WO2020241690A1 - Particule de caoutchouc acrylique et composition de résine méthacrylique - Google Patents

Particule de caoutchouc acrylique et composition de résine méthacrylique Download PDF

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WO2020241690A1
WO2020241690A1 PCT/JP2020/020929 JP2020020929W WO2020241690A1 WO 2020241690 A1 WO2020241690 A1 WO 2020241690A1 JP 2020020929 W JP2020020929 W JP 2020020929W WO 2020241690 A1 WO2020241690 A1 WO 2020241690A1
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mass
acrylic rubber
rubber particles
methacrylic resin
layer
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PCT/JP2020/020929
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English (en)
Japanese (ja)
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坂本　滋
康成 梅田
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株式会社クラレ
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Priority to JP2021522814A priority Critical patent/JPWO2020241690A1/ja
Publication of WO2020241690A1 publication Critical patent/WO2020241690A1/fr

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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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to acrylic rubber particles having a high gel content but improved solvent dispersibility, a methacrylic resin composition containing the rubber particles, a molded product, and agglomerated particles.
  • Methacrylic resin has high transparency and is useful as a material for molded products used for optical members, lighting members, signboard members, decorative members, and the like.
  • methacrylic resins have the property of being easily broken and brittle, and are difficult to handle. Therefore, in order to eliminate the brittleness of the acrylic film, a technique of adding acrylic rubber particles is disclosed (Patent Document 1).
  • Patent Document 1 describes that the gel content of the crosslinked rubber particles is 75% by mass or less in order to enhance the dispersibility of the crosslinked rubber in the solvent. However, Patent Document 1 describes that such a rubber has a high gel content and poor dispersibility in a solvent.
  • the rubber particles disclosed in Patent Document 1 have a two-layer structure, and the dispersibility effect on a solvent in a three-layer structure or more is not disclosed.
  • An object of the present invention is an acrylic rubber particle having improved solvent dispersibility while imparting sufficient impact resistance, an aggregated powder thereof, a methacrylic resin composition containing the acrylic rubber particle, and molding using the same. To provide the body.
  • Acrylic rubber particles (C) having a multilayer structure of three or more layers having at least a core layer (a-1) containing a crosslinked polymer containing 0.01 to 1% by mass of a monomer unit.
  • the weight average molecular weight of the hard polymer in the outer layer (b) is 30,000 or more.
  • the gel content of the acrylic rubber particles (C) is larger than 75% by mass,
  • the particle size (DW) of the acrylic rubber particles (C) in water is 50 to 350 nm.
  • Acrylic rubber particles (C) according to any one of [1] to [3] or a non-crosslinked methacrylic resin containing 60% by weight or more of the agglomerated powder and methyl methacrylate unit according to [4].
  • the mass ratio of the acrylic rubber particles (C) to 100 parts by mass in total of the acrylic rubber particles (C) and the methacrylic resin (D) is in the range of 2 to 90 parts by mass [5].
  • the methacrylic resin composition according to. [7] A molded product containing the methacrylic resin composition according to [5] or [6].
  • the methacrylic resin composition of the present invention contains (1) acrylic rubber particles (C) obtained by an emulsion polymerization method and (2) methacrylic resin (D), and the methacrylic resin (D) contains 60 methyl methacrylate units. It is a non-crosslinked polymer containing mass% or more, and is a resin having a weight average molecular weight (Mw) of 100,000 or more.
  • methyl methacrylate unit means a structural unit derived from methyl methacrylate, and is specifically represented by the following formula (1).
  • alkyl acrylate unit means a structural unit derived from alkyl acrylate, and is specifically represented by the following formula (2).
  • a copolymerizable crosslinkable monomer unit means a structural unit derived from a copolymerizable crosslinkable monomer.
  • Acrylic rubber particles (C) The acrylic rubber particles (C) of the present invention have an outer layer (b) containing a non-crosslinked hard polymer containing 70% by mass or more of methyl methacrylate units, and an alkyl acrylate unit 60 to 99.8% by mass inscribed therein.
  • An intermediate layer (a-2) containing an elastic copolymer containing 0.2 to 10% by mass of a copolymerizable crosslinkable monomer unit, and 40 to 98.9% by mass of a methyl methacrylate unit and alkyl.
  • the weight average molecular weight of the hard polymer of the outer layer (b) is 30,000 or more, the gel content of the acrylic rubber particles is larger than 75% by mass, and the acrylic rubber particles (C) are in water.
  • the particle size (DW) of the above is 50 to 350 nm
  • the particle size (DW) of the acrylic rubber particles (C) in water and the dispersed particle size (DW) of the aggregated particles of the rubber particles (C) in methylene chloride ( DM) is an acrylic rubber particle characterized by DM / DW ⁇ 10.
  • DW collects a polymerized latex containing a core layer (a-1), an intermediate layer (a-2), and an outer layer (b), and obtains an average particle size by a light scattering method.
  • This is a measurement, and can be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device LA-950 manufactured by Horiba Seisakusho Co., Ltd.
  • DM is an agglomerated powder obtained by coagulating, washing and dehydrating a polymerized latex containing a core layer (a-1), an intermediate layer (a-2) and an outer layer (b).
  • the (coagulated product) was dispersed in methylene chloride by stirring overnight at room temperature using a shaker at a concentration of 5%, and dropped into 10 mL of methylene chloride, and the scattering intensity was 70 to 90%.
  • the particle size can be measured by the light scattering method (volume conversion) using the laser diffraction / scattering type particle size distribution measuring device LA-300 manufactured by Horiba Seisakusho Co., Ltd.
  • the particle size is the median diameter.
  • the acrylic rubber particles of the present invention are defined by using DW measured using a latex after polymerization and DM measured using a coagulated powder obtained by coagulating the latex, and include a coagulated product.
  • the coagulated product includes coagulated powder, granules and the like.
  • the multilayer structure means a core-shell structure having three or more layers, preferably 3 to 5 layers, more preferably 3 to 4 layers, and particularly 3 layers.
  • the multilayer structure may be composed of an outer layer (b), an intermediate layer (a-2), and a core layer (a-1), and in the case of four layers, two outer layers (b) (b).
  • It may be composed of -1 layer and b-2 layer, 1 layer intermediate layer (a-2), 1 layer core layer (a-1), 1 layer outer layer (b), and 2 layers intermediate. It may be composed of layers (a-2-1 layer and a-2-2 layer) and one core layer (a-1).
  • the acrylic rubber particles are multi-layered acrylic rubber particles produced by emulsion polymerization, and the rubber particles are supplied as agglomerated powder.
  • the method for producing agglomerated powder of acrylic rubber particles includes a step of aggregating the polymer from an emulsion of a polymer having a multi-layer structure obtained in a polymerization step such as emulsion polymerization by a coagulation step, washing and drying.
  • the weight average molecular weight of the hard polymer of the outer layer (b) is preferably 30,000 or more, more preferably 40,000 to 500,000, and further preferably 50,000 to 400,000.
  • the particle size (DW) of the acrylic rubber particles (C) in water is preferably 50 to 350 nm, more preferably 55 to 340 nm, and even more preferably 60 to 330 nm.
  • the dispersed particle size (DM) in which the aggregated powder of the acrylic rubber particles (C) is dispersed in methylene chloride is preferably less than 10 times the particle size (DW) in water, more preferably 0.1 to It is 8 times, more preferably 0.2 to 4 times.
  • the lower limit of the particle size of the acrylic rubber particles (C) of the present invention in water is preferably 0.01 ⁇ m, more preferably 0.04 ⁇ m, still more preferably 0.07 ⁇ m, still more preferably 0.1 ⁇ m.
  • the upper limit of the average particle size is preferably 1 ⁇ m, more preferably 0.5 ⁇ m, still more preferably 0.4 ⁇ m, and even more preferably 0.3 ⁇ m.
  • the weight average particle size of the agglomerated powder composed of the acrylic rubber particles (C) of the present invention before being dispersed in methylene chloride is preferably 100 to 1000 ⁇ m, more preferably 200 to 900 ⁇ m.
  • the weight average particle diameter of the rubber particles (C) can be measured by the following method.
  • the preferable acrylic rubber particles (C) of the present invention contain an acetone-soluble component and an acetone-insoluble component.
  • the acetone-soluble component and the acetone-insoluble component can be measured as follows. That is, 2 g of the acrylic rubber particles (C) of the present invention were placed in 50 mL of acetone and stirred at room temperature for 24 hours, and the total amount of the obtained liquid was subjected to a rotation speed of 20000 rpm, a temperature of 0 ° C., and 180 minutes using a centrifuge. Under the above conditions, centrifuge to separate the supernatant and the precipitate, and dry each at 50 ° C.
  • Acetone-soluble components and acetone-insoluble components can be measured by obtaining insoluble components (precipitates) and measuring their masses.
  • the mass ratio of the acetone-insoluble content to 2 g of the acrylic rubber particles (C) was defined as the gel content (%).
  • the gel content of the acrylic rubber particles (C) of the present invention is preferably larger than 75% by mass, more preferably 76 to 95% by mass, and further preferably 80 to 90% by mass.
  • the acetone-insoluble component is present in the core layer (a-1) and the intermediate layer (a-2) of the acrylic rubber particles (C), and the acetone-soluble component is the acrylic rubber. It exists in the outer layer (b) of the particle (C).
  • the outer layer (b) of the acrylic rubber particles (C) contains both an acetone-insoluble component and an acetone-soluble component.
  • composition of the acrylic rubber particles (C) of the present invention in the case of a three-layer structure of a core layer (a-1), an intermediate layer (a-2), and an outer layer (b) will be described below.
  • the preferred core layer (a-1) contains a crosslinked weight containing a structural unit derived from methyl methacrylate, a structural unit derived from an alkyl acrylate, and a structural unit derived from a copolymerizable crosslinkable monomer (grafting agent). Including coalescence.
  • the crosslinked polymer contains structural units derived from other monomers copolymerizable, if desired.
  • the amount of the structural unit (methyl methacrylate unit) derived from methyl methacrylate in the core layer (a-1) is preferably 40 to 98.9% by mass, based on the total structural unit of the core layer (a-1). It is preferably 90 to 96.9% by mass.
  • the amount of the structural unit (alkyl acrylate unit) derived from the alkyl acrylate in the core layer (a-1) is preferably 1 to 59.99% by mass, based on the total structural unit of the core layer (a-1). It is preferably 3 to 9.9% by mass.
  • the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of structural units derived from alkyl acrylate, the lower the heat-decomposability of the multi-layer acrylic polymer tends to be. The larger the amount of structural units derived from alkyl acrylate, the warmer water or boiling water whitening resistance of the film. Tends to decrease.
  • the amount of structural units derived from the copolymerizable crosslinkable monomer (grafting agent) in the core layer (a-1) is preferably 0, relative to all structural units in the core layer (a-1). It is 01 to 1% by mass, more preferably 0.1 to 0.5% by mass.
  • the larger the amount of structural units derived from the copolymerizable crosslinkable monomer (grafting agent) the lower the impact resistance of the film tends to be.
  • the amount of structural units derived from other copolymerizable monomers in the core layer (a-1) is preferably 0 to 20% by mass, based on the total structural units of the core layer (a-1). It is preferably 0 to 10% by mass.
  • the intermediate layer (a-2) is a structural unit derived from an alkyl acrylate, a structural unit derived from a copolymerizable crosslinkable monomer (grafting agent), and a structural unit derived from methyl methacrylate, if necessary. , And a polymer consisting of structural units derived from other copolymerizable monomers.
  • the amount of the structural unit derived from the alkyl acrylate in the intermediate layer (a-2) is 60 to 99.8% by mass, preferably 70 to 99.5% by mass, based on the total structural units of the intermediate layer (a-2). %, More preferably 80 to 99% by mass.
  • the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of structural units derived from alkyl acrylate, the lower the impact resistance of the film, and the larger the amount of structural units derived from alkyl acrylate, the lower the stress whitening resistance and transparency of the film. is there.
  • the amount of structural units derived from the copolymerizable crosslinkable monomer (grafting agent) in the intermediate layer (a-2) is 0.2 to 0.2 with respect to all the structural units in the intermediate layer (a-2). It is 10% by mass, preferably 0.2 to 5% by mass, and more preferably 1 to 3% by mass.
  • the DM / DW ratio tends to be smaller and the impact resistance of the film tends to be lower as the amount of the structural unit derived from) is larger.
  • the amount of the structural units derived from methyl methacrylate in the intermediate layer (a-2) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, based on all the structural units in the intermediate layer (a-2). Is. The larger the amount of structural units derived from methyl methacrylate, the lower the impact resistance of the film tends to be.
  • the amount of structural units derived from other copolymerizable monomers in the intermediate layer (a-2) is preferably 0 to 39.8% by mass based on the total structural units of the intermediate layer (a-2). , More preferably 0 to 29.8% by mass.
  • the outer layer (b) contains 70% by mass or more of a structural unit derived from methyl methacrylate (methyl methacrylate unit), and further contains a structural unit derived from another monomer copolymerizable as needed.
  • a hard polymer comprising a structural unit derived from methyl methacrylate and a structural unit derived from an alkyl acrylate (alkyl acrylate unit) is included.
  • the amount of the structural unit derived from methyl methacrylate in the outer layer (b) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total structural units of the outer layer (b).
  • the amount of structural units derived from other copolymerizable monomers in the outer layer (b) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, based on the total structural units of the outer layer (b). %.
  • the amount thereof is preferably 1 to 20% by mass, more preferably 2 to 2 to the total structural units of the outer layer (b). It is 5% by mass.
  • the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of structural units derived from alkyl acrylate, the lower the thermostable decomposition property of the multilayer structure acrylic polymer tends to be, and the larger the amount of structural units derived from alkyl acrylate, the lower the stress whitening resistance of the film. Tend.
  • the outer layer (b) has a glass transition temperature of preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and even more preferably 100 ° C. or higher.
  • the mass ratio of each layer is preferably 1 to 50% by mass for the core layer (a-1), and 2 to 45% by mass. Is more preferable, and 3 to 40% by mass is further preferable.
  • the intermediate layer (a-2) is preferably 30 to 69% by mass, more preferably 35 to 65% by mass, and even more preferably 40 to 60% by mass.
  • the outer layer (b) is preferably 5 to 69% by mass, more preferably 10 to 63% by mass, and even more preferably 15 to 57% by mass in that the DM / DW ratio can be in the above range. ..
  • examples of the "other copolymerizable monomer” include aromatic vinyl monomers such as styrene, p-methylstyrene, o-methylstyrene and vinylnaphthalene, and unsaturated nitriles such as acrylonitrile.
  • Monomers such as ethylene and propylene, vinyl halide monomers such as vinyl chloride, vinylidene chloride and vinylidene fluoride, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride
  • vinyl halide monomers such as vinyl chloride, vinylidene chloride and vinylidene fluoride
  • unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride
  • Maleimide-based monomers such as system monomers, vinyl acetate, N-propyl maleimide, N-cyclohexyl maleimide, and NO-chlorophenyl maleimide can be mentioned, and these monomers may be used alone or in combination of two or more. Can be used in combination.
  • alkyl acrylate examples include alkyl acrylates having an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and s-butyl. Examples thereof include acrylate, t-butyl acrylate, n-butylmethyl acrylate, n-heptyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate and benzyl acrylate. These alkyl acrylates can be used alone or in combination of two or more. Of these, methyl acrylate and / or n-butyl acrylate are preferred.
  • the "copolymerizable crosslinkable monomer” is a monomer having two or more polymerizable groups, for example, allyl methacrylate, allyl acrylate, mono- or di-allyl maleate, mono.
  • a monomer (or grafting agent) having a dissimilar polymerizable group such as di-allyl fumarate, crotyl acrylate, crotyl methacrylate, diacrylic compound, dimethacryl compound, diallyl compound, divinyl compound, diene compound, Examples thereof include monomers having the same type of polymerizable group as a trivinyl compound.
  • Examples of the monomer (or cross-linking agent) having the same type of polymerizable group include ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polyethylene glycol di (meth). Examples thereof include acrylate, divinylbenzene, trivinylbenzene, ethylene glycol diallyl ether, propylene glycol diallyl ether, and butadiene.
  • the copolymerizable crosslinkable monomer may be used alone or in combination of two or more.
  • the method for producing the acrylic rubber particles (C) of the present invention is not particularly limited.
  • the core layer (a-1), the intermediate layer (a-2), and the outer layer (b) are sequentially formed by a seed emulsification polymerization method to form a core-shell multilayer layer.
  • Acrylic rubber particles (C) having a structure can be obtained.
  • a preferred method for producing the acrylic rubber particles (C) of the present invention is to carry out emulsion polymerization of an acrylic monomer to obtain a latex containing a multilayer acrylic polymer; a latex containing a multilayer acrylic polymer.
  • a slurry containing the acrylic rubber particles (C) is washed and dehydrated; the step of drying the dehydrated slurry is included.
  • a more preferable method for producing the acrylic rubber particle (C) of the present invention having a three-layer structure is a methyl methacrylate of 40 to 98.9% by mass, more preferably 90 to 96.9% by mass in the presence of an emulsifier.
  • alkyl acrylate having 1 to 8 carbon atoms of the alkyl group preferably 70 to 99.5% by mass, more preferably 80 to 99% by mass, and 0 to 30% by mass of methyl methacrylate.
  • other copolymerizable monomers are preferably 0 to 39.8% by mass, more preferably 0 to 29.8% by mass, and copolymerizable crosslinkable monomers ( A latex (II) containing a core layer (a-1) and an intermediate layer (a-2) by polymerizing (2nd polymerization) 0.2 to 5% by mass, more preferably 1 to 3% by mass of a grafting agent).
  • methyl methacrylate is 70% by mass or more, preferably 80 to 99% by mass, more preferably 95 to 98% by mass, and an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms.
  • the core layer (a-1), the intermediate layer (a-2), and the outer layer (b) are polymerized from 0 to 30% by mass, preferably 1 to 20% by mass, more preferably 2 to 5% by mass (3rd polymerization).
  • the latex (III) containing the above is obtained; the latex (III) is coagulated to obtain a slurry; the slurry is washed and dehydrated; and the dehydrated slurry is dried.
  • Polymerization can be performed by a known method. Of the polymerizations carried out in the presence of latex, seed emulsion polymerization is preferably used to obtain a core-shell multilayer acrylic polymer. Emulsion polymerization or seed polymerization is a well-known method in the art and can be carried out according to a conventional method.
  • the monomers used in each polymerization are specifically methyl methacrylate, alkyl acrylate, other copolymerizable monomers, and copolymerizable crosslinkable monomers (grafting agents) as described above.
  • the speed at which the mixture of Is 0.1 to 1% by mass / min, more preferably 0.2 to 0.8% by mass / min.
  • the polymerization initiator used in each polymerization is not particularly limited.
  • the polymerization initiator include water-soluble inorganic initiators such as potassium persulfate and ammonium persulfate; redox initiators obtained by using a sulfite or thiosulfate in combination with the inorganic initiators; and organic peroxides. Examples thereof include a redox initiator obtained by using a ferrous salt or sodium sulfoxylate in combination.
  • the polymerization initiator may be added to the reaction system all at once at the start of polymerization, or may be added to the reaction system separately at the start of polymerization and during the polymerization in consideration of the reaction rate and the like.
  • the amount of the polymerization initiator used can be appropriately set so that the average particle size of the core-shell multilayer structure acrylic rubber particles (C) is within the above range, for example.
  • the emulsifier used in each polymerization is not particularly limited.
  • the emulsifier include anionic emulsifiers such as long-chain alkyl sulfonates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates; nonionic emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene.
  • Nonylphenyl ether sulfate such as nonylphenyl ether sulfate, polyoxyethylene alkyl ether sulfate such as polyoxyethylene alkyl ether sulfate, alkyl ether carboxylate such as polyoxyethylene tridecyl ether sodium acetate, etc.
  • Nonionic / anionic emulsifiers can be mentioned.
  • the amount of the emulsifier used can be appropriately set so that the DW and DM of the acrylic rubber particles are in the above range, for example.
  • the 1st polymerization, the 2nd polymerization and the 3rd polymerization may be sequentially carried out in one polymerization tank, or the polymerization tank may be changed sequentially for each 1st polymerization, 2nd polymerization and 3rd polymerization. In the present invention, it is preferable to carry out each polymerization sequentially in one polymerization tank.
  • the temperature of the reaction system during the polymerization is preferably 30 to 120 ° C, more preferably 50 to 100 ° C.
  • a reactive ultraviolet absorber for example, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] -2H-1, 2,3-Benzotriazole and the like can be added.
  • the reactive UV absorber is introduced into the molecular chain of the multilayer acrylic polymer, and the UV resistance of the multilayer acrylic polymer is improved.
  • the amount of the reactive ultraviolet absorber added is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the monomers used for the polymerization.
  • the chain transfer agent can be used in each polymerization for the regulation of molecular weight.
  • a chain transfer agent can be added to the reaction system to adjust the weight average molecular weight of the hard polymer (c).
  • the chain transfer agent used for each polymerization is not particularly limited.
  • chain transfer agent examples include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-hexadecyl mercaptan; xanthogen disulfides such as dimethylxanthogen disulfide and diethylxantogen disulfide; tetrathiuram disulfide. Thiol disulfides such as; carbon tetrachloride, halogenated hydrocarbons such as ethylene bromide, etc. can be mentioned.
  • the amount of the chain transfer agent used can be appropriately set within a range in which the polymer can be adjusted to a predetermined molecular weight in each polymerization.
  • the amount of the chain transfer agent used in the 3rd polymerization is an amount that can bring the weight average molecular weight of the hard polymer and the DM / DW ratio within the above range.
  • the amount of the chain transfer agent used in the 3rd polymerization varies depending on the amount of the polymerization initiator used in the 3rd polymerization, but the monomer used in the 3rd polymerization, specifically, methyl methacrylate and alkyl acrylate. It is preferably 0.05 to 2 parts by mass, and more preferably 0.08 to 1 part by mass with respect to 100 parts by mass of the total amount.
  • the acrylic rubber particles (C) are recovered from the emulsified latex by coagulating the emulsified latex.
  • the coagulation of the latex can be performed by a known method.
  • the coagulation method include a freeze coagulation method, a salting out coagulation method, and an acid coagulation method. Of these, a salting-out coagulation method capable of continuously producing a high-quality coagulated product is preferable.
  • the coagulant that can be used in the present invention may be an inorganic acid or a salt thereof having a property of coagulating and coagulating the emulsion-polymerized latex, or an aqueous solution of an organic acid or a salt thereof.
  • inorganic acid solution inorganic acid salt solution, organic acid solution or organic acid salt solution
  • sodium chloride potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide and iodine.
  • Alkali metal halides such as potassium chloride and sodium iodide; alkali metal sulfides such as potassium sulfate and sodium sulfate; ammonium sulfate; ammonium chloride; alkali metal nitrates such as sodium nitrate and potassium nitrate; calcium ferrous sulfate, magnesium sulfate , Calcium acetate, zinc sulfate, copper sulfate, barium chloride, ferrous chloride, ferric chloride, magnesium chloride, ferric sulfate, aluminum sulfate, potassium myoban, iron myoban, etc. A mixture of the above can be mentioned.
  • an aqueous solution of a salt of a monovalent or divalent inorganic acid such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride, calcium acetate can be preferably used.
  • the method of adding the coagulant is not particularly limited, and batch addition, divided addition, or continuous addition can be used.
  • the emulsified latex is a three-layer structure acrylic polymer latex composed of a core layer (a-1), an intermediate layer (a-2), and an outer layer (b), or a mixture of two or more kinds, or a core layer (a).
  • a coagulant By adding a coagulant to a mixture of a multilayer structure acrylic polymer latex composed of -1), an intermediate layer (a-2), and an outer layer (b) and at least one single-layer acrylic polymer latex. Can be solidified.
  • the methacrylic resin (D) is a non-crosslinked polymer containing 60% by mass or more of methyl methacrylate units, and has a weight average molecular weight of 100,000 or more.
  • the methacrylic resin (D) is derived from a polymer containing only a structural unit derived from methyl methacrylate (hereinafter, this may be referred to as methacrylic resin [D0]) or methyl methacrylicate. It is a random copolymer (hereinafter, this may be referred to as a methacrylic resin [D1]) containing a structural unit to be used and a structural unit derived from another monomer.
  • the methacrylic resin [D1] used in the present invention contains 60 to 99.8% by mass of a methyl methacrylate unit and 0.2 to 40% by mass of a structural unit derived from a monomer other than methyl methacrylate.
  • the amount of the structural unit derived from the monomer other than methyl methacrylate contained in the methacrylic resin (D) is preferably 0.3 to 30% by mass, more preferably 0.4 to 20% by mass.
  • the methacrylic resin [D1] contains a structural unit derived from a monomer other than methyl methacrylate.
  • the monomer other than methyl methacrylate include (meth) acrylic acids such as methacrylic acid and acrylic acid; alkyl methacrylates other than methyl methacrylate such as ethyl methacrylate and butyl methacrylate; and phenyl methacrylate and the like.
  • Aryl Methacrylic Acid Ester Cycloalkyl Methacrylic Acid such as Cyclohexyl Methacrylate, Norbornyl Methacrylate, Tricyclodecanyl Methacrylate; Methyl Acrylic Acid, Ethyl Acrylic Acid, propyl Acrylate, Butyl Acrylate, 2-Eethyl Acrylate Acrylic acid alkyl ester such as hexyl; Acrylic acid aryl ester such as phenyl acrylate; Acrylic acid cycloalkyl ester such as cyclohexyl acrylate and norbornyl acrylate; Aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; acrylamide A vinyl-based monomer having only one polymerizable carbon-carbon double bond in one molecule such as methacrylicamide; acrylonitrile; methacrylic nitrile; can be mentioned.
  • the methacrylic resin [D1] may have a ring structure in the main chain.
  • a cyclization reaction is carried out after copolymerizing a methacrylic acid ester monomer and a monomer having a ring structure, or polymerizing a group of monomers containing a methacrylic acid ester monomer.
  • the ring structure that the methacrylic resin may have in the main chain is, for example, at least one selected from an N-substituted maleimide structure, a maleic anhydride structure, a glutarimide structure, a glutaric anhydride structure, and a lactone ring structure. is there.
  • the N-substituted maleimide structure is, for example, a cyclohexylmaleimide structure, a methylmaleimide structure, a phenylmaleimide structure, or a benzylmaleimide structure.
  • the ring structure includes a lactone ring structure, a cyclic imide structure (for example, an N-alkyl substituted maleimide structure, a glutarimide structure), a cyclic anhydride structure (for example, a maleic anhydride structure and the like. (Glutaric anhydride structure) is preferable.
  • the weight average molecular weight of the methacrylic resin [D0] or [D1] is 100,000 g / mol or more, for example, 105,000 to 2,000,000 g / mol, preferably 110,000 to 1,800,000 g / mol. Is.
  • the weight average molecular weight can be measured by gel permeation chromatography. The measurement by gel permeation chromatography can be performed as follows. Tetrahydrofuran is used as the eluent, and TSKgelSuperMultipole HZM-M manufactured by Tosoh Corporation and SuperHZ4000 are connected in series as the column.
  • HLC-8320 product number
  • RI detector differential refractive index detector
  • a resin material to be tested that is, 4 mg of a hydroxyl group-containing methacrylic polymer is dissolved in 5 ml of tetrahydrofuran, and further filtered through a 0.1 ⁇ m filter to prepare a solution to be tested.
  • the temperature of the column oven is set to 40 ° C., the eluent flow rate is 0.35 ml / min, 20 ⁇ l of the test target solution is injected, and the chromatogram is measured.
  • the methacrylic resin [D0] or [D1] of the present invention can be obtained by a commercially available product or a known synthetic method.
  • a method for producing a methacrylic resin that can be used for the methacrylic resin [D0] or [D1] of the present invention a radical polymerization method of emulsion polymerization, solution polymerization, bulk polymerization, and suspension polymerization; and anion weight Legal etc. can be applied.
  • emulsion polymerization, bulk polymerization, and suspension polymerization are preferable from the viewpoint of productivity and the possibility of producing a high molecular weight compound.
  • the mass ratio of the acrylic rubber particles (C) is in the range of 2 to 90 parts by mass with respect to a total of 100 parts by mass of the acrylic rubber particles (C) and the methacrylic resin (D). It is characterized by being.
  • the acrylic rubber particles (C) in the above range, a molded product having excellent impact resistance can be obtained.
  • the methacrylic resin composition of the present invention preferably contains 2 to 90 parts by mass of acrylic rubber particles (C) with respect to a total of 100 parts by mass of acrylic rubber particles (C) and methacrylic resin (D).
  • the content of the acrylic rubber particles (C) is more preferably 5 to 70 parts by mass, and further preferably 10 to 50 parts by mass.
  • the methacrylic resin composition of the present invention can be produced or prepared by mixing acrylic rubber particles (C), methacrylic resin (D), and if necessary, other components.
  • the mixing method is not particularly limited, and is, for example, melt-kneading using a mixer such as a ribbon blender, a tumble mixer, or a Henschel mixer, or a mixing means using a kneader such as an open roller, a kneader, a Banbury mixer, or an extruder. The method is available. These mixing methods may be used alone or in combination of two or more.
  • the methacrylic resin composition may be in the form of a coating liquid mixed with a solvent.
  • the solvent constituting the coating liquid is not particularly limited as long as both can be dissolved, and for example, hydrocarbons (benzene, toluene, etc.), halogen-based solvents (diethyl, etc.), ethers (diethyl ether, etc.) Examples thereof include alcohols (methanol, ethanol, butanol, etc.) such as tetrahydrofuran (such as tetrahydrofuran), esters (ethyl acetate, etc.), ketones (acetone, ethylmethyl ketone, diisopropyl ketone, cyclohexanone, etc.). These solvents may be used alone or in combination of two or more.
  • the ratio of the solvent may be as long as it does not impair the coatability, and is 1 to 100 parts by mass, preferably 2 to 50 parts by mass, and more preferably 3 to 3 parts by mass with respect to 1 part by mass of the solid content of the methacrylic resin composition. It may be about 30 parts by mass.
  • the molded body is an optical member.
  • the molded body (or optical member) of the present invention has a known molding method, for example, an injection molding method, an injection compression molding method, or an extrusion molding, depending on the form (resin pellet, coating liquid, etc.) of the resin composition for optical use.
  • the resin composition is molded by a method (for example, T-die method, inflation method, etc.), calendar method, heat molding method (particularly, heat pressing method), transfer molding method, blow molding method, casting molding method, or the like. Can be obtained by a method (for example, T-die method, inflation method, etc.), calendar method, heat molding method (particularly, heat pressing method), transfer molding method, blow molding method, casting molding method, or the like. Can be obtained by
  • the molded product of the present invention When the molded product of the present invention is in the form of a film (or sheet), it may be an unstretched film, or it may be a stretched (or stretched) film.
  • the film-shaped molded product may form an optical film or a sheet.
  • the stretching may be either uniaxial stretching (for example, longitudinal stretching or transverse stretching) or biaxial stretching (for example, iso-stretching or partial stretching).
  • the draw ratio may be, for example, about 1.1 to 10 times in each direction (or one direction) in uniaxial stretching and biaxial stretching, preferably 1.2 to 5 times, and more preferably 1.3. It is about 3 times.
  • the elastic modulus can be improved even if the stretching treatment is performed.
  • the film thickness may be, for example, 1 to 1000 ⁇ m, preferably 3 to 800 ⁇ m, and more preferably about 5 to 500 ⁇ m.
  • the methacrylic resin composition of the present invention can be in the form of pellets or the like in order to enhance convenience during storage, transportation, or molding.
  • the methacrylic resin composition of the present invention can be made into a molded product (a molded product made of the methacrylic resin composition of the present invention) by a known molding method.
  • the molding method include a T-die method (lamination method, coextrusion method, etc.), inflation method (coextrusion method, etc.), compression molding method, blow molding method, calendar molding method, vacuum forming method, injection molding method (insert).
  • a melt molding method such as a method, a two-color method, a pressing method, a core back method, a sandwich method, etc., and a solution casting method can be mentioned.
  • the present invention includes a molded product using the methacrylic resin composition of the present invention.
  • Apps of the molded product using the methacrylic resin composition of the present invention include, for example, signboard parts such as advertising towers, stand signs, sleeve signs, column signboards, and roof signboards; display parts such as showcases, partition plates, and store displays.
  • Lighting parts such as fluorescent lamp covers, mood lighting covers, lamp shades, light ceilings, light walls, chandeliers; Interior parts such as pendants and mirrors; Doors, dome, safety window glass, partitions, staircase wainscots, balcony wainscots, for leisure Building parts such as building roofs, resin sashes, kitchen doors, door surfaces; aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shading plates, automotive side visors, rear visors, head wings, headlight covers, etc.
  • Transportation equipment parts Electronic equipment parts such as audiovisual nameplates, stereo covers, TV protective masks, display covers for vending machines; Medical equipment parts such as incubators and roentgen parts; Machine covers, instrument covers, experimental equipment, Equipment-related parts such as rulers, dials, and observation windows; light guide plates and films for front lights of display devices, light guide plates and films for backlights, liquid crystal protective plates, frennel lenses, lenticular lenses, front plates of various displays, diffusers , Optical parts such as reflective materials; Traffic related parts such as road signs, guide boards, curved mirrors, soundproof walls; Surface materials for automobile interiors, Surface materials for mobile phones, Film members such as marking films; Canopy materials for washing machines Parts for home appliances such as control panels, top panels of rice cookers; others, greenhouses, large water tanks, box water tanks, clock panels, bathtubs, sanitary, desk mats, game parts, toys, face protection masks during welding, etc. Can be mentioned.
  • the particle size was measured by a light scattering method (volume conversion) using a laser diffraction / scattering type particle size distribution measuring device LA-300 manufactured by Horiba Seisakusho Co., Ltd. A median diameter was adopted as the particle diameter.
  • MMA Methyl Methacrylate
  • MA Methyl Acrylate
  • MAA BA Methacrylate: n-butyl
  • BzA Acrylate: Benzyl Acrylate
  • ALMA Allyl Acrylate
  • 1,3-BD 1,3-butylene
  • nOM n-octyl mercaptan
  • MSt ⁇ -methylstyrene
  • Example 1 Manufacturing of acrylic rubber particles (C-1)] In a reactor equipped with a stirrer, thermometer, nitrogen gas introduction part, monomer introduction tube and reflux condenser, 900 parts by mass of deionized water, 6 parts by mass of sodium alkyldiphenyl ether sulfonate 50% aqueous solution (emulsifier) and After charging 0.3 parts by mass of sodium carbonate and sufficiently replacing the inside of the container with nitrogen gas to make it substantially oxygen-free, the internal temperature was set to 80 ° C.
  • the emulsion containing the acrylic rubber particles (C-1) was frozen at ⁇ 30 ° C. for 4 hours. Frozen emulsion is added to twice the amount of frozen emulsion in warm water at 80 ° C., dissolved to form a slurry, held at 80 ° C. for 20 minutes, dehydrated, dried at 70 ° C., and acrylic rubber particles (C-).
  • the coagulated powder of 1) was obtained. With respect to the obtained aggregated powder, the gel content (acetone insoluble matter), the outermost layer weight average molecular weight Mw, and the dispersed particle size (DM) in methylene chloride were measured, and DM / DW was calculated. The results are shown in Table 2.
  • Example 2 [Manufacturing of acrylic rubber particles (C-2)] Polymerization and extraction were carried out in the same manner as in Example 1 except that the amount of the 50% aqueous solution of sodium alkyldiphenyl ether sulfonate added was 1.2 parts by mass to obtain aggregated powder of acrylic rubber particles (C-2). .. With respect to the obtained aggregated powder, the gel content (acetone insoluble matter), the outermost layer weight average molecular weight Mw, and the dispersed particle size (DM) in methylene chloride were measured, and DM / DW was calculated. The results are shown in Table 2.
  • Example 3 Manufacturing of acrylic rubber particles (C-3)
  • Polymerization and extraction were carried out in the same manner as in Example 1 except that the amount of the 50% aqueous solution of sodium alkyldiphenyl ether sulfonate added was 12.6 parts by mass to obtain agglomerated powder of acrylic rubber particles (C-3). ..
  • the gel content acetone insoluble matter
  • the outermost layer weight average molecular weight Mw the dispersed particle size (DM) in methylene chloride were measured, and DM / DW was calculated. The results are shown in Table 2.
  • Example 4 [Manufacturing of acrylic rubber particles (C-4)] Acrylic rubber particles (C-) were polymerized and taken out in the same manner as in Example 1 except that the emulsifier was sodium alkyl ether carboxylate, the addition amount was 0.16 parts by mass, and the monomer composition was changed as shown in Table 1. The coagulated powder of 4) was obtained. With respect to the obtained aggregated powder, the gel content (acetone insoluble matter), the outermost layer weight average molecular weight Mw, and the dispersed particle size (DM) in methylene chloride were measured, and DM / DW was calculated. The results are shown in Table 2.
  • Example 5 [Manufacturing of acrylic rubber particles (C-5)] Acrylic rubber particles (C-) were polymerized and taken out in the same manner as in Example 1 except that the emulsifier was sodium alkyl ether carboxylate, the addition amount was 0.16 parts by mass, and the monomer composition was changed as shown in Table 1. The coagulated powder of 5) was obtained. With respect to the obtained aggregated powder, the gel content (acetone insoluble matter), the outermost layer weight average molecular weight Mw, and the dispersed particle size (DM) in methylene chloride were measured, and DM / DW was calculated. The results are shown in Table 2.
  • Example 6 Manufacturing of acrylic rubber particles (C-6)
  • Acrylic rubber particles (C-) were polymerized and taken out in the same manner as in Example 1 except that the emulsifier was sodium alkyl ether carboxylate, the addition amount was 0.16 parts by mass, and the monomer composition was changed as shown in Table 1.
  • the coagulated powder of 6) was obtained. With respect to the obtained aggregated powder, the gel content (acetone insoluble matter), the outermost layer weight average molecular weight Mw, and the dispersed particle size (DM) in methylene chloride were measured, and DM / DW was calculated. The results are shown in Table 2.
  • Example 7 Manufacturing of acrylic rubber particles (C-7)
  • Polymerization was carried out in the same manner as in Example 1 except that the layer composition and the monomer composition were changed as shown in Table 1 with the addition amount of the 50% aqueous solution of sodium alkyldiphenyl ether sulfonate being 0.18 parts by mass, and then the fourth layer was formed.
  • Polymerization and extraction were carried out according to the composition shown in Table 1 to obtain agglomerated powder of acrylic rubber particles (C-7). With respect to the obtained aggregated powder, the gel content (acetone insoluble matter), the outermost layer weight average molecular weight Mw, and the dispersed particle size (DM) in methylene chloride were measured, and DM / DW was calculated. The results are shown in Table 2.
  • the following polymers were prepared as the methacrylic resin [D].
