the vinyl copolymer (A), the refractive index of the acetone-soluble portion of the rubber-reinforced graft copolymer (B), and the refractive index of the polyamide elastomer (C) is 0.03 or less. In particular, it is preferably 0.01 or less from the viewpoint of transparency of the molded product obtained.
  • the melting point of the polyamide elastomer (C) is measured by the method described in the Examples section below.
  • the refractive index of the polyamide elastomer (C) can be measured by the method described in the Examples section below. However, for commercially available products, catalog values can be used.
  • polyamide elastomer (C) only one type of polyamide elastomer (C) may be used, or two or more types having different segment compositions, physical properties, etc. may be used as a mixture.
  • a nylon 6-based polyamide elastomer and a nylon 12-based polyamide elastomer can be used together, or polyamide elastomers having different melting points can be used together.
  • polyamide elastomer (C) A commercially available product may be used as the polyamide elastomer (C).
  • Commercially available polyamide elastomers (C) include Pellestat M-140, Pellestat NC6321, Pellestat M-330, Pellestat N1200, and Pellestat AS manufactured by Sanyo Chemical Co., Ltd.
  • the thermoplastic resin composition of the present invention includes a vinyl copolymer (A) (the vinyl copolymer (A) may be only a vinyl copolymer (A1), and a vinyl copolymer (A1)). and a vinyl copolymer (A2)), the rubber-reinforced graft copolymer (B), and the polyamide elastomer (C) (hereinafter referred to as "(A) to (C)").
  • 100 parts by mass, a total of 60 to 92 parts by mass of the vinyl copolymer (A) and the rubber-reinforced graft copolymer (B), and 100 parts by mass of the polyamide elastomer (C ) is a thermoplastic resin composition containing 8 to 40 parts by mass.
  • the proportion of the vinyl copolymer (A) out of the total 100% by mass of the vinyl copolymer (A) and the rubber-reinforced graft copolymer (B) is preferably is 20 to 80% by weight, more preferably 25 to 75% by weight, and even more preferably 30 to 70% by weight.
  • the proportion of one rubber-reinforced graft copolymer (B) is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass. This is because, if the content ratio of the vinyl copolymer (A) and the rubber-reinforced graft copolymer (B) is within the above range, chemical resistance and transparency will be excellent.
  • thermoplastic resin composition of the present invention contains a total of 60 to 92 parts of vinyl copolymer (A) and rubber-reinforced graft copolymer (B) in 100 parts by mass of (A) to (C). 8 to 40 parts by mass of polyamide elastomer (C). This blending ratio can be adjusted as appropriate within the above range depending on the purpose.
  • the content of the rubbery polymer (r) in 100% by mass of the thermoplastic resin composition of the present invention (hereinafter sometimes referred to as "rubber content") is preferably 8 to 35% by mass, and more preferably Preferably it is 10 to 30% by mass.
  • the lower limit of the content of the rubbery polymer (r) is more preferably 11% by mass or more, particularly preferably 12% by mass or more, and most preferably 13% by mass or more.
  • the upper limit of the content of the rubbery polymer (r) is more preferably 28% by mass or less, particularly preferably 25% by mass or less, most preferably 23% by mass or less. This is because if the content of the rubbery polymer (r) in the thermoplastic resin composition is within the above range, the chemical resistance, transparency, and sheet appearance will be excellent.
  • the rubber content in the thermoplastic resin composition can be calculated by a blending ratio using the content of the rubbery polymer (r) in the rubber-reinforced graft copolymer (B), or by an infrared spectrometer. It can be determined by measuring the rubber content.
  • the content of the vinyl cyanide monomer component in 100% by mass of the acetone soluble content of the thermoplastic resin composition is preferably 0.5 to 10% by mass. If the content of the vinyl cyanide monomer component is less than 0.5% by mass, the dispersibility will be poor and antistatic properties will be difficult to obtain when mixed with the polyamide elastomer (C).
