WO2023153391A1 - 組成物及び樹脂成形体 - Google Patents

組成物及び樹脂成形体 Download PDF

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WO2023153391A1
WO2023153391A1 PCT/JP2023/003952 JP2023003952W WO2023153391A1 WO 2023153391 A1 WO2023153391 A1 WO 2023153391A1 JP 2023003952 W JP2023003952 W JP 2023003952W WO 2023153391 A1 WO2023153391 A1 WO 2023153391A1
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mass
composition
meth
antioxidant
composition according
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English (en)
French (fr)
Japanese (ja)
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祐次朗 濱田
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to JP2023580258A priority Critical patent/JPWO2023153391A1/ja
Priority to EP23752855.9A priority patent/EP4477709A4/en
Priority to KR1020247026504A priority patent/KR20240148830A/ko
Priority to CN202380020192.XA priority patent/CN118647668A/zh
Publication of WO2023153391A1 publication Critical patent/WO2023153391A1/ja
Priority to US18/795,046 priority patent/US20250051561A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
    • B65D1/22—Boxes or like containers with side walls of substantial depth for enclosing contents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • 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
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08L51/006—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 block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
    • A63H33/00—Other toys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/012—Additives improving oxygen scavenging properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the present invention relates to compositions and resin moldings.
  • (meth)acrylic resins Due to its excellent appearance, transparency, dimensional stability, and chemical resistance, (meth)acrylic resins are used as materials for housing equipment such as vanities, bathtubs, and flush toilets; building materials; vehicles such as interior and exterior materials for vehicles; It is widely used in many applications, such as for materials. On the other hand, (meth)acrylic resins have insufficient impact resistance.
  • a methacrylic thermoplastic polymer (B) having a specific monomer composition ratio and multi-layer acrylic polymer particles having a specific structure are described as a methacrylic resin composition having excellent moldability and impact resistance.
  • a methacrylic resin composition formulated by combining (A) and a specific additive is disclosed, but this resin composition has a problem that the amount of resin composition components eluted when immersed in a solvent is large. there were.
  • An object of the present invention is to provide a composition containing rubber particles for improving impact resistance, which is excellent in the original transparency of (meth)acrylic resin and excellent in solvent elution resistance, and a resin molded product. to do.
  • [1] Contains a (meth)acrylic polymer (A), an antioxidant (B), and rubber particles (C), and the mass ratio of the rubber particles (C)/antioxidant (B) is 8 or more.
  • a composition that is greater than or equal to 1000.
  • antioxidant (B) described in any one of [1] to [8], wherein the antioxidant (B) is selected from at least one of a phenol antioxidant, a phosphorus antioxidant and a sulfur antioxidant. composition.
  • [17] A food packaging container obtained by molding the composition according to any one of [1] to [14].
  • a method for manufacturing a food packaging container wherein the food packaging container is manufactured by the method for manufacturing a resin molding described in [19] or [20].
  • composition and resin molded article of the present invention are compositions containing rubber particles for improving impact resistance, and are excellent in the original transparency of (meth)acrylic resin, and the resin composition when immersed in a solvent.
  • the elution amount of substance components is small.
  • the composition of the present invention and its resin molded product have a small amount of elution of the resin composition components when immersed in a solvent, and are excellent in impact resistance and transparency. It is suitably used for containers and toys that come into contact with food.
  • (meth)acrylic resin means at least one selected from “acrylic resin” and “methacrylic resin”.
  • (Meth)acrylic polymer means at least one selected from “acrylic polymer” and “methacrylic polymer”.
  • (Meth)acrylate means at least one selected from “acrylate” and “methacrylate”.
  • (Meth)acrylic acid means at least one selected from “acrylic acid” and "methacrylic acid”. The same applies to "(meth)acrylonitrile” and "(meth)acrylamide”.
  • “monomer (monomer)” means an unpolymerized compound
  • “repeating unit” means a unit derived from the monomer formed by polymerization of the monomer.
  • the repeating unit may be a unit directly formed by a polymerization reaction, or may be a unit in which some of the units are converted to another structure by treating the polymer.
  • “% by mass” and “parts by mass” and “% by weight” and “parts by weight” are synonymous, and “% by mass” means the content of a predetermined component contained in the total amount 100% by mass Show a percentage.
  • the numerical range represented by “to” in this specification means the range including the numerical values described before and after "to” as lower and upper limits.
  • “AB” means from A to B inclusive.
  • composition of the present invention (hereinafter sometimes referred to as the "composition of the present invention") comprises a (meth)acrylic polymer (A), an antioxidant (B) and rubber particles (C). , a composition in which the mass ratio of the rubber particles (C)/antioxidant (B) is greater than 8 and less than 1,000.
  • the (meth)acrylic polymer (A) is one of the constituent components of the composition of the present invention.
  • the (meth)acrylic polymer (A) according to the present invention is preferably a homopolymer of methyl methacrylate or derived from methyl methacrylate with respect to 100% by mass of the total mass of the (meth)acrylic polymer (A).
  • a methyl methacrylate copolymer containing 80% by mass or more and less than 100% by mass of repeating units (hereinafter referred to as "MMA units") can be used.
  • MMA units methyl methacrylate copolymer containing 80% by mass or more and less than 100% by mass of repeating units
  • the (meth)acrylic polymer (A) contains 80% by mass or more and less than 100% by mass of MMA units and an alkyl other than methyl methacrylate (A copolymer containing more than 0% by mass and 20% by mass or less of repeating units derived from meth)acrylate (M) (hereinafter referred to as “alkyl (meth)acrylate (M) units”) can be used.
  • the copolymer is more preferably a copolymer containing 80% by mass or more and 99.5% by mass or less of MMA units and 0.5% by mass or more and 20% by mass or less of alkyl (meth)acrylate (M) units.
  • a copolymer containing 90% by mass or more and 98% by mass or less and 2% by mass or more and 10% by mass or less of alkyl (meth)acrylate (M) units is more preferable.
  • the (meth)acrylic polymer (A) may be a homopolymer of MMA from the viewpoint that the obtained resin molding has good transparency.
  • alkyl (meth)acrylate (M) examples include the following a). a) methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate , tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate , stearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)
  • alkyl (meth)acrylates may be used alone, or two or more thereof may be used in combination.
  • alkyl (meth)acrylates (M) methyl acrylate, Ethyl acrylate and n-butyl acrylate are more preferred, and methyl acrylate and ethyl acrylate are even more preferred.
  • (meth)acrylic polymer (A) In the (meth)acrylic polymer (A) according to the present invention, other monomer units copolymerizable with these other than MMA units and alkyl (meth)acrylate (M) units are added to the (meth)acrylic polymer. (A) It may be contained in the (meth)acrylic polymer (A) in a proportion of 30% by mass or less, for example, as long as the original properties are not impaired. Other monomers are not particularly limited as long as they are copolymerizable with methyl methacrylate, and examples thereof include the following b) to h).
  • the method for producing the (meth)acrylic polymer (A) is not particularly limited, and examples thereof include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Among these polymerization methods, from the viewpoint of excellent productivity, the (meth)acrylic polymer (A) is preferably produced by a bulk polymerization method or a suspension polymerization method, and is preferably produced by a bulk polymerization method. more preferred.
  • the (meth)acrylic polymer (A) preferably has a mass average molecular weight of 20,000 to 200,000, more preferably 50,000 to 150,000.
  • mass-average molecular weight of the (meth)acrylic polymer (A) is at least the lower limit, the resulting resin molding tends to have excellent mechanical properties. tend to be more sexual.
  • the mass average molecular weight is a value measured using standard polystyrene as a standard sample and using gel permeation chromatography.
  • the lower limit of the content of the (meth)acrylic polymer (A) contained in the total mass (100% by mass) of the composition of the present invention is not particularly limited, and is preferably 30% by mass or more. 40% by mass or more is more preferable, and 50% by mass or more is even more preferable.
  • the upper limit of the content of the (meth)acrylic polymer (A) is not particularly limited, and is preferably 99% by mass or less, more preferably 90% by mass or more, and even more preferably 80% by mass or more. .
  • the content of the (meth)acrylic polymer (A) in the total mass (100% by mass) of the composition of the present invention is preferably 30% by mass or more and 99% by mass or less, and 50% by mass or more and 90% by mass. % by mass or less is more preferable, and 60% by mass or more and 80% by mass or less is even more preferable.
  • the resulting resin molded article has transparency, heat resistance and The inherent properties of the (meth)acrylic resin, such as weather resistance, are less likely to be impaired, and if the amount is less than the above upper limit, the impact resistance of the resulting resin molding tends to be less likely to be impaired.
  • the antioxidant (B) according to the present invention is not particularly limited, but from the viewpoint of the transparency of the resulting resin molded product, phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants are preferable. is mentioned. Among these, phenolic antioxidants are more preferred, and hindered phenolic antioxidants are particularly preferred. These antioxidants may be used individually by 1 type, and may use 2 or more types together.
  • a hindered phenolic antioxidant is a phenolic compound having a substituent at the ortho-position to the phenolic OH group.
  • Hindered phenol antioxidants include triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octyl)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3 ,5-triazine, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di- t-butyl-4-hydroxyphenylpropionate)], octadecyl-3-(3,5
  • octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate for example, Adekastab AO-50 manufactured by ADEKA
  • pentaerythrityl-tetrakis[3-(3,5- di-t-butyl-4-hydroxyphenyl)propionate] for example, Adekastab AO-60 manufactured by ADEKA
  • Phosphorus-based antioxidants include, for example, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, and 4,4'-butylidene-bis(3-methyl-6-t-butylphenylditridecyl)phosphite.
  • cyclic neopentanetetrayl bis(nonylphenyl) phosphite cyclic neopentanetetrayl bis(dinonylphenyl) phosphite, cyclic neopentanetetrayl tris(nonylphenyl)phosphite, cyclic neopentanetetrayl Tris(dinonylphenyl)phosphite, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diisodecylpentaerythritol diphosphite, tris(2,4-di -t-butylphenyl)phosphite and the like.
  • Sulfur-based antioxidants such as dilauryl-(3,3-thiodipropionate, dimyristyl-3,3-thiodipropionate, distearyl-3,3-thiodipropionate, lauryl-stearyl-3,3 -thiodipropionate, pentaerythrityl-tetrakis(3-laurylthiopropionate), etc.
  • distearyl-3,3-thiodipropionate for example, manufactured by BASF, Irganox PS 802FL. preferable.
  • the lower limit of the content of the antioxidant (B) contained in the total mass (100 mass%) of the methacrylic resin composition of the present invention is preferably more than 0.1 mass%, more preferably 0.2. It is at least 0.25% by mass, and more preferably at least 0.25% by mass.
  • the upper limit of the content of the antioxidant (B) is preferably less than 5.0% by mass, preferably 2.0% by mass or less, and more preferably 1.5% by mass or less.
  • the content of the antioxidant (B) in the total mass (100% by mass) of the methacrylic resin composition of the present invention is preferably more than 0.1% by mass and less than 5.0% by mass.
  • the content of the antioxidant (B) in the total mass (100% by mass) of the methacrylic resin composition of the present invention is at least the above lower limit, the obtained resin molded product is immersed in a solvent. When the amount of elution is small and is equal to or less than the above upper limit, there is a tendency that the transparency of the obtained resin molded article is hardly impaired.
  • the rubber particles (C) according to the present invention are preferably particles with a two-layer structure or more, and more preferably particles with a three-layer structure or more, from the viewpoint of the flexibility of the resin molding.
  • particles having a multilayer structure of two or more layers at least one selected from methyl methacrylate units, alkyl (meth)acrylate units other than methyl methacrylate units, and aromatic vinyl units, from the viewpoint of the transparency of the resin molding. and a graft layer (b) containing methyl methacrylate units.
  • the inner layer (a) includes the innermost layer (a-1) (hereinafter simply referred to as "inner layer (a-1)”) and the intermediate layer (a-2). , that is, a multilayer structure of three or more layers including at least an inner layer (a-1), an intermediate layer (a-2), and a graft layer (b).
  • the glass transition temperature of the rubber portion of the rubber particles (C) is preferably -20°C or lower, more preferably -25°C or lower, even more preferably -30°C or lower, and particularly preferably -35°C or lower.
  • Each layer in the multi-layer structure has a three-layer structure consisting of an inner layer (a-1) 1, an intermediate layer (a-2) 2, and an outer graft layer (b) 3 from the center side, as shown in FIG. do.
  • a-1 inner layer
  • a-2 intermediate layer
  • b outer graft layer
  • the inner layer (a-1) in the rubber particle (C) according to the present invention contains 40 to 80% by mass of methyl methacrylate units, particularly 45 to 70% by mass, and 1 to 60% by mass of alkyl (meth)acrylate units other than methyl methacrylate. , Especially 10 to 50% by weight, 0 to 10% by weight of aromatic vinyl units, especially 1 to 7% by weight, and copolymerizable crosslinkable monomer units (hereinafter referred to as "polyfunctional monomers" 0.01 to 1% by weight, particularly 0.02 to 0.8% by weight of the crosslinked polymer.
  • the inner layer (a-1) comprises a monomer mixture containing methyl methacrylate, a cross-linkable monomer copolymerizable with an alkyl (meth) acrylate other than methyl methacrylate, and an aromatic vinyl compound used as necessary. It can be formed by polymerizing so as to have the above monomer composition.
  • the composition of the present invention can have excellent impact resistance and transparency.
  • the amount of the alkyl methacrylate having 1 to 4 carbon atoms in the alkyl group in the monomer mixture is 40% by mass or more, a resin composition having higher transparency can be obtained.
  • the content of the polyfunctional monomer used in the inner layer (a-1) is 0.01 to 1 part by mass with respect to 100 parts by mass of the above monomer mixture. It is preferable in terms of gender balance. In addition, even if it consists of a single monomer, it will be referred to as a "monomer mixture" for convenience.
  • alkyl (meth)acrylate other than methyl methacrylate used for the alkyl (meth)acrylate unit other than methyl methacrylate in the inner layer (a-1) an alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms or an alkyl group having 2 to 4 carbon atoms is preferable from the viewpoint of the transparency of the resin molding from which the alkyl acrylate having a is of 1 to 8 is obtained.
  • alkyl methacrylates having an alkyl group having 2 to 4 carbon atoms include ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and the like. These can be used alone or in combination of two or more.
  • alkyl acrylates having 1 to 8 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These can be used alone or in combination of two or more. Of these, n-butyl acrylate is preferred.
  • the aromatic vinyl compound used for the aromatic vinyl unit of the inner layer (a-1) is not particularly limited as long as it can be copolymerized with the above monomers.
  • Group vinyl compounds may be mentioned. These can be used alone or in combination of two or more. Of these, styrene is preferred.
  • a monomer having two or more copolymerizable functional groups is classified as a polyfunctional monomer shown below, and is not classified as an aromatic vinyl compound.
  • polyfunctional monomer used in the inner layer (a-1) examples include ethylene glycol diacrylate, 1,3-butanediol diacrylate, allyl acrylate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, Methacrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, divinylbenzene, diallyl phthalate, diallyl fumarate, and triallyl trimellitate. These can be used alone or in combination of two or more. Of these, 1,3-butanediol dimethacrylate and allyl methacrylate are preferred.
  • the intermediate layer (a-2) in the rubber particles (C) according to the present invention contains 60 to 99.8% by mass, particularly 70 to 90% by mass of alkyl (meth)acrylate units, and 0 to 39.8% by mass of aromatic vinyl units. % by mass, particularly 5.0 to 20.0 mass %, and copolymerizable crosslinkable monomer (polyfunctional monomer) unit 0.2 to 10.0 mass %, particularly 0.5 to 5.0 mass %. It is preferably a layer containing an elastic copolymer containing 0% by mass.
  • the intermediate layer (a-2) contains an alkyl (meth)acrylate, an aromatic vinyl compound, and a polyfunctional monomer in the presence of the inner layer (a-1) with the above monomer unit composition. It can be formed by polymerizing so that
  • an alkyl acrylate having an alkyl group with 1 to 8 carbon atoms is preferable.
  • the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group the same alkyl acrylate having 1 to 8 carbon atoms in the alkyl group that can be used in the inner layer (a-1) described above can be used. can be mentioned. These can be used alone or in combination of two or more. Of these, n-butyl acrylate is preferred.
  • aromatic vinyl compound used for forming the intermediate layer (a-2) include the same aromatic vinyl compounds as those exemplified as the aromatic vinyl compounds that can be used for the inner layer (a-1). . These can be used alone or in combination of two or more. Of these, styrene is preferred.
  • polyfunctional monomer used for forming the intermediate layer (a-2) include the same polyfunctional monomers as those exemplified as the polyfunctional monomer that can be used for the inner layer (a-1). can be done. These can be used alone or in combination of two or more. Of these, 1,3-butanediol dimethacrylate and allyl methacrylate are preferred.
  • the graft layer (b) in the rubber particles (C) according to the present invention contains 70 to 100% by mass of methyl methacrylate units, particularly 80 to 100% by mass, and 1 to 30% by mass of alkyl (meth)acrylate units other than methyl methacrylate. A layer containing 1 to 20% by mass of a non-crosslinkable hard polymer is particularly preferred.
  • the graft layer (b) is an inner layer obtained by polymerizing a monomer component in the presence of the polymer formed up to the intermediate layer (a-2), that is, in the presence of the inner layer (a-1).
  • methyl methacrylate and optionally an alkyl (meth)acrylate other than methyl methacrylate are added so as to have the above monomer unit composition. It can be formed by polymerization.
  • the composition of the present invention can have excellent impact resistance.
  • a proportion of 70 to 100% by weight of methyl methacrylate units results in a composition with high impact resistance.
  • the alkyl (meth)acrylate other than methyl methacrylate used as the alkyl (meth)acrylate unit other than methyl methacrylate in the graft layer (b) includes an alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms or an alkyl group having 1 carbon atom.
  • Alkyl acrylates of ⁇ 8 are preferable from the viewpoint of the transparency of the resin molding. Examples of such alkyl (meth)acrylates include the same alkyl (meth)acrylates other than methyl methacrylate used in the inner layer (a-1) or alkyl acrylates having 1 to 8 carbon atoms in the alkyl group. Specific examples can be given, and preferable ones are also the same.
  • an aromatic vinyl compound may be used in combination with the above monomers.
  • Specific examples of the aromatic vinyl compound used in the graft layer (b) include the same aromatic vinyl compounds as those exemplified as the aromatic vinyl compound that can be used in the inner layer (a-1). These can be used alone or in combination of two or more. Of these, styrene is preferred.
  • the respective monomer components for obtaining the inner layer (a-1), the intermediate layer (a-2) and the graft layer (b) may contain components other than the above monomers.
  • a component compatibility with the (meth)acrylic polymer (A) serving as the matrix resin in the polymerization of these monomer components, particularly in the polymerization of the monomer component for obtaining the rubber particles (C).
  • chain transfer agents such as alkyl mercaptans used to improve fluidity and impact resistance.
  • alkyl mercaptan examples include n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like.
  • the chain transfer agent may be used in an amount of 0.1 to 2 parts by mass per 100 parts by mass of the monomer component used.
  • the mass ratio (a-1)/(a-2) between the inner layer (a-1) and the intermediate layer (a-2) in the rubber particles (C) is preferably 10/90 to 90/10, more preferably 15 /85 to 25/75.
  • mass percentage of the inner layer (a-1) in the total mass of the inner layer (a-1) and the intermediate layer (a-2) is 10 or more, impact is applied to the resin molded article made of the composition of the present invention. Suppresses whitening when added. If this ratio is 90 or less, the composition will have sufficient impact resistance.
  • the graft layer (b) is preferably 30 to 100 parts by mass, more preferably 50 to 100 parts by mass. 80 parts by mass.
  • the content of the graft layer (b) is 30 to 100 parts by mass based on 100 parts by mass of the polymer formed up to the intermediate layer (a-2), the impact resistance of the composition of the present invention is sufficient. become a thing.
  • the mass of each layer is calculated as the sum of the masses of the monomer components that make up each layer.
  • a latex of the polymer constituting each layer is sequentially obtained by emulsion polymerization of the monomer components forming the structural units of the polymer of each layer. and a method of recovering it as a graft polymer having a multilayer structure.
  • Emulsion polymerization can be carried out according to a known method.
  • the polymerization initiator used in the polymerization reaction for forming the polymer of each layer of the rubber particles (C) for example, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, peroxides such as hydrogen peroxide substances; azo compounds such as azobisisobutyronitrile; persulfate compounds such as potassium persulfate and ammonium persulfate; perchloric acid compounds; radical polymerization initiators such as perboric acid compounds. These may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • Initiators such as these peroxides are alkali metal salts of sulfite, alkali metal salts of thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetone acid, ferrous sulfate, ferrous sulfate and ethylenediaminetetraacetic acid. It may also be used as a redox initiator in combination with a reducing agent such as a complex of sodium. In particular, it is preferable to use an alkali metal salt of thiosulfate such as sodium thiosulfate from the viewpoint of the transparency of the resulting resin molding. Therefore, the composition obtained by using the above-described initiator contains compounds derived from the initiator.
  • the composition may contain an alkali metal salt of thiosulfate and/or a derivative of an alkali metal salt of thiosulfate. preferable.
  • the amount of these radical polymerization initiators to be added can be appropriately selected depending on the type and blending ratio of the radical polymerization initiator and the monomer component to be used. It can be about 10 parts by mass.
  • anionic, cationic, and nonionic emulsifiers can be used in the emulsion polymerization of the monomer components constituting the polymer of each layer to obtain the rubber particles (C).
  • anionic emulsifiers are particularly preferred.
  • anionic emulsifiers include carboxylates such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, and dipotassium alkenyl succinate; sulfate ester salts such as sodium lauryl sulfate; Examples include sulfonates such as sodium dioctylsulfosuccinate, sodium alkylbenzenesulfonate, sodium alkyldiphenylether disulfonate, and phosphate salts such as sodium polyoxyethylene alkyl ether phosphate. These may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • an alkali metal salt of alkylbenzenesulfonic acid particularly sodium alkylbenzenesulfonate
  • the number of carbon atoms in the alkyl group of the alkali metal salt of alkylbenzenesulfonic acid to be used is preferably 8 or more and 14 or less.
  • the alkali metal salt of alkylbenzenesulfonic acid it is most preferable to use sodium dodecylbenzenesulfonate.
  • the composition obtained by using the above emulsifier contains a compound derived from the emulsifier.
  • the composition preferably contains an alkali metal salt of alkylbenzenesulfonic acid, and further an alkali metal salt of dodecylbenzenesulfonic acid. It preferably contains salt.
  • Various methods such as an acid coagulation method, a salt coagulation method, a freeze coagulation method, and a spray drying method can be used as methods for recovering a polymer having a multilayer structure from the above latex.
  • the recovery agent used in the salt coagulation method include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate. Calcium acetate is particularly preferred in order to suppress coloration of resin moldings obtained by molding the composition used as the impact strength modifier.
  • the recovery agent concentration in the recovery agent aqueous solution is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass. If the recovery agent concentration in the recovery agent aqueous solution is 0.1% by mass or more, it is possible to stably recover the rubber particles (C), and if the concentration is 20% by mass or less, the recovered multilayer A large amount of the recovery agent is not mixed in the rubber particles (C) having the structure, and deterioration in performance such as increased coloration can be suppressed in the resin molded product of the composition containing the recovery agent.
  • the collected rubber particles (C) can be dried and obtained as powder. After the rubber particles (C) are dried and obtained as a powder, a lubricant such as silica gel fine particles is added to the rubber particles (C) in order to suppress blocking of the rubber particles (C) and improve handleability. They can also be mixed.
  • a lubricant such as silica gel fine particles is added to the rubber particles (C) in order to suppress blocking of the rubber particles (C) and improve handleability. They can also be mixed.
  • the mass average particle diameter of the polymer of the inner layer (a-1) of the rubber particles (C) according to the present invention is preferably 150-250 nm, particularly preferably 170-200 nm. If the mass average particle size of the polymer of the inner layer (a-1) is at least the above lower limit, the impact resistance of the obtained resin molded article is good, and if it is at most the above upper limit, the obtained resin molded article has good transparency. Good.
  • the mass average particle diameter of the polymer in which the intermediate layer (a-2) is further formed on the inner layer (a-1) is preferably 220 to 300 nm, particularly 240 to 280 nm. If the mass average particle diameter of the polymer forming up to the intermediate layer (a-2) is at least the above lower limit, the resulting resin molded article has good impact resistance, and if it is below the above upper limit, the obtained resin molded article. transparency is good.
  • the mass average particle diameter of the rubber particles (C) of the present invention comprising the inner layer (a-1), the intermediate layer (a-2) and the graft layer (b) is 240 to 400 nm, particularly 260 to 320 nm. is preferred. If the mass average particle size of the rubber particles (C) is at least the above lower limit, the resulting resin molding will have good impact resistance, and if it is at most the above upper limit, the resulting resin molding will have good transparency.
  • the mass-average particle diameters of the inner layer (a-1), rubber particles (C), etc. are values measured by the method described in the Examples section below.
  • the lower limit of the content of the rubber particles (C) contained in the total mass (100% by mass) of the composition of the present invention is not particularly limited, and is preferably 1% by mass or more, and 10% by mass or more. More preferably, 20% by mass or more is even more preferable.
  • the upper limit of the content of the rubber particles (C) is not particularly limited, and is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less.
  • the content of the rubber particles (C) in the total mass (100% by mass) of the composition of the present invention is preferably 1% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 70% by mass or less.
  • the content of the rubber particles (C) in the total mass (100% by mass) of the composition of the present invention is at least the above lower limit, the impact resistance of the resulting resin molding can be increased, and the above upper limit If it is less than the value, it is possible to sufficiently maintain the original performance of the (meth)acrylic resin such as transparency, heat resistance and weather resistance of the resin molded product obtained, and the amount of elution when immersed in a solvent is small. tend to become
  • the ratio represented by [mass ratio of rubber particles (C)/antioxidant (B)] is greater than 8 and less than 1,000.
  • the [rubber particle (C)/antioxidant (B) mass ratio] is less than 1000, preferably 450 or less, more preferably 350 or less, further preferably 250 or less, particularly 230. The following are preferred.
  • the [mass ratio of rubber particles (C)/antioxidant (B)] is greater than 8, preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, and particularly preferably is 35 or more.
  • the [rubber particle (C)/antioxidant (B) mass ratio] is in the range of greater than 8 and less than 1000, preferably 10 or more and 450 or less, more preferably 20 or more and 350 or less, and 30 or more. 250 or less is more preferable, and 35 or more and 230 or less is particularly preferable.
  • the antioxidant (B) removes radicals and inert substances generated in the composition. Supplementally, it is thought that the elution amount can be suppressed when the resultant resin molded article is immersed in a solvent.