  • the pellet-shaped methacrylic resin composition was heat-press molded at 230 ° C. to produce a flat plate (pressed plate) having a predetermined size, and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 2-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-2), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 3-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-3), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 4-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-4), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 5-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-5), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 6-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-6), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 7-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-7), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 1-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-8), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 2-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-9), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 3-2 A press plate was prepared in the same manner as in Example 1-2 except that the type of acrylic rubber particles was changed to (C-10), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 4.
  • Example 1-3 A press plate was prepared in the same manner as in Example 1-2 except that the type of methacrylic resin was changed to (D-2), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 5.
  • Example 1-4 A press plate was prepared in the same manner as in Example 1-2 except that the type of methacrylic resin was changed to (D-3), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 5.
  • Example 1-5 A press plate was prepared in the same manner as in Example 1-2 except that the type of methacrylic resin was changed to (D-4), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 5.
  • Example 1-6 A press plate was prepared in the same manner as in Example 1-2 except that the type of methacrylic resin was changed to (D-5), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 5.
  • Example 1-7 A press plate was prepared in the same manner as in Example 1-2 except that the type of methacrylic resin was changed to (D-6), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 5.
  • Example 4 A press plate was prepared in the same manner as in Example 1-2 except that the type of methacrylic resin was changed to (D-7), and the Charpy impact strength and flexural modulus were measured. The results are shown in Table 5.
  • acrylic rubber particles (C) having a high gel content of C-1 to C-7 As shown in Tables 4 and 5, methacrylic resins (D-1 to D-6) having a weight average molecular weight of more than 100,000 and acrylic rubber particles (C) having a high gel content of C-1 to C-7.
  • Comparative Examples 1-2, 2-2, 3- Impact resistance is improved as compared with 2 and 4.

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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)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une particule de caoutchouc acrylique (C) qui présente une structure multicouche d'au moins trois couches, la particule de caoutchouc acrylique (C) comprenant au moins une couche externe (b) qui contient un polymère dur non réticulé contenant au moins 70 % en masse de motif de type méthacrylate de méthyle ; une couche intermédiaire (a-2) qui contient un copolymère élastique contenant 60 à 99,8 % en masse de motif de type acrylate d'alkyle et 0,2 à 10 % en masse de motif monomère réticulable copolymérisable ; et une couche centrale (a-1) qui contient un polymère réticulé contenant 40 à 98,99 % en masse de motif de type méthacrylate de méthyle, 1 à 59,99 % en masse de motif de type acrylate d'alkyle et 0,01 à 1 % en masse de motif monomère réticulable copolymérisable. La particule de caoutchouc acrylique (C) est caractérisée en ce que le poids moléculaire moyen en poids du polymère dur de la couche externe (b) est d'au moins 30 000 ; la teneur en gel de la particule de caoutchouc acrylique (C) est supérieure à 75 % en masse ; le diamètre de particule dans l'eau (DW) de la particule de caoutchouc acrylique (C) est de 50 à 350 nm ; et le diamètre de particule de dispersion obtenu par dispersion d'une poudre agrégée de la particule de caoutchouc acrylique (C) dans le chlorure de méthylène (DM) est inférieur à 10 fois le diamètre de particule dans l'eau (DW).
PCT/JP2020/020929 2019-05-28 2020-05-27 Particule de caoutchouc acrylique et composition de résine méthacrylique WO2020241690A1 (fr)

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Citations (7)

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JPS59202213A (ja) * 1983-05-02 1984-11-16 Asahi Chem Ind Co Ltd 耐衝撃性アクリル系重合体の製造方法
JPH11322860A (ja) * 1998-05-12 1999-11-26 Mitsubishi Rayon Co Ltd 耐衝撃性アクリル系重合体の製造方法
WO2016139927A1 (fr) * 2015-03-02 2016-09-09 株式会社カネカ Composition de résine acrylique, produit moulé et film obtenu à partir de cellei-ci
WO2017141873A1 (fr) * 2016-02-15 2017-08-24 株式会社クラレ Film de résine thermoplastique et son procédé de production, et stratifié
WO2018062378A1 (fr) * 2016-09-29 2018-04-05 株式会社クラレ Film de résine acrylique et son procédé de production
WO2018155677A1 (fr) * 2017-02-27 2018-08-30 株式会社クラレ Composition de résine comprenant des particules polymères
WO2018181897A1 (fr) * 2017-03-31 2018-10-04 株式会社クラレ Composition de résine contenant une structure multicouche et son procédé de production

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW419494B (en) * 1997-02-05 2001-01-21 Mitsubishi Rayon Co Impact resistant acrylic polymer pellet and preparation thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59202213A (ja) * 1983-05-02 1984-11-16 Asahi Chem Ind Co Ltd 耐衝撃性アクリル系重合体の製造方法
JPH11322860A (ja) * 1998-05-12 1999-11-26 Mitsubishi Rayon Co Ltd 耐衝撃性アクリル系重合体の製造方法
WO2016139927A1 (fr) * 2015-03-02 2016-09-09 株式会社カネカ Composition de résine acrylique, produit moulé et film obtenu à partir de cellei-ci
WO2017141873A1 (fr) * 2016-02-15 2017-08-24 株式会社クラレ Film de résine thermoplastique et son procédé de production, et stratifié
WO2018062378A1 (fr) * 2016-09-29 2018-04-05 株式会社クラレ Film de résine acrylique et son procédé de production
WO2018155677A1 (fr) * 2017-02-27 2018-08-30 株式会社クラレ Composition de résine comprenant des particules polymères
WO2018181897A1 (fr) * 2017-03-31 2018-10-04 株式会社クラレ Composition de résine contenant une structure multicouche et son procédé de production

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