  • the content of the vinyl cyanide monomer component is more preferably 1.0% by mass or more, even more preferably 2.0% by mass or more, particularly preferably 3.0% by mass or more, and most preferably 4.0% by mass. % or more.
  • the content of the vinyl cyanide monomer component is more preferably 9.0% by mass or less, further preferably 8.0% by mass or less, particularly preferably 7.0% by mass or less, and most preferably 6.5% by mass. % or less, more preferably in the order of 6.0% by mass or less, 5.5% by mass or less, and 5.0% by mass or less.
  • the content of the vinyl cyanide monomer component in 100% by mass of the acetone soluble content of the thermoplastic resin composition can be set to the above range, transparency can be achieved in sheet processing with lower shear force compared to injection molding. While maintaining this, chemical resistance can also be sufficiently developed.
  • the content of the vinyl cyanide monomer component in the acetone-soluble portion of the thermoplastic resin composition can be determined by preparing a calibration curve in advance using an infrared spectrometer. After extracting, it is measured by a measuring device described in the Examples section below.
  • the extraction of the acetone-soluble portion of the polymer was performed as follows. 2 g of each thermoplastic resin composition obtained in Examples and Comparative Examples was added to 40 mL of acetone, shaken for 2 hours with a shaker at a temperature of 25°C, and then shaken at a temperature of 5°C. The mixture was centrifuged for 60 minutes using a centrifuge (rotation speed: 23,000 rpm) to separate acetone-soluble and acetone-insoluble components. The obtained acetone-soluble content was dropped into methanol to precipitate the polymer component, and then the solid content was filtered out and dried in a vacuum dryer for 24 hours to obtain the acetone-soluble content in the thermoplastic resin composition.
  • Extract as a polymer component The content of the vinyl cyanide monomer component in the acetone-soluble matter can be measured by direct extraction and measurement as described above, or by measuring the content of the vinyl cyanide monomer component in the acetone-soluble matter of each raw material used. It can be determined by calculating from the blending ratio using the amount.
  • the weight average molecular weight of the acetone soluble portion of the thermoplastic resin composition is preferably 60,000 to 280,000. Being within this range is preferable because transparency can be maintained even during sheet molding and subsequent processing steps.
  • the weight average molecular weight of the acetone soluble component is more preferably 65,000 to 250,000, still more preferably 70,000 to 200,000, particularly preferably 75,000 to 150,000.
  • the weight average molecular weight of the acetone soluble component in the thermoplastic resin composition can be measured as a polystyrene equivalent value by GPC.
  • the weight average molecular weight of the acetone-soluble component can be measured by the measuring device described in the Examples section below after extracting the acetone-soluble polymer by the method described above.
  • thermoplastic resin composition of the present invention contains 20 to 65 parts by mass of a vinyl copolymer (A) and a rubber-reinforced graft copolymer (B) based on a total of 100 parts by mass of (A) to (C). It is preferable to contain 5 to 72 parts by mass of polyamide elastomer (C) and 8 to 30 parts by mass of polyamide elastomer (C).
  • the thermoplastic resin composition of the present invention contains 20 to 40 parts by mass of the vinyl copolymer (A) and a rubber-reinforced graft copolymer (100 parts by mass in total of (A) to (C)). Even if it contains 47 to 65 parts by mass of B), 8 to 13 parts by mass of polyamide elastomer (C), and 35 parts by mass or less of the vinyl copolymer (A1) in the vinyl copolymer (A). good.
  • the content of the vinyl copolymer (A) in the total of 100 parts by mass of (A) to (C) is less than the above lower limit, the rigidity of the molded product obtained by containing the vinyl copolymer (A) Therefore, the effect of improving heat resistance cannot be sufficiently obtained. If the content of the vinyl copolymer (A) exceeds the above upper limit, the moldability of the sheet will decrease.
  • a more preferable content of the vinyl copolymer (A) in a total of 100 parts by mass of (A) to (C) is as described above.
