WO2021060709A1 - Copolymère cœur-écorce et composition de résine le contenant - Google Patents

Copolymère cœur-écorce et composition de résine le contenant Download PDF

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WO2021060709A1
WO2021060709A1 PCT/KR2020/010947 KR2020010947W WO2021060709A1 WO 2021060709 A1 WO2021060709 A1 WO 2021060709A1 KR 2020010947 W KR2020010947 W KR 2020010947W WO 2021060709 A1 WO2021060709 A1 WO 2021060709A1
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Prior art keywords
core
weight
parts
repeating unit
unit derived
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PCT/KR2020/010947
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English (en)
Korean (ko)
Inventor
남상일
유기현
김윤호
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020200085311A external-priority patent/KR102532948B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/423,360 priority Critical patent/US11746173B2/en
Priority to JP2021539850A priority patent/JP7205985B2/ja
Priority to EP20869461.2A priority patent/EP3892657B1/fr
Priority to CN202080009226.1A priority patent/CN113302218B/zh
Publication of WO2021060709A1 publication Critical patent/WO2021060709A1/fr

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Classifications

    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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 a core-shell copolymer, and more particularly, to a core-shell copolymer and a resin composition comprising the same.
  • Polyvinyl chloride (PVC) resin is widely used in various fields due to its low price and easy adjustment of hardness, various applications, and excellent physical and chemical properties.
  • the vinyl chloride resin may be mixed and molded with various additives in order to supplement various physical properties including impact resistance of the vinyl chloride resin, rather than being used alone when molding a product.
  • polyvinyl chloride resins have been appropriately selected and used with additives such as impact modifiers, processing aids, stabilizers, and fillers.
  • additives such as impact modifiers, processing aids, stabilizers, and fillers.
  • butadiene-based impact modifiers such as methacrylate butadiene stylene (MBS)-based impact modifiers, acrylonitrile butadiene styrene (ABS) impact modifiers as impact modifiers for vinyl chloride resin, claw Chlorinated polyethylene (CPE) impact modifiers, silicone impact modifiers, etc. are generally used, and MBS impact modifiers are mainly used among butadiene impact modifiers.
  • a film manufactured by mixing a PVC resin with an impact modifier is used for packaging of finished products or for transparent decorative sheet products.
  • the product made of the PVC film containing the impact modifier is folded or when an external force is applied, the whitening phenomenon of turning white occurs, and the customer's demand for improvement of the whitening phenomenon is increasing, so research on this is actively progressing. Has become.
  • the PVC resin is a product that can be recycled, a problem arising from a decrease in thermal stability occurring during reprocessing has been caused, and research and development to improve thermal stability in addition to the whitening phenomenon are continuously required.
  • the problem to be solved in the present invention is, in order to solve the problems mentioned in the technology behind the background of the present invention, in the core-shell copolymer, a repeating unit derived from an aromatic vinyl monomer and an aromatic (meth)acrylic as a core and shell component
  • a repeating unit derived from a rate monomer By introducing a repeating unit derived from a rate monomer, the particle size and refractive index of the core and core-shell copolymer are controlled, thereby simultaneously improving the impact strength, whitening properties, and thermal stability of a molded article made of a polyvinyl resin composition comprising the same. It is aimed at.
  • the present invention is a core-shell copolymer comprising a core and a shell surrounding the core, wherein the core is a repeating unit derived from a conjugated diene-based monomer, an aromatic vinyl It contains a repeating unit derived from a monomer and a repeating unit derived from an aromatic (meth)acrylate monomer, and the shell is a repeating unit derived from an alkyl (meth)acrylate-based monomer, a repeating unit derived from an aromatic vinyl monomer, and a repeating unit derived from an aromatic (meth)acrylate monomer.
  • the core has a particle size of 800 ⁇ to 900 ⁇
  • the core-shell copolymer has a particle size of 900 ⁇ to 1000 ⁇
  • the core has a refractive index of 1.5355 to 1.5425, and the core-shell copolymer
  • the coalescence provides a core-shell copolymer having a refractive index of 1.5415 to 1.5440.
  • the present invention provides a resin composition comprising the core-shell copolymer and a vinyl chloride polymer.
  • the particle size of the core and the core-shell copolymer by introducing a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from an aromatic (meth)acrylate monomer as a core component and a shell component, the particle size of the core and the core-shell copolymer and By controlling the refractive index, the impact strength, whitening characteristics, and thermal stability of a molded article made of a polyvinyl resin composition including the same can be improved at the same time.
  • the term'monomer-derived repeating unit' may refer to a component, structure, or substance itself derived from a monomer, and refers to a repeating unit formed in the polymer by participating in the polymerization reaction of the introduced monomer during polymerization of the polymer. It can be.
  • the term'core' may mean a polymer component or a copolymer component forming a core or core layer of a core-shell copolymer by polymerizing a monomer forming a core. .
  • the term'shell' means that a monomer forming a shell is graft-polymerized on a core of a core-shell copolymer, and the shell encloses the core, forming a shell or a shell layer of a core-shell copolymer. It may mean a polymer component or a copolymer component.