  • the [rubber particle (C) / antioxidant (B) mass ratio] is set to a range greater than 8, the elution of the antioxidant (B) itself is suppressed, or the antioxidant (B) itself is It is possible to prevent the influence of the tint and maintain the transparency of the obtained resin molding.
  • the composition of the present invention contains components other than the (meth)acrylic polymer (A), the antioxidant (B) and the rubber particles (C) within a range that does not impair the purpose of the present invention. can do.
  • Other components that the composition of the present invention may contain include UV absorbers, light stabilizers, release agents, pigments, dyes, and the like. These other components can be contained in the composition of the present invention in the range of 5.0% by mass or less.
  • the composition of the present invention can be produced by using an alkali metal salt of alkylbenzenesulfonic acid and an alkali metal salt of thiosulfate as an emulsifier and a polymerization initiator, respectively, in the production of the rubber particles (C) according to the present invention. and/or an alkali metal salt derivative of alkylbenzenesulfonic acid, an alkali metal salt of thiosulfuric acid and/or an alkali metal salt derivative of thiosulfuric acid are contained in the rubber particles (C) to form the composition of the present invention. contained in
  • the content of the alkali metal salt of alkylbenzenesulfonic acid and/or the derivative of the alkali metal salt of alkylbenzenesulfonic acid in the composition of the present invention is 0.01 to 10.0% by weight, especially 0.05 to 5.0% by weight. is preferably When the content of the alkali metal salt of alkylbenzenesulfonic acid and/or the derivative of the alkali metal salt of alkylbenzenesulfonic acid is at least the above lower limit, the stability of the latex during polymerization is good, and when it is at most the above upper limit, the obtained resin molding. Good body transparency.
  • the content of the alkali metal thiosulfate and/or the derivative of the alkali metal thiosulfate in the composition of the present invention is 0.001 to 5.0% by mass, particularly 0.005 to 1.0% by mass. is preferably If the content of the alkali metal salt of thiosulfate and/or the derivative of the alkali metal salt of thiosulfate is at least the above lower limit, the amount of elution when the obtained resin molded product is immersed in a solvent is kept small, and is below the above upper limit. If it is, the transparency of the resin molding obtained will become favorable.
  • the solvent is The amount of elution of the resin composition component when immersed is small, and the transparency and impact resistance are excellent. The reason for this is presumed as follows. An alkali metal salt of alkylbenzenesulfonic acid is used as an emulsifier in the production of rubber particles (C).
  • Alkylbenzenesulfonic acid derivatives have excellent thermal stability and do not generate substances that promote decomposition of the (meth)acrylic polymer (A) and rubber particles (C). It is presumed that the elution amount of the composition components can be kept small.
  • the alkali metal salt of thiosulfate acts as a reducing agent and produces an alkali metal salt of sulfite and an alkali metal salt of sulfuric acid when it is oxidized by a redox reaction. The reaction proceeds without producing substances that promote decomposition of the rubber particles (C). Therefore, it is presumed that the elution amount of the resin composition components when immersed in the solvent can be suppressed.
  • the composition of the present invention contains the above-described (meth)acrylic polymer (A), antioxidant (B) and rubber particles (C), and optionally other components at a predetermined compounding ratio. It can be produced by blending. At this time, the order of mixing the (meth)acrylic polymer (A), the antioxidant (B), the rubber particles (C) and other optional components is not particularly limited, and all components are They may be mixed all at once, each component may be mixed sequentially, or some components may be mixed in advance and then mixed with other components.
  • the composition of the present invention has a small amount of elution of resin composition components when immersed in a solvent, and preferably satisfies the following (I).
  • (I) A resin molded article obtained by molding the composition of the present invention is subjected to a 120° F. The maximum absorbance in the ultraviolet region of the extract extracted for 24 hours at the temperature is less than 1.5.
  • the maximum ultraviolet absorbance of (I) is preferably 1.0 or less, more preferably 0.95 or less, and still more preferably 0.90 or less.
  • composition of the present invention When the composition of the present invention is immersed in a solvent, the amount of resin composition components eluted is small, and the composition is excellent in impact resistance and transparency. It is preferable as a composition for use, and particularly suitable as a composition for food packaging containers.
  • the molding method for molding the composition of the present invention to obtain the resin molded article of the present invention includes, for example, injection molding, extrusion molding, and pressure molding. Further, the obtained resin molded body may be subjected to secondary molding such as air pressure molding or vacuum molding. Among these, injection molding is preferable because it can cope with particularly complicated shapes. Molding conditions such as molding temperature and molding pressure may be appropriately set.
  • the resin molded article of the present invention comprising the composition of the present invention preferably has such excellent transparency that the yellow index at a molded piece thickness of 3 mm measured in accordance with ISO 17223 is 1.5 or less.
  • This yellow index is more preferably 1.4 or less, still more preferably 1.3 or less.
  • the resin molded article of the present invention has a small amount of elution of the resin composition components when immersed in a solvent, and is excellent in impact resistance and transparency. It is suitable for use as a toy that is put in a child's mouth.
  • SFS sodium formaldehyde sulfoxylate
  • Na 2 S 2 O 3 sodium thiosulfate (Na thiosulfate)
  • ST styrene
  • BA n-butyl acrylate
  • AMA allyl methacrylate
  • TBHP t-butyl hydroperoxide
  • MMA methyl methacrylate
  • nOM n-octyl mercaptan
  • MA methyl acrylate emulsifier
  • D-1) sodium dodecylbenzenesulfonate emulsifier
  • D -2) Polyoxyethylene alkyl ether phosphate (meth)acrylic polymer
  • A-1) ACRYPET (registered trademark) VH (manufactured by Mitsubishi Chemical Corporation, mass average molecular weight: 80,000)
  • the mass average particle size of the rubber particles (C) was measured as follows.
  • the obtained latex was diluted with distilled water to obtain a diluted latex having a solid concentration of about 3%. , a pressure of about 2.76 MPa (about 4000 psi), and a temperature of 35°C.
  • a capillary cartridge for particle separation and a carrier liquid were used, and the liquid was almost neutral.
  • monodisperse polystyrene with a known particle size manufactured by DUKE, USA was used as a standard particle size substance, and the particle size was measured at a total of 12 points from 20 nm to 800 nm to create a calibration curve.
  • Charpy notched resin molded body Impact strength (kJ/m 2 ) was measured. A higher Charpy impact strength means better impact resistance. As a judgment, if it is 2.0 or more, it is “O”, and if it is less than 2.0, it is "X".
  • Component 2 Ferrous sulfate 8.0 ⁇ 10 ⁇ 4 parts Disodium ethylenediaminetetraacetate 2.4 ⁇ 10 ⁇ 3 parts Na 2 S 2 O 3 0.50 parts
  • a mixture (a-1) having the following composition for the inner layer (a-1) was added over 2 hours, and maintained at 80° C. for 1 hour to form a polymer for the inner layer (a-1). to complete the polymerization.
  • the obtained latex (A-1) had a polymerization rate (unreacted monomers measured by gas chromatography, the same applies hereinafter) of 99% or more, and the mass average particle diameter of the polymer for the inner layer (a-1) was was 190 nm.
  • Matture (a-1)) MMA 22.0 parts BA 16.0 parts ST 2.0 parts AMA 0.2 parts TBHP 0.07 parts Emulsifier (D-1) 1.0 parts
  • antioxidants As antioxidants, the following antioxidants (B-1) to (B-3) were used.
  • Examples 2 to 18, Comparative Examples 1 to 11 The rubber particles ( A composition was obtained in the same manner as in Example 1, except that C) was used in the amounts shown in Tables 1B and 2B. The evaluation results of each composition are shown in Tables 1A, 1B, 2A and 2B.
  • Tables 1A and 1B reveal the following.
  • the compositions and resin moldings of Examples 1 to 12 had a small amount of elution upon contact with a solvent, and were excellent in impact resistance and transparency.
  • compositions and resin moldings of Comparative Examples 1 and 2 did not contain the antioxidant (B), they had good transparency, but had a large amount of elution upon contact with the solvent.
  • the compositions of Comparative Examples 3 to 5 had a small mass ratio of rubber particles (C)/antioxidant (B), insufficient transparency, or a large amount of elution upon contact with a solvent. Since Reference Example 1 does not contain rubber particles (C), the amount of elution is small and the transparency is excellent, but the impact resistance is poor.
  • Tables 2A and 2B reveal the following.
  • the compositions and resin moldings of Examples 13 to 18 had a small amount of elution upon contact with a solvent, and were excellent in impact resistance and transparency.
  • compositions and resin moldings of Comparative Examples 6 to 11 are of the same system (the (meth)acrylic polymer (A) and the rubber particles (C) have the same mass parts), Since the antioxidant (B) was not contained, the transparency was good, but the amount of elution was large when it came into contact with the solvent.
  • Reference Example 1 does not contain rubber particles (C), the amount of elution is small and the transparency is excellent, but the impact resistance is poor.
  • the composition of the present invention and its resin molded product have a small amount of elution of the resin composition components when immersed in a solvent, and are excellent in impact resistance and transparency. It is suitable for use as a food packaging container and as a toy that children put in their mouths.

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