  • the content of the vinyl copolymer (A1) in the vinyl copolymer (A) is determined from the viewpoint of transparency and rigidity of the obtained molded product, out of a total of 100 parts by mass of (A) to (C). It is preferably 35 parts by mass or less, more preferably 30 mass% or less.
  • the content of the vinyl copolymer (A2) is determined by the heat resistance and chemical resistance. From the viewpoint of sheet formability, it is preferably 20 parts by mass or less, more preferably 5 to 20 parts by mass, and even more preferably 8 to 18 parts by mass, based on a total of 100 parts by mass of (A) to (C).
  • the content of the graft copolymer (B) in the total of 100 parts by mass of (A) to (C) is less than the above lower limit, the chemical resistance of the molded product due to the inclusion of the rubber-reinforced graft copolymer (B) In this case, the effect of improving fluidity suitable for sheet molding cannot be sufficiently obtained. If the content of the graft copolymer (B) exceeds the above upper limit, the rigidity and heat resistance of the molded article will not be sufficiently improved.
  • a more preferable content of the graft copolymer (B) in a total of 100 parts by mass of (A) to (C) is as described above.
  • the content of the polyamide elastomer (C) in the total of 100 parts by mass of (A) to (C) is less than 8 parts by mass, the effect of improving chemical resistance due to the inclusion of the polyamide elastomer (C) cannot be sufficiently obtained. However, the chemical resistance of the resulting molded product decreases.
  • the content of the polyamide elastomer (C) is 8 parts by mass or more, particularly preferably 10 parts by mass or more.
  • the content of the polyamide elastomer (C) in the total of 100 parts by mass of (A) to (C) is 40 parts by mass or less, preferably 30 parts by mass.
  • the amount is more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, particularly preferably 18 parts by mass or less, particularly preferably 13 parts by mass or less.
  • the thermoplastic resin composition of the present invention contains resins and elastomers other than the vinyl copolymer (A), the graft copolymer (B), and the polyamide elastomer (C) within a range that does not impair the effects of the present invention. can do.
  • these other resins and elastomers include one or more transparent resins such as polycarbonate resin and polymethyl methacrylate.
  • the content is the vinyl copolymer (A), the graft copolymer (B), the polyamide elastomer (C) and the other It is preferably 10 parts by mass or less in a total of 100 parts by mass of the resin and elastomer. If the content is below the above upper limit, the effects of the present invention can be effectively obtained by using the vinyl copolymer (A), the graft copolymer (B), and the polyamide elastomer (C) in a predetermined ratio. be able to.
  • the thermoplastic resin composition of the present invention may contain antioxidants such as hindered phenols, sulfur-containing organic compounds, and phosphorus-containing organic compounds; Heat stabilizers; ultraviolet absorbers such as benzotriazole, benzophenone, and salicylates; various stabilizers such as organic nickel and hindered amine light stabilizers; lubricants such as metal salts of higher fatty acids and higher fatty acid amides; Plasticizers such as phthalates and phosphates; anti-drip agents such as polytetrafluoroethylene; nonionic, anionic, cationic or amphoteric surfactants; pigments such as carbon black and titanium oxide; A dye; a liquid such as water, silicone oil, or liquid paraffin can also be blended. In addition, fillers can also be blended.
  • antioxidants such as hindered phenols, sulfur-containing organic compounds, and phosphorus-containing organic compounds
  • Heat stabilizers such as benzotriazole, benzophenone, and salicylates
  • various stabilizers
  • the filler examples include those in the form of fibers, plates, powders, particles, etc., and any of them may be used in the present invention. Specifically, polyacrylonitrile (PAN)-based and pitch-based carbon fibers; stainless steel fibers, metal fibers such as aluminum fibers and brass fibers; organic fibers such as aromatic polyamide fibers; gypsum fibers, ceramic fibers, asbestos fibers, and zirconia fibers.
  • PAN polyacrylonitrile
  • pitch-based carbon fibers such as stainless steel fibers, metal fibers such as aluminum fibers and brass fibers
  • organic fibers such as aromatic polyamide fibers
  • gypsum fibers ceramic fibers, asbestos fibers, and zirconia fibers.
  • Fibrous or whisker-like fillers such as fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, glass fibers, rock wool, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers; Powdered materials such as mica, talc, kaolin, silica, calcium carbonate, glass flakes, glass beads, glass microballoons, clay, molybdenum disulfide, wollastenite, montmorillonite, titanium oxide, zinc oxide, barium sulfate, calcium polyphosphate, graphite, etc. Examples include granular or plate-shaped fillers. Two or more types of these may be used. Among these, glass fiber is preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resins. For example, long fiber type or short fiber type chopped strands, milled fibers, etc. can be mentioned.
  • the surface of the filler may be treated with an arbitrary coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or other surface treatment agent.
  • the filler may be coated or bundled with a thermoplastic resin such as an ethylene/vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.
  • the filler may be treated with a coupling agent such as aminosilane or epoxysilane.
  • thermoplastic resin composition of the present invention contains a filler
  • the content thereof is 100 parts by mass in total of the vinyl copolymer (A), graft copolymer (B), and polyamide elastomer (C). It is preferably 0.01 to 10 parts by mass.
  • thermoplastic resin composition contains a vinyl copolymer (A), a graft copolymer (B), a polyamide elastomer (C), and other components used as necessary in the above-mentioned predetermined ratios.
  • thermoplastic resin composition of the present invention can be molded by known methods such as injection molding, extrusion molding, calendar molding, blow molding, vacuum molding, compression molding, and gas-assisted molding.
  • the melt volume rate (MVR) of the thermoplastic resin composition of the present invention measured by the method described in the Examples section below is preferably 50 cm 3 /10 minutes or less, more preferably is 30 cm 3 /10 minutes or less, more preferably 20 cm 3 /10 minutes or less.
  • the MVR of the thermoplastic resin composition of the present invention is preferably 2 cm 3 /10 minutes or more, more preferably 4 cm 3 /10 minutes or more, from the viewpoint of sheet moldability and sheet appearance. More preferably, it is 6 cm 3 /10 minutes or more.
  • the total light transmittance of the thermoplastic resin composition of the present invention measured by the method described in the Examples section below is preferably 85% or more, and preferably 87% or more. It is more preferable.
  • the bending modulus of the thermoplastic resin composition of the present invention measured by the method described in the Examples section below is preferably 900 MPa or more, more preferably 1,000 MPa or more. .
  • the heat distortion temperature of the thermoplastic resin composition of the present invention measured by the method described in the Examples section below is preferably 58°C or higher, and preferably 60°C or higher. More preferably, the temperature is 63°C or higher.
  • the molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention using the various molding methods described above.
  • the molded article of the present invention can be applied to a wide range of fields of use, such as home appliances, communication-related equipment, transportation containers, general miscellaneous goods, and medical-related equipment.
  • thermoplastic resin composition of the present invention is preferably used as a film or sheet by T-die molding or calendar molding because of its excellent sheet formability, chemical resistance, transparency, rigidity, and heat resistance.
  • the molded article of the present invention is particularly suitable for use as transportation equipment or transportation containers for precision parts, and in this case, even if a chemical solution such as a cleaning agent is attached, the molded article of the present invention maintains high transparency and is free from cracks and cracks. can be prevented.
  • the molded product of the present invention can be widely used not only for general products such as transparent storage cases, but also as parts for producing industrial products such as photomasks.
  • the obtained suspended acetone solution was centrifuged at 14,000 rpm for 30 minutes using a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.) to separate the precipitate component (acetone insoluble component) and the acetone solution (acetone soluble component). was separated. Then, the precipitated component (acetone-insoluble component) was dried, its weight (Q (g)) was measured, and the grafting rate was calculated using the following formula (1).