  • the term'(meth)acrylate' may mean acrylate or methacrylate.
  • the term'latex' may mean that a polymer or copolymer polymerized by polymerization exists in a dispersed form in water. It may mean that the particulates exist in a colloidal state and dispersed in water.
  • a core-shell copolymer comprising a core and a shell surrounding the core
  • the core includes a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an aromatic vinyl monomer, and a repeating unit derived from an aromatic (meth)acrylate monomer
  • the shell includes a repeating unit derived from an alkyl (meth)acrylate monomer, a repeating unit derived from an aromatic vinyl monomer, and a repeating unit derived from an aromatic (meth)acrylate monomer
  • the particle size of the core is 800 ⁇ to 900 ⁇
  • the The core-shell copolymer may have a particle size of 900 ⁇ to 1000 ⁇
  • the core may have a refractive index of 1.5355 to 1.5425, and the core-shell copolymer may have a refractive index of 1.5415 to 1.5440.
  • the particle size of the core and the core-shell copolymer By controlling the refractive index within the above range, the impact strength, whitening characteristics, and thermal stability of a molded article made of a polyvinyl resin composition including the same can be simultaneously improved.
  • the core may be a core polymer constituting the core of the core-shell copolymer, and specific examples include a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an aromatic vinyl monomer, and an aromatic (meth)acrylic. It may include a repeating unit derived from a rate monomer, and the shell may be a shell polymer that is grafted onto the core polymer and surrounds the core, and specific examples are repeating units derived from a methyl (meth)acrylate monomer, derived from an aromatic vinyl monomer. It may include a repeating unit and a repeating unit derived from an aromatic (meth)acrylate monomer.
  • the conjugated diene-based monomer forming the repeating unit derived from the conjugated diene-based monomer included in the core is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, It may contain at least one selected from the group consisting of 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene.
  • the content of the repeating unit derived from the conjugated diene-based monomer included in the core may be 60 parts by weight to 85 parts by weight based on 100 parts by weight of the total core.
  • the content of the repeating unit derived from the conjugated diene-based monomer contained in the core is 65 to 83 parts by weight, 65 to 81 parts by weight, or 65 to 79 parts by weight based on 100 parts by weight of the total core. It can be wealth. In this case, there is an effect of excellent impact resistance of a molded article manufactured from a resin composition containing a core-shell copolymer.
  • the aromatic vinyl monomer forming the repeating unit derived from the aromatic vinyl monomer contained in the core is styrene, alpha methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-propyl styrene, isopro Phenylnaphthalene, 1-vinylnaphthalene, styrene substituted with an alkyl group having 1 to 3 carbon atoms, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and at least one selected from the group consisting of halogen-substituted styrene.
  • the aromatic vinyl monomer may be alpha methyl styrene represented by Formula 1 below.
  • the content of the repeating unit derived from the aromatic vinyl monomer included in the core may be 4 parts by weight to 20 parts by weight based on 100 parts by weight of the total core.
  • compatibility between the vinyl chloride resin and the core is imparted, and the refractive index is high as 1.5350 to 1.5420, and when a core-shell copolymer containing it is used as an impact modifier, the thermal stability and transparency of the thermoplastic resin can be improved.
  • the refractive index of the repeating unit derived from the aromatic vinyl monomer may be 1.5360 to 1.5410, 1.5370 to 1.5400, or 1.5380 to 1.5400.
  • the aromatic (meth)acrylate monomer forming the repeating unit derived from the aromatic (meth)acrylate monomer included in the core is biphenylmethyl acrylate and phenoxy benzyl acrylate. It may contain at least one selected from the group consisting of (phenoxy benzyl acrylate).
  • the aromatic (meth)acrylate monomer may be biphenylmethyl acrylate represented by Formula 2 below.
  • the content of the repeating unit derived from the aromatic (meth)acrylate monomer included in the core may be 4 parts by weight to 27 parts by weight, 4 parts by weight to 25 parts by weight, or 4 parts by weight to 20 parts by weight based on 100 parts by weight of the total core. .
  • compatibility between the vinyl chloride resin and the core is imparted, and the refractive index is high as 1.5950 to 1.6100, and when a core-shell copolymer containing the same is used as an impact modifier, the thermal stability, transparency, and whitening properties of the thermoplastic resin Can be improved.
  • the refractive index of the repeating unit derived from the aromatic (meth)acrylate monomer may be 1.5960 to 1.6090, 1.5980 to 1.6050, or 1.5980 to 1.6020.
  • the weight ratio of the repeating unit derived from the aromatic vinyl monomer and the repeating unit derived from the aromatic (meth)acrylate monomer included in the core may be 1:0.2 to 1:5.
  • the weight ratio of the repeating unit derived from the aromatic vinyl monomer and the repeating unit derived from the aromatic (meth)acrylate monomer contained in the core is 1:0.23 to 1:5, 1:0.25 to 1:4.5 or 1:0.25 to 1 May be :4.
  • the refractive index of the core may be controlled to 1.5355 to 1.5425.
  • the core may further include a repeating unit derived from a crosslinkable monomer in addition to the repeating unit derived from the conjugated diene-based monomer.
  • the crosslinkable monomers are ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.
  • (Meth)acrