WO2023100903A1 - Particules de copolymère greffé de type noyau/enveloppe, leur procédé de fabrication et composition de résine - Google Patents

Particules de copolymère greffé de type noyau/enveloppe, leur procédé de fabrication et composition de résine Download PDF

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WO2023100903A1
WO2023100903A1 PCT/JP2022/044060 JP2022044060W WO2023100903A1 WO 2023100903 A1 WO2023100903 A1 WO 2023100903A1 JP 2022044060 W JP2022044060 W JP 2022044060W WO 2023100903 A1 WO2023100903 A1 WO 2023100903A1
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core
weight
particles
graft copolymer
layer
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PCT/JP2022/044060
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Japanese (ja)
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薫 波多江
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株式会社カネカ
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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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • 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
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • 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

Definitions

  • the present invention relates to core-shell type graft copolymer particles, a method for producing the same, and a resin composition containing the particles.
  • ABS resin acrylonitrile-butadiene-styrene
  • ABS resin has excellent rigidity, impact resistance, heat deformation resistance, etc., so it is used for various miscellaneous goods, interior and exterior materials for automobiles, housings for household appliances such as jar rice cookers, microwave ovens, and vacuum cleaners. It is widely used for parts, housings and parts of OA equipment such as telephones and facsimiles, but it has the disadvantage of low weather resistance.
  • ASA resin acrylonitrile-styrene- acrylic
  • ABS resin acrylonitrile-styrene- acrylic
  • Patent Document 1 describes blending such a composite rubber-containing graft copolymer with a thermoplastic resin such as an acrylonitrile-styrene resin.
  • the impact resistance of the resin can be improved, but the color development tends to decrease, and both impact resistance and color development are satisfied. was difficult to do.
  • the present inventors have found that the above problems can be solved by adopting a specific configuration in a composite rubber-containing graft copolymer, and have completed the present invention.
  • the present invention provides a core-shell type graft copolymer particle comprising a core particle (A) and a shell layer (B) covering the core particle (A), wherein the core particle (A) comprises a polyorgano
  • the core particle (A ) is 50 to 65% by weight, the volume average particle diameter of the core particles (A) is 85 to 150 nm, and the shell layer (B) comprises an aromatic vinyl compound unit and a vinyl cyanide compound
  • a core-shell type graft copolymer particle comprising a layer (b1) formed from a copolymer containing units.
  • the present invention also provides a method for producing the core-shell type graft copolymer particles, comprising: a step of polymerizing a polyorganosiloxane rubber-forming component to form polyorganosiloxane rubber particles (a1); the step of polymerizing an alkyl (meth)acrylate and a crosslinkable monomer in the presence of (a1) to form a polyalkyl (meth)acrylate rubber layer (a2) to obtain a core particle (A); A step of copolymerizing a monomer component containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the core particle (A) to form a layer (b1) to obtain the core-shell type graft copolymer particles.
  • the present invention also provides a resin composition containing 100 parts by weight of a thermoplastic resin and 10 to 100 parts by weight of the core-shell type graft copolymer particles, or a molded article obtained by molding the resin composition. related.
  • the core-shell type graft copolymer particle which can exhibit favorable color development property while improving impact resistance by mix
  • the molded article molded from the thermoplastic resin composition containing the core-shell type graft copolymer particles has extremely good color developability and has a good appearance without coating. can have
  • a core-shell type graft copolymer particle according to the present disclosure has a core-shell structure including a core particle (A) and a shell layer (B) covering the core particle (A).
  • a core particle (A) refers to a particle located inside a core-shell type graft copolymer particle.
  • the shell layer (B) is located on the surface side of the core-shell type graft copolymer particle, refers to the polymer layer constituting the surface of the core particle (A), and is also called a graft layer.
  • the shell layer (B) covers the surface of the core particle (A), but is not limited to covering the entire surface of the core particle (A), and covers at least part of the surface of the core particle (A). It should be covered.
  • the core particle (A) contains polyorganosiloxane rubber particles (a1) and a polyalkyl (meth)acrylate rubber layer (a2) positioned outside the rubber particles (a1).
  • rubber means a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer). Since the core particles (A) are formed from a crosslinked polymer, the addition of the core-shell type graft copolymer particles to the matrix resin can impart impact resistance to the matrix resin.
  • the polyorganosiloxane rubber particles (a1) are composed mainly of polyorganosiloxane rubber (hereinafter also referred to as silicone rubber) having a structure linked by siloxane bonds.
  • the silicone rubber can be obtained by condensation polymerization of organosiloxane and any silane compound.
  • the organosiloxane refers to a monomer component that forms the main skeleton of the silicone rubber.
  • Specific examples include cyclic organosiloxanes, linear organosiloxane oligomers, and bifunctional silane compounds. Of these, cyclic organosiloxanes are preferred from the viewpoints of applicability to emulsion polymerization systems and economic efficiency.
  • the cyclic organosiloxane may be, for example, a 6- to 12-membered ring, and specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyl triphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. These may be used alone or in combination of two or more. Among them, octamethylcyclotetrasiloxane is preferred.
  • the optional silane compound examples include a cross-linking agent and a graft crossing agent.
  • the cross-linking agent is a component that is copolymerized with the organosiloxane to introduce a cross-linked structure into the silicone rubber to develop rubber elasticity, and is used as a cross-linking agent for the silicone rubber.
  • tetrafunctional or trifunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, N-(2-aminoethyl )-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane silane, trifluoropropyltrimethoxysilane, octadecyltrimethoxysilane, and the like. These may be used alone or in combination of two or more. Among them, tetraethoxysilane is preferable because
  • the graft crossing agent is a component for introducing polymerizable unsaturated bonds or mercapto groups to the side chains and/or terminals of the silicone rubber by copolymerizing with the organosiloxane and/or the cross-linking agent.
  • the polymerizable unsaturated bond or mercapto group can serve as a graft active site for alkyl (meth)acrylate.
  • the polymerizable unsaturated bond or mercapto group can also serve as a cross-linking point when radically reacted using a radical polymerization initiator. Even when cross-linked by a radical reaction, grafting is possible because a part of it remains as a grafting active site.
  • graft crossing agent examples include reactive silane compounds having polymerizable unsaturated bonds or mercapto groups, or organosiloxanes having polymerizable unsaturated bonds or mercapto groups.
  • Examples of the reactive silane compound having a polymerizable unsaturated bond include ⁇ -methacryloyloxyethyldimethoxymethylsilane, ⁇ -methacryloyloxypropyldimethoxymethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropyldimethyl methoxysilane, ⁇ -methacryloyloxypropyltriethoxysilane, ⁇ -methacryloyloxypropyldiethoxymethylsilane, ⁇ -methacryloyloxypropyltripropoxysilane, ⁇ -methacryloyloxypropyldipropoxymethylsilane, p-vinylphenyldimethoxymethylsilane, p - vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, p-vinylphenyldieth
  • Examples of the reactive silane compound having a mercapto group include mercaptopropyltrimethoxysilane and mercaptopropyldimethoxymethylsilane.
  • the proportions of the organosiloxane, cross-linking agent, and graft crossing agent described above are, for example, 70 to 99.9% by weight, preferably 85 to 99.5% by weight, of the total amount of polyorganosiloxane rubber-forming components. , a cross-linking agent of 0-10% by weight, preferably 0-5% by weight, a grafting agent of 0-10% by weight, preferably 0.3-5% by weight. It is preferable to use 0.1% by weight or more of either the cross-linking agent or the graft crossing agent.
  • the method for producing the polyorganosiloxane rubber particles (a1) is not particularly limited, but a mixture of organosiloxane, an optional cross-linking agent and a graft crossing agent is emulsified and dispersed in water by mechanical shearing in the presence of an emulsifier. Therefore, a method of obtaining a latex of polyorganosiloxane rubber particles (a1) by polymerization under specific conditions is preferred. Details will be described later.
  • the polyorganosiloxane rubber particles (a1) may consist of only the polyorganosiloxane rubber component, or may contain a vinyl polymer in addition to the polyorganosiloxane rubber component.
  • the polyorganosiloxane rubber particles (a1) containing the vinyl polymer as seed particles inside are preferable because the stability of the emulsion during production is good and the particle size can be controlled to be small.
  • Such polyorganosiloxane rubber particles (a1) are obtained by first obtaining seed particles made of a vinyl polymer by emulsion polymerization or the like, and then polymerizing the polyorganosiloxane rubber-forming components in the presence of the seed particles. Just do it.
  • the monomer used for producing the vinyl polymer is not particularly limited, and examples include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, paramethylstyrene, and parabutylstyrene; Vinyl cyanide monomers such as lonitrile, vinyl halide monomers such as vinyl chloride, vinylidene chloride, and vinylidene fluoride, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid (Meth)acrylate monomers such as 2-ethylhexyl, glycidyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, itacones carboxyl group-containing vinyl-based monomers such as acids, (meth)acrylic
  • butyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, butadiene, and acrylonitrile in an amount of 20 to 100% by weight, and more preferably 30 to 100% by weight, stabilize the emulsion during production. It is preferable because it has high properties and the particle size of the resulting polyorganosiloxane rubber particles (a1) tends to be small.
  • the vinyl-based polymer constituting the seed particles may be a polymer containing a crosslinked structure, but since the particle size of the polyorganosiloxane rubber particles (a1) becomes smaller, it should be a non-crosslinked polymer. is preferred.
  • the proportion of the polyorganosiloxane rubber component in the total of both components is 55% by weight or more and 99.9%. % by weight or less, more preferably 65% by weight or more and 99.4% by weight or less, and even more preferably 88% by weight or more and 99% by weight or less.
  • the proportion of the vinyl polymer is preferably 0.1% by weight or more and 45% by weight or less, more preferably 0.6% by weight or more and 35% by weight or less, and even more preferably 1% by weight or more and 12% by weight or less. .
  • the particle size of the polyorganosiloxane rubber particles (a1) can be made smaller while exhibiting the characteristics of silicone rubber.
  • the ratio of the polyorganosiloxane rubber particles (a1) in the core particles (A) can be appropriately set, but from the viewpoint of impact resistance, color development, and weather resistance, it is 5% by weight or more and 40% by weight or less. , more preferably 8% by weight or more and 30% by weight or less, and even more preferably 10% by weight or more and 25% by weight or less.
  • the lower limit may be 15% by weight or more, or 20% by weight or more.
  • the volume average particle size of the polyorganosiloxane rubber particles (a1) is appropriately set in consideration of the proportion of the particles (a1) in the core particles (A) and the volume average particle size of the core particles (A) described below. do it. Specifically, it may be about 40 nm or more and 120 nm or less, preferably 40 nm or more and 110 nm or less, more preferably 50 nm or more and 100 nm or less.
  • the polyalkyl (meth)acrylate rubber layer (a2) is positioned outside the polyorganosiloxane rubber particles (a1) and constitutes the core particles (A) together with the polyorganosiloxane rubber particles (a1).
  • the polyalkyl (meth)acrylate rubber layer (a2) is preferably grafted onto the polyorganosiloxane rubber particles (a1).
  • the grafting can be achieved through the use of graft crossing agents as described above.
  • the polyalkyl (meth)acrylate rubber is a crosslinked product obtained by polymerizing a monomer component containing an alkyl (meth)acrylate and a crosslinkable monomer.
  • (meth)acryl collectively describes acryl and methacryl.
  • the alkyl (meth)acrylate is not particularly limited, but examples include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate , propyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. These monomers may be used alone or in combination of two or more.
  • Alkyl acrylate is preferable as the alkyl (meth)acrylate.
  • the content of the acrylic acid alkyl ester is preferably 50 to 100% by weight, preferably 70 to 100% by weight. 100% by weight is more preferred, 80 to 100% by weight is more preferred, 90 to 100% by weight is even more preferred, and 95 to 100% by weight is particularly preferred.
  • the number of carbon atoms in the alkyl group of the acrylic acid alkyl ester is preferably 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 2 to 12 carbon atoms, and even more preferably 2 to 8 carbon atoms.
  • Butyl acrylate is particularly preferred as the alkyl acrylate.
  • butyl acrylate In view of the low glass transition temperature of the resulting polymer and economic efficiency, it is preferable that 40 to 100% by weight, more preferably 60 to 100% by weight, of butyl acrylate is contained among the monomer components. preferable.
  • Preferred alkyl (meth)acrylates used in combination with butyl acrylate are methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • the monomer component for forming the polyalkyl(meth)acrylate rubber may consist only of the alkyl(meth)acrylate, but the unsaturated bond copolymerizable with the alkyl(meth)acrylate may further contain other monomers having one in one molecule.
  • the other monomer is not particularly limited, but includes, for example, (meth)acrylic monomers other than alkyl (meth)acrylates, aromatic vinyl compounds, vinyl cyanide compounds, and vinyl halides such as vinyl chloride and chloroprene. compounds, vinyl acetate, alkenes such as ethylene and propylene, and the like.
  • the crosslinkable monomer used for forming the polyalkyl(meth)acrylate rubber is a compound having two or more unsaturated bonds copolymerizable with the alkyl(meth)acrylate in one molecule.
  • specific examples include (meth)acrylates having an allyl group such as allyl (meth)acrylate, allylalkyl (meth)acrylate, and allyloxyalkyl (meth)acrylate; ) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, poly (meth) having two or more acrylic groups Functional (meth)acrylates; diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene and the like.
  • a crosslinkable monomer may use only 1 type, and may use 2 or more types together. Among them, allyl methacrylate, triallyl isocyanurate, butanediol di(meth)acrylate, and divinylbenzene are preferred, and allyl methacrylate is particularly preferred.
  • the ratio of the polyalkyl (meth)acrylate rubber layer (a2) in the core particles (A) can be appropriately set, but from the viewpoint of impact resistance, color development, and weather resistance, it is 60% by weight or more and 95% by weight. % by weight or less, more preferably 70% by weight or more and 92% by weight or less, and even more preferably 75% by weight or more and 90% by weight or less.
  • the upper limit may be 85% by weight or less, or 80% by weight or less.
  • the proportion of the core particles (A) in the core-shell type graft copolymer particles is set in the range of 50% by weight or more and 65% by weight or less. If the proportion of the core particles (A) is less than 50% by weight, the impact resistance will be insufficient. On the other hand, if the proportion of the core particles (A) exceeds 65% by weight, the compatibility between the core-shell type graft copolymer particles and the matrix resin may decrease, resulting in a decrease in impact resistance or color developability.
  • the proportion of the core particles (A) is preferably 53% by weight or more, more preferably 55% by weight or more, still more preferably 58% by weight or more, and 60% by weight or more. Especially preferred.
  • the upper limit of the ratio may be 64% by weight or less.
  • the volume average particle diameter of the core particles (A) is set to 85 nm or more and 150 nm or less from the viewpoint of productivity and the balance between impact resistance and color development. Core particles (A) having a volume average particle diameter of less than 85 nm are difficult to produce because the emulsion is unstable during production. When the volume average particle size of the core particles (A) exceeds 150 nm, the color developability becomes insufficient.
  • the lower limit of the volume average particle diameter of the core particles (A) is preferably 90 nm or more, more preferably 95 nm or more.
  • the upper limit of the volume average particle size of the core particles (A) is preferably 140 nm or less, more preferably 130 nm or less, even more preferably 120 nm or less, and more preferably 115 nm or less, in order to achieve better color development properties. More preferably, 110 nm or less is particularly preferable.
  • the volume-average particle size of the core particles (A) and the polyorganosiloxane rubber particles (a1) can be determined by using a particle size measuring device in the state of polymer particle latex, as shown in the Examples section. It is the measured value.
  • the particle diameters of the core particles (A) and the polyorganosiloxane rubber particles (a1) are controlled by the types and amounts of emulsifiers, polymerization initiators, reducing agents, etc. used during production, polymerization temperature, polymerization time, and the like. can be done.
  • the shell layer (B) is a polymer layer that covers the core particles (A) and is located on the surface of the graft copolymer particles. At least a portion of the shell layer (B) is preferably grafted to the core particle (A), but may also contain a non-grafted shell layer (B).
  • the shell layer (B) improves compatibility between the graft copolymer particles and the matrix resin, and enables the graft copolymer particles to be dispersed in the resin composition in the form of primary particles.
  • the shell layer (B) includes at least a layer (b1) formed from a copolymer containing aromatic vinyl compound units and vinyl cyanide compound units in order to improve compatibility with the matrix resin.
  • the copolymer may further contain a (meth)acrylate unit.
  • the aromatic vinyl compound is not particularly limited, but examples include styrene, ⁇ -methylstyrene, p-methylstyrene, p-isopropylstyrene, o-chlorostyrene, p-chlorostyrene, dichlorostyrene and the like. Of these, styrene is preferred.
  • vinyl cyanide compound is not particularly limited, examples thereof include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred.
  • the (meth)acrylic acid ester is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylic ester.
  • (meth)acrylic acid alkyl esters such as octyl acid, dodecyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, etc.
  • aromatic ring-containing (meth)acrylates aromatic ring-containing (meth)acrylates; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; glycidyls such as glycidyl (meth)acrylate and glycidylalkyl (meth)acrylate (Meth)acrylates; alkoxyalkyl (meth)acrylates, and the like.
  • the proportion of the aromatic vinyl compound unit in the entire copolymer constituting the layer (b1) is preferably 30% by weight or more and 95% by weight or less, more preferably 50% by weight or more and 90% by weight. % by weight or less is more preferable, 60% by weight or more and 85% by weight or less is even more preferable, and 70% by weight or more and 82% by weight or less is particularly preferable.
  • the proportion of the vinyl cyanide compound unit is preferably 5% by weight or more and 70% by weight or less, more preferably 10% by weight or more and 50% by weight or less, further preferably 15% by weight or more and 40% by weight or less, and 18% by weight or more. 30% by weight or less is particularly preferred.
  • the shell layer (B) may consist of the layer (b1) only, or may further include an outer layer (b2) positioned outside the layer (b1) in addition to the layer (b1).
  • the outer layer (b2) is preferably formed from a polymer containing aromatic vinyl compound units. By including such an outer layer (b2), the impact resistance of the thermoplastic resin can be further improved.
  • the aromatic vinyl compound that can be used in the outer layer (b2) is not particularly limited, and specific examples of the aromatic vinyl compound described above for the layer (b1) can be mentioned.
  • the polymer constituting the outer layer (b2) may be composed only of aromatic vinyl compound units, but may further contain vinyl cyanide compound units and/or (meth)acrylic acid ester units. .
  • the ratio of the aromatic vinyl compound units to the total polymer constituting the outer layer (b2) is preferably higher than the ratio of the aromatic vinyl compound units to the total copolymer constituting the layer (b1).
  • the ratio of the aromatic vinyl compound units to the total polymer constituting the outer layer (b2) is preferably 50% by weight or more and 100% by weight or less, more preferably 70% by weight or more, and 80% by weight. % by weight or more is more preferred, 90% by weight or more is even more preferred, and 95% by weight or more is particularly preferred.
  • the weight ratio of layer (b1):outer layer (b2) is not particularly limited, but may be, for example, about 50:50 to 99:1. From the viewpoint of improving the compatibility with the matrix resin and improving the impact resistance, 60:40 to 98:2 is preferable, 70:30 to 97:3 is more preferable, and 80:20 to 95:5 is particularly preferable. .
  • the shell layer (B) may be composed of only the layer (b1) and the outer layer (b2), or in addition to these two layers, a layer that is neither the layer (b1) nor the outer layer (b2) may be added. may contain.
  • the shell layer (B), layer (b1), and outer layer (b2) may be formed from a polymer having a crosslinked structure, but are preferably formed from a polymer having no crosslinked structure. That is, the shell layer (B), layer (b1) and outer layer (b2) are preferably formed from a polymer produced without using a crosslinkable monomer.
  • the proportion of the core-shell type graft copolymer particles occupied by the shell layer (B) is preferably 35% by weight or more and 50% by weight or less from the viewpoint of the balance between impact resistance and color development. 47% by weight or less is more preferable, 45% by weight or less is even more preferable, 42% by weight or less is even more preferable, and 40% by weight or less is particularly preferable.
  • the lower limit of the ratio may be 36% by weight or more.
  • the production of the graft copolymer particles is not particularly limited, but for example, emulsion polymerization, miniemulsion polymerization, microemulsion polymerization, or soap-free emulsion polymerization can be used. Among them, emulsion polymerization is preferred.
  • the emulsifier that can be used in emulsion polymerization is not particularly limited, and anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. can be used. Dispersants such as polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone and polyacrylic acid derivatives may also be used in combination.
  • the anionic surfactant is not particularly limited, but includes, for example, the following compounds: potassium laurate, potassium coconut fatty acid, potassium myristate, potassium oleate, potassium oleate diethanolamine salt, sodium oleate, palmitic acid.
  • Fatty acid soaps such as potassium, potassium stearate, sodium stearate, mixed fatty acid soda soap, semi-hardened tallow fatty acid soda soap, castor oil potassium soap; sodium dodecyl sulfate, sodium higher alcohol sulfate, triethanolamine dodecyl sulfate, ammonium dodecyl sulfate, poly Alkyl sulfate ester salts such as sodium oxyethylene alkyl ether sulfate, triethanolamine polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium 2-ethylhexyl sulfate; sodium alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate; sodium dialkylsulfosuccinate such as sodium di-2-ethylhexylsulfosuccinate; sodium alkylnaphthalenesulfon
  • the nonionic surfactant is not particularly limited, but includes, for example, the following compounds: polyoxyethylene alkylallyl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether; Polyoxyethylene alkyl ethers, polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate polyoxyethylene fatty acid esters such as ate, oxyethylene/oxypropylene block copolymers, and the like.
  • polyoxyethylene alkylallyl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether
  • Polyoxyethylene alkyl ethers, polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbit
  • the cationic surfactant is not particularly limited, but includes, for example, the following compounds: alkylamine salts such as coconutamine acetate, stearylamine acetate, octadecylamine acetate, tetradecylamine acetate; lauryltrimethylammonium chloride; quaternary ammonium salts such as stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride;
  • amphoteric surfactant is not particularly limited, but includes, for example, the following compounds: laurylbetaine, stearylbetaine, alkylbetaines such as dimethyllaurylbetaine; sodium lauryldiaminoethylglycinate; amidobetaine; imidazoline; Ethylimidazolinium betaine, etc.
  • emulsifiers may be used alone or in combination of two or more.
  • the amount of the emulsifier to be used may be appropriately set, but the average particle size of the polymer particles can be controlled by adjusting the amount to be used.
  • thermo decomposition initiators such as 2,2′-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate and ammonium persulfate can be used as thermal decomposition initiators.
  • organic peroxides such as t-butylperoxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and t-hexyl peroxide Oxides; peroxides such as inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate; sodium formaldehyde sulfoxylate; glucose; transition metal salts such as iron (II) sulfate; a chelating agent; and at least one reducing agent selected from the group consisting of pyrophosphates such as sodium pyrophosphate.
  • peroxides such as inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate; sodium formaldehyde sulfoxylate; glucose; transition metal salts such as iron (II) sul
  • a redox initiator When a redox initiator is used, polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set within a wide range, which is preferable.
  • organic peroxides such as cumene hydroperoxide, dicumyl peroxide and t-butyl hydroperoxide are preferably used as redox initiators.
  • the amount of the initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when a redox initiator is used may be within a known range.
  • a known chain transfer agent can be used in a known amount when polymerizing the crosslinkable monomer.
  • Surfactants can additionally be used and are within the known range.
  • any solvent may be used as long as it allows the emulsion polymerization to proceed stably.
  • water or the like can be suitably used.
  • the temperature during emulsion polymerization is not particularly limited as long as the emulsifier is uniformly dissolved in the solvent.
  • the core-shell type graft copolymer particles according to the present disclosure can be produced by sequentially performing the following steps (I) to (V). However, step (I) and step (V) are optional steps and may not be performed.
  • Polymerization of the polyorganosiloxane rubber-forming component can be carried out by mixing the polyorganosiloxane rubber-forming component, an emulsifier, and water to form an emulsion, and heating under acidic or basic conditions. Thereby, a polyorganosiloxane rubber particle (a1)-containing latex can be obtained.
  • the particle size of the resulting polyorganosiloxane rubber particles (a1) can be reduced.
  • the polyorganosiloxane rubber-forming component is added to the system containing the seed particles obtained in the step (I), and the polyorganosiloxane rubber-forming component is produced in the presence of the seed particles. is polymerized to form polyorganosiloxane rubber particles (a1) containing seed particles inside.
  • the emulsion may be added all at once, or may be added in portions.
  • the emulsion of the polyorganosiloxane rubber-forming component is prepared by using a mixture of the polyorganosiloxane rubber-forming component, an emulsifier, and water using a high-speed stirrer such as a homomixer, or a dispersing machine such as a high-pressure homogenizer or an ultrasonic disperser. can do.
  • an inorganic acid such as sulfuric acid or hydrochloric acid
  • an organic acid such as alkylsulfonic acid, alkylbenzenesulfonic acid or trifluoroacetic acid
  • Emulsifiers used under acidic conditions are preferably anionic surfactants or nonionic surfactants.
  • an inorganic base such as sodium hydroxide, potassium hydroxide or ammonia or an organic base such as pyridine or benzylmethyldodecyl ammonium hydroxide is added to the system to adjust the pH of the system, for example It may be adjusted to 11-13.5, preferably 11.5-13.
  • Emulsifiers used under basic conditions are preferably cationic surfactants.
  • the heating temperature during polymerization may be, for example, about 60 to 120° C., preferably about 70 to 100° C. from the viewpoint of achieving an appropriate polymerization rate.
  • the polyorganosiloxane rubber particle (a1)-containing latex obtained by polymerization is preferably neutralized by adding a basic aqueous solution or an acidic aqueous solution.
  • JP-A-11-293115 can be referred to.
  • a polyalkyl (meth)acrylate rubber layer (a2) is formed by polymerizing an alkyl (meth)acrylate and a crosslinkable monomer in the presence of polyorganosiloxane rubber particles (a1).
  • the core particles (A) containing the polyorganosiloxane rubber particles (a1) and the polyalkyl (meth)acrylate rubber layer (a2) can be obtained.
  • the latex is coagulated by adding one or more coagulants selected from the group consisting of acids and salts, and heat-treated at a temperature of, for example, 40° C. or higher and 110° C. or lower. Then, the core-shell type graft copolymer particles can be separated by washing, dehydrating, drying, and sieving through a sieve of a predetermined size.
  • ⁇ Resin composition> By blending the core-shell type graft copolymer particles according to the present disclosure with a thermoplastic resin to form a resin composition, the impact resistance of the thermoplastic resin is improved, and the resin composition exhibits good color development. .
  • thermoplastic resin is not particularly limited, it preferably contains a copolymer (hereinafter also referred to as a copolymer) containing an aromatic vinyl compound unit and a vinyl cyanide compound unit and/or an acrylic resin.
  • a copolymer hereinafter also referred to as a copolymer
  • the aromatic vinyl compound constituting the copolymer is not particularly limited, but examples include styrene, ⁇ -methylstyrene, p-methylstyrene, p-isopropylstyrene, o-chlorostyrene, p-chlorostyrene, dichlorostyrene, and the like. is mentioned. These may use only 1 type and may use 2 or more types together. Among these, styrene and ⁇ -methylstyrene are preferred, and styrene is particularly preferred.
  • the vinyl cyanide compound that constitutes the copolymer is not particularly limited, but examples include acrylonitrile and methacrylonitrile. These may use only 1 type and may use 2 types together. Acrylonitrile is preferred.
  • the copolymer may be a copolymer composed only of aromatic vinyl compound units and vinyl cyanide compound units. It may be a copolymer further containing.
  • the other copolymerizable vinyl compound is not particularly limited, but examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and acrylic acid.
  • (Meth)acrylic acid alkyl esters having an alkyl group of 1 to 12 carbon atoms such as 2-ethylhexyl
  • maleimide compounds such as maleimide, N-phenylmaleimide, cyclohexylmaleimide, acrylic acid, methacrylic acid, isopropenylnaphthalene, acrylamide , methacrylamide, glycidyl acrylate, glycidyl methacrylate, and the like. These may use only 1 type and may use 2 or more types together.
  • the content of the aromatic vinyl compound in the copolymer is not particularly limited, it is preferably 60 to 85% by weight, more preferably 65 to 80% by weight.
  • the content of the vinyl cyanide compound is not particularly limited, it is preferably 15 to 40% by weight, more preferably 20 to 35% by weight.
  • the content of the other copolymerizable vinyl compound is also not particularly limited, but is preferably 0 to 25% by weight, more preferably 0 to 15% by weight.
  • copolymer examples include styrene-acrylonitrile copolymer, ⁇ -methylstyrene-acrylonitrile copolymer, styrene- ⁇ -methylstyrene-acrylonitrile copolymer, styrene-maleimide-acrylonitrile copolymer, styrene- ⁇ -methylstyrene-maleimide-acrylonitrile copolymer, styrene-acrylonitrile-methyl methacrylate copolymer, ⁇ -methylstyrene-acrylonitrile-methyl methacrylate copolymer, styrene- ⁇ -methylstyrene-acrylonitrile-methyl methacrylate copolymer, Styrene-maleimide-acrylonitrile-methyl methacrylate copolymer, styrene- ⁇ -methylstyrene-maleimide-acrylonitrile-methyl methacrylate copolymer,
  • the acrylic resin is not particularly limited, examples thereof include poly(meth)acrylic acid esters such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymers, and methyl methacrylate-(meth)acrylic acid esters.
  • Copolymers methyl methacrylate-acrylic acid ester-(meth)acrylic acid copolymers, methyl methacrylate-styrene copolymers (MS resins, etc.), polymers having alicyclic hydrocarbon groups (e.g., methacrylic acid methyl-cyclohexyl methacrylate copolymer, methyl methacrylate-norbornyl (meth)acrylate copolymer, etc.).
  • the copolymer and the acrylic resin may be used alone, or both may be used in combination.
  • the usage ratio is not particularly limited. : 80 to 80:20 is more preferable, and 30:70 to 70:30 is more preferable.
  • the resin composition may further contain a thermoplastic resin other than the copolymer and the acrylic resin.
  • thermoplastic resins are not particularly limited, but examples thereof include vinyl chloride resins, polycarbonate resins, amide resins, polyester resins, and the like. These may use only 1 type and may use 2 or more types together.
  • the content of the core-shell type graft copolymer particles in the resin composition is 10 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the total amount of the thermoplastic resin, from the viewpoint of impact resistance and color development. 15 parts by weight to 80 parts by weight is more preferred, 20 parts by weight to 70 parts by weight is even more preferred, and 25 parts by weight to 60 parts by weight is particularly preferred.
  • the resin composition may optionally contain a flame retardant, an antibacterial agent, a release agent, a nucleating agent, a plasticizer, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a compatibilizer, a pigment, and a dye. , an antistatic agent, a lubricant, and the like may be added as appropriate.
  • a blending amount of each additive can be appropriately determined by those skilled in the art. These may use only 1 type and may use 2 or more types together.
  • phenol-based, sulfur-based, phosphorus-based, and hindered amine-based antioxidants or stabilizers include benzophenone-based, benzotriazole-based UV absorbers; organopolysiloxanes, aliphatic hydrocarbons, esters of higher fatty acids and higher alcohols, Internal lubricants and external lubricants such as amides or bisamides of higher fatty acids and modified products thereof, oligoamides, and metal salts of higher fatty acids can be preferably added.
  • the resin composition can be produced, for example, by mixing the core-shell type graft copolymer particles and the thermoplastic resin in the form of latex, slurry, solution, powder, pellets, or a combination thereof.
  • the core-shell type graft copolymer particles and the thermoplastic resin are latex
  • the latex contains alkaline earth metal salts such as calcium chloride, magnesium chloride and magnesium sulfate, and alkali metal salts such as sodium chloride and sodium sulfate.
  • an inorganic or organic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or acetic acid may be added to coagulate the latex into a slurry, followed by dehydration and drying.
  • a spray drying method can also be used. At this time, some of the additives such as stabilizers may be added in the form of a dispersion to the latex or slurry.
  • the resin composition is prepared by blending the core-shell type graft copolymer particles and the thermoplastic resin powder, pellets, etc. with optional additives as necessary, followed by Banbury mixer, roll mill, single-screw extruder, or twin-screw extruder. It can be kneaded by a known melt-kneader such as an extruder, and shaped into a target molded body by a known molding method such as injection molding, extrusion molding, blow molding, and the like.
  • the resin composition can be used in various applications such as electrical/electronic applications, construction applications, and vehicle applications.
  • personal computers liquid crystal displays, projectors, PDAs, printers, copiers, fax machines, video cameras, digital cameras, mobile phones (smartphones), portable audio equipment, game machines, DVD recorders, microwave ovens, rice cookers, etc.
  • Electrical and electronic applications such as translucent plates for roads, lighting windows, carports, lighting lenses, lighting covers, sizing for building materials, doors; It can be used for vehicle applications such as display, illumination, driver's seat panel, and the like.
  • a core-shell type graft copolymer particle comprising a core particle (A) and a shell layer (B) covering the core particle (A),
  • the core particle (A) includes polyorganosiloxane rubber particles (a1) and a polyalkyl (meth)acrylate rubber layer (a2) located outside the rubber particles (a1),
  • the proportion of the core particles (A) in the core-shell type graft copolymer particles is 50 to 65% by weight,
  • the volume average particle diameter of the core particles (A) is 85 to 150 nm
  • the core-shell type graft copolymer particles, wherein the shell layer (B) includes a layer (b1) formed of a copolymer containing aromatic vinyl compound units and vinyl cyanide compound units.
  • the shell layer (B) further includes an outer layer (b2) located outside the layer (b1), 2.
  • the core-shell graft according to item 1 or 2 wherein the polyorganosiloxane rubber particles (a1) contain 55 to 99.9% by weight of the polyorganosiloxane rubber component and 0.1 to 45% by weight of the vinyl polymer. Copolymer particles.
  • a manufacturing method including steps.
  • [Item 10] A molded article obtained by molding the resin composition according to item 8 or 9.
  • the volume average particle diameter of polymer particles was measured in the state of polymer particle latex. Nanotrac Wave manufactured by Nikkiso Co., Ltd. was used as a measuring device. The calculation mode was set to UPA compatible mode.
  • Polymerization conversion rate (total weight of charged raw materials ⁇ solid content ratio - total weight of raw materials other than monomer) / weight of charged monomer ⁇ 100 (%)
  • Synthesis example 1 ⁇ Production of polyorganosiloxane-containing latex (C-1)> 190 parts by weight of deionized water and 1.5 parts by weight of sodium dodecylbenzenesulfonate (SDBS) are charged into a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. , and the temperature was raised to 40° C. while stirring in a nitrogen stream.
  • SDBS sodium dodecylbenzenesulfonate
  • BA butyl acrylate
  • CHP cumene hydroperoxide
  • the seed particle latex was kept at 80° C., and 2 parts by weight of 10% by weight dodecylbenzenesulfonic acid (DBSA) was added to the system to adjust the pH of the system to 1.2.
  • DBSA dodecylbenzenesulfonic acid
  • the emulsion of forming ingredients was added hourly in four equal portions. After the addition was completed, stirring was continued for 2 hours, then the mixture was cooled to 25° C. and allowed to stand for 20 hours. Thereafter, the pH was adjusted to 7.2 with sodium hydroxide to terminate the polymerization, and the polyorganosiloxane-containing latex (C-1 ).
  • Example 1 (rubber particles) 35.7 parts by weight of the polyorganosiloxane-containing latex (C-1) obtained in Synthesis Example 1 ( 8 parts by weight as solid content), 106.6 parts by weight of deionized water, and stirred, followed by 42 parts by weight of BA, 0.59 parts by weight of allyl methacrylate (ALMA) (concentration of 1.4% by weight with respect to BA), and 0 CHP 0.39 parts by weight of the mixture was added, and the temperature was raised to 60° C. over 30 minutes while stirring in a nitrogen stream.
  • BA allyl methacrylate
  • shell layer 31.3 parts by weight of deionized water and 0.25 parts by weight of sodium formaldehyde sulfoxylate having a concentration of 5% by weight were charged thereinto, 37.5 parts by weight of styrene (ST), 12.5 parts by weight of acrylonitrile (AN), A mixture of 0.2 parts by weight of t-butyl hydroperoxide (t-BH) was added over 100 minutes. After the addition, t-BH and sodium formaldehyde sulfoxylate at a concentration of 5% by weight are added as appropriate to form a shell layer (B) composed of the layer (b1), with a polymerization conversion rate of 100% and a solid content concentration of 35.8. % of graft copolymer latex was obtained.
  • ST styrene
  • AN acrylonitrile
  • t-BH t-butyl hydroperoxide
  • Example 2 (rubber particles) First, in the same manner as in Example 1, a composite rubber latex having a polymerization conversion rate of 100%, a solid content concentration of 27.1% and a volume average particle size of 133 nm was obtained.
  • shell layer 31.3 parts by weight of deionized water and 0.25 parts by weight of sodium formaldehyde sulfoxylate having a concentration of 5% by weight were added thereto, and a mixture of 35 parts by weight of ST, 10 parts by weight of AN, and 0.067 parts by weight of t-BH was added thereto for 90 minutes. added over time. After the addition, 0.067 parts by weight of t-BH was added, followed by the addition of a mixture of 5 parts by weight of ST and 0.067 parts by weight of t-BH over 10 minutes.
  • t-BH and sodium formaldehyde sulfoxylate having a concentration of 5% by weight are added as appropriate to form a shell layer (B) consisting of a layer (b1) and an outer layer (b2), a polymerization conversion rate of 100%, a solid A graft copolymer latex having a concentration of 35.4% was obtained.
  • ⁇ Comparative Example 1> Rubber particles 174.6 parts by weight of deionized water and 15% by weight beef tallow fatty acid (LUNAC TH manufactured by Kao Corporation) were added to a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. ) and 0.05 parts by weight of sodium carbonate having a concentration of 2% by weight were charged, and the temperature was raised to 45° C. while stirring in a nitrogen stream.
  • LNAC TH beef tallow fatty acid
  • shell layer 0.00144 parts by weight of a mixed solution of disodium ethylenediaminetetraacetate and ferrous sulfate dissolved in deionized water at a mixing ratio of 5:3 to a concentration of 0.5% by weight was added thereto and heated to 70°C.
  • t-BH and sodium formaldehyde sulfoxylate at a concentration of 5% by weight are added as appropriate to form a shell layer, to obtain a graft copolymer latex having a polymerization conversion rate of 100% and a solid content concentration of 33.1%. rice field.
  • Examples 3-6 In Examples 3 and 4, graft copolymer powder was obtained in the same manner as in Example 1, except that the amount of each component used was changed according to Tables 2-4.
  • Example 5 graft copolymer powder was prepared in the same manner as in Example 1, except that the polyorganosiloxane-containing latex (C-2) obtained in Synthesis Example 2 was used according to Tables 2 to 4. got a body
  • Example 6 is the same as Example 2, except that the polyorganosiloxane-containing latex (C-2) obtained in Synthesis Example 2 is used according to Tables 2 to 4, and the amount of each component used is changed.
  • a powder of the graft copolymer was obtained by the method of .
  • Comparative Examples 2-3 In Comparative Example 2, a graft copolymer powder was obtained in the same manner as in Example 1, except that the amount of each component used was changed according to Tables 2-4. Comparative Example 3 was prepared in the same manner as in Example 1, except that the polyorganosiloxane-containing latex (C-3) obtained in Synthesis Example 3 was used according to Tables 2 to 4. got a body
  • Examples 1-1 to 6-1 (particularly Examples 3-1, 4-1, and 6-1) have higher Izod impact strength than Comparative Examples 1-1 and 2-1. value is large, indicating excellent impact resistance. In addition, Examples 1-1 to 6-1 (especially Examples 5-1 and 6-1) have a smaller L value than Comparative Example 3-1 and are excellent in color development. .
  • the core particles contained polyorganosiloxane rubber particles, the core particles (A) accounted for 50 to 65% by weight of the graft copolymer, and the core particles (A ) using core-shell type graft copolymer particles having a volume average particle diameter of 85 to 150 nm.
  • Comparative Example 1-1 does not contain polyorganosiloxane rubber particles in the core particles.
  • Comparative Example 2-1 contains polyorganosiloxane rubber particles in the core particles, but the proportion of the core particles is less than 50% by weight of the graft copolymer.
  • Comparative Example 3-1 contains polyorganosiloxane rubber particles in the core particles, the core particles are in the range of 50 to 65% by weight of the graft copolymer, and the volume average particle diameter of the core particles exceeds 150 nm. It is a thing.
  • the examples and comparative examples shown in Tables 3 and 4 differ in the type or amount of the thermoplastic resin (matrix resin) used in the evaluation, but are the same as the examples and comparative examples shown in Table 2.
  • the core-shell type graft copolymer particles were evaluated. Both Tables 3 and 4 show that each example has a large Izod impact strength value, a small L value, and excellent color developability.

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Abstract

L'invention concerne des particules de copolymère greffé de type noyau/enveloppe, comprenant des particules de noyau (A) et une couche d'enveloppe (B) recouvrant chaque particule de noyau (A). Chacune des particules de noyau (A) comprend une particule de caoutchouc au polyorganosiloxane (a1) et une couche de caoutchouc au poly (méth)acrylate d'alkyle) (a2) située sur le côté extérieur de la particule de caoutchouc (a1). Les particules de noyau (A) représentent 50 à 65 % en poids des particules de copolymère greffé de type noyau/enveloppe et ont un diamètre de particule moyen en volume de 85 à 150 nm. La couche de coque (B) comprend une couche (b1) formée à partir d'un copolymère comprenant une unité de composé de vinyle aromatique et une unité de composé de cyanure de vinyle.
PCT/JP2022/044060 2021-11-30 2022-11-29 Particules de copolymère greffé de type noyau/enveloppe, leur procédé de fabrication et composition de résine WO2023100903A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019147868A (ja) * 2018-02-26 2019-09-05 ユーエムジー・エービーエス株式会社 熱可塑性樹脂組成物およびその成形品
WO2021065721A1 (fr) * 2019-09-30 2021-04-08 テクノＵｍｇ株式会社 Agent conférant une hydrophobicité, composition de résine thermoplastique et article moulé associé

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019147868A (ja) * 2018-02-26 2019-09-05 ユーエムジー・エービーエス株式会社 熱可塑性樹脂組成物およびその成形品
WO2021065721A1 (fr) * 2019-09-30 2021-04-08 テクノＵｍｇ株式会社 Agent conférant une hydrophobicité, composition de résine thermoplastique et article moulé associé

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