  • Q in formula (1) is the weight (g) of the acetone-insoluble portion of the graft copolymer (B).
  • W is the total weight (g) of the graft copolymer (B) used when determining Q.
  • the rubber fraction is the content of the rubbery polymer (r) contained in the graft copolymer (B).
  • Grafting rate (%) ⁇ (Q-W ⁇ rubber fraction)/W ⁇ rubber fraction ⁇ 100...(1)
  • Polymerization conversion rate (%) (total weight of charged raw materials x solid component ratio - total weight of raw materials other than monomers) / weight of charged monomers x 100...
  • the glass transition temperature (Tg) of the vinyl copolymer (A-2-1) was determined by differential scanning calorimetry (DSC) by heating a sample from 35°C to 250°C at a rate of 10°C/min in a nitrogen atmosphere. After that, it was cooled to 35°C, and the glass transition temperature observed when the temperature was raised again to 250°C was measured.
  • DSC differential scanning calorimetry
  • Tm melting point
  • MVR Liquidity
  • the thickness of the test piece is 2.5 mm.
  • the following evaluations were conducted regarding environmental impacts. After measuring the total transmittance of the test piece, the test piece was placed in a constant temperature and high humidity bath at a temperature of 40° C. and a humidity of 70% for one week. Thereafter, the test piece was taken out and the total light transmittance was measured again. The difference between the total light transmittance before placing in the constant temperature and high humidity tank and the total light transmittance after placing in the constant temperature and high humidity tank was checked and judged according to the following rank. The smaller the difference, the smaller the environmental impact, and the A judgment is the best.
  • D More than 5%
  • a test piece was molded from a pelletized thermoplastic resin composition using an ESC mold (thickness 2 mm, width 12 mm, length 15 mm) using an injection molding machine ("IS55FP-1.5A" manufactured by Toshiba Machinery Co., Ltd.). .
  • This test piece was set in a constant strain jig with a strain rate of 0.2 to 1.6%, and isopropyl alcohol (Wako Pure Chemical Industries, Ltd.) was dropped onto it. After that, 23°C, 50% R. H. After being left in the atmosphere for 48 hours, the test piece was removed from the jig, and the critical strain (%) of the material at which deterioration and cracking occurred was determined. The larger the critical strain (%), the better the chemical resistance.
  • thermoplastic resin composition was manufactured by the following method. Alternatively, the following commercially available products were used.
  • the polymerization temperature of the first unit was controlled at 110°C, and the average residence time was 2.0 hours.
  • the obtained polymer solution was continuously taken out in an amount equal to the amount supplied of styrene, acrylonitrile, methyl methacrylate, toluene, a molecular weight regulator, and a polymerization initiator using a pump installed outside the first reaction vessel. It was supplied to the first reaction vessel.
  • the polymerization temperature of the second reaction vessel was 130°C.
  • the copolymer solution obtained in the second reaction vessel was used to directly devolatilize the unreacted monomers and solvent using a two-screw three-stage vented extruder, and then the vinyl copolymer (A-1 -1) was obtained.
  • the analysis results of this vinyl copolymer (A-1-1) were as follows. Weight average molecular weight (Mw): 120,000 Refractive index: 1.517
  • Vinyl copolymer (A-1-2) except that 21 parts of styrene, 13 parts of acrylonitrile, 67 parts of methyl methacrylate, 0.4 parts of tert-dodecyl mercaptan, and 0.1 part of dicumyl peroxide were used.
  • a powdered vinyl copolymer (A-1-2) was obtained in the same manner as in the production.
  • the analysis results of this vinyl copolymer (A-1-2) were as follows. Weight average molecular weight (Mw): 80,000 Refractive index: 1.517
  • Vinyl copolymer (A-1) was produced in the same manner as in the production of vinyl copolymer (A-1-1), except that the amount of tert-dodecyl mercaptan used as a molecular weight regulator was 0.27 parts. -3) was obtained.
  • the analysis results of this vinyl copolymer (A-1-3) were as follows. Weight average molecular weight (Mw): 85,000 Refractive index: 1.517
  • Latex (r-1) solid content concentration 50% containing 45 parts of polybutadiene rubber with a volume average particle diameter of 280 nm and a gel content of 90% was charged into a separable flask with an internal volume of 10 L equipped with a stirrer. Thereafter, 0.5 parts of potassium oleate, 0.2 parts of glucose, 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate, and 100 parts of deionized water were added.
  • the grafting rate of the grafted polybutadiene (acetone insoluble portion) obtained by acetone treatment of the graft copolymer (B-1) was 52%, and the volume average particle diameter was 260 nm. Furthermore, the liberated methyl methacrylate/styrene/acrylonitrile copolymer (acetone soluble portion) had a refractive index of 1.517 and a weight average molecular weight of 54,000.
  • Polyamide elastomer (C) As the polyamide elastomer (C), "Pellestat M-140 (refractive index: 1.510)" manufactured by Sanyo Chemical Co., Ltd., which is a polyether ester amide block polymer based on nylon 6, was used. The melting point of this polyamide elastomer (C) was measured and found to be as follows. Melting point: 192°C
  • ⁇ Compatibilizer (E-1)> As the compatibilizer (E-1), acrylonitrile/ ⁇ -methylstyrene/acrylic acid copolymer (acrylonitrile/ ⁇ -methylstyrene/acrylic acid 20/75/5 (mass ratio)), weight average molecular weight: 67, 000) was used.
  • Examples 1 to 24, Comparative Examples 1 to 8 The components shown in Tables 1 to 3 were blended in the amounts shown in Tables 1 to 3, and 0.00005 parts of Solvent Blue 97 was added as a dye, and mixed at 23°C using a Henschel mixer. The obtained mixture was melt-kneaded at an extrusion temperature of 230° C. using a 30 mm ⁇ twin-screw extruder, and extruded into strands to form pellets. Using the obtained pellets of the thermoplastic resin composition, evaluation was performed by the method described above. The results are shown in Tables 1 to 3.
  • Comparative Examples 1, 2, and 4 that do not contain polyamide elastomer (C) have significantly inferior chemical resistance.
  • Comparative Example 3 which contains the polyamide elastomer (C) in a small amount, has poor chemical resistance.
  • Comparative Example 5 in which polyamide, which is a hard segment of polyamide elastomer (C), was used instead of polyamide elastomer (C) had poor transparency. In addition, the sheet appearance and readability are also poor.
  • Comparative Example 6 in which polyethylene glycol, which is a soft segment of polyamide elastomer (C), was used instead of polyamide elastomer (C), low fluidity (sheet moldability) tended to be poor.
  • Comparative Example 7 which does not contain the vinyl copolymer (A1) component, has too low a fluidity value and is poor in moldability, and is also poor in transparency, sheet appearance, and readability.
  • Comparative Example 8 in which polyamide elastomer (C) was blended in excess had poor transparency, sheet appearance, and readability, and had low rigidity. It also has poor chemical resistance.
  • the drawbacks of the compositions shown in these comparative examples are not at a level that can be adjusted by setting conditions such as molding processing, so they are not practical.
  • thermoplastic resin compositions of Examples 1 to 24 that meet the specifications of the present invention have low fluidity (sheet formability), transparency, sheet appearance, readability, impact resistance, chemical resistance, and heat resistance. Excellent balance in all aspects.
  • Example 7 which contains a large amount of the graft copolymer (B) even though it contains a sufficient amount of the polyamide elastomer (C), the heat resistance is slightly inferior to the other examples.
  • Example 8 which contains a large amount of vinyl copolymer (A1), sheet formability tends to be poor, but these are all at a practical level.
  • Example 9 which contains a relatively large amount of polyamide elastomer (C), tends to have lower rigidity than other Examples, it can be used depending on the application.
  • Example 10 using a vinyl copolymer (A-1-2) with a weight average molecular weight of 80,000 tends to have low fluidity (sheet formability) and poor chemical resistance, but can be used. be.
  • Examples 11 to 24 are excellent in low fluidity (sheet formability), transparency, impact resistance, chemical resistance, and heat resistance in a well-balanced manner. Furthermore, the environmental impact of the total light transmittance is small, the sheet appearance is excellent, and the readability (distance) is also excellent. Therefore, it can be suitably used for applications such as photomask cases.
  • the polyamide elastomer (C) is also expected to have an antistatic effect. For example, after leaving a disc (diameter 100 mm, thickness 2 mm) obtained by molding pellets of the thermoplastic resin composition of Example 23 under conditions of a temperature of 23° C. and a humidity of 50% RH for one day, When the surface resistivity ( ⁇ ) was measured at an applied voltage of 500 V, it showed a good value of 5 ⁇ 10 10 .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition de résine thermoplastique contenant un copolymère vinylique (A), obtenu par copolymérisation d'un mélange de monomères vinyliques (ma) contenant un monomère vinylique aromatique (a1) et un monomère ester de l'acide (méth)acrylique (a2), un copolymère greffé renforcé de caoutchouc (B), obtenu par copolymérisation greffée d'au moins un monomère vinylique aromatique (b1), un monomère ester d'acide (méth)acrylique (b2), et un monomère cyanure de vinyle (b3) en présence d'un polymère caoutchouteux (r), et d'un élastomère polyamide (C), le copolymère vinylique (A) contenant un copolymère vinylique (A1) présentant une masse moléculaire moyenne en poids de 50, 000 à 300 000, obtenu par copolymérisation d'un mélange de monomères vinyliques (ma1) contenant un monomère vinylique aromatique (a1), un monomère ester de l'acide (méth)acrylique (a2) et un monomère cyanure de vinyle (a3), et la composition de résine thermoplastique contient un total de 60 à 92 parties en masse de copolymère vinylique (A) et de copolymère greffé renforcé au caoutchouc (B) et de 8 à 40 parties en masse d'élastomère polyamide (C) pour 100 parties en masse totales de copolymère vinylique (A), de copolymère greffé renforcé au caoutchouc (B) et d'élastomère polyamide (C).
PCT/JP2023/030921 2022-09-16 2023-08-28 Composition de résine thermoplastique et article moulé associé WO2024057891A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02292353A (ja) * 1989-05-02 1990-12-03 Japan Synthetic Rubber Co Ltd 熱可塑性樹脂組成物
JP2006219643A (ja) * 2005-02-14 2006-08-24 Techno Polymer Co Ltd 熱可塑性樹脂組成物及び成形品
JP2016175971A (ja) * 2015-03-19 2016-10-06 東レ株式会社 熱可塑性樹脂組成物
JP2017145365A (ja) * 2016-02-19 2017-08-24 東レ株式会社 熱可塑性樹脂組成物、その製造方法および成形品
JP2021091836A (ja) * 2019-12-12 2021-06-17 東レ株式会社 変性ビニル系共重合体、その製造方法、それを含む熱可塑性樹脂組成物、および成形品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02292353A (ja) * 1989-05-02 1990-12-03 Japan Synthetic Rubber Co Ltd 熱可塑性樹脂組成物
JP2006219643A (ja) * 2005-02-14 2006-08-24 Techno Polymer Co Ltd 熱可塑性樹脂組成物及び成形品
JP2016175971A (ja) * 2015-03-19 2016-10-06 東レ株式会社 熱可塑性樹脂組成物
JP2017145365A (ja) * 2016-02-19 2017-08-24 東レ株式会社 熱可塑性樹脂組成物、その製造方法および成形品
JP2021091836A (ja) * 2019-12-12 2021-06-17 東レ株式会社 変性ビニル系共重合体、その製造方法、それを含む熱可塑性樹脂組成物、および成形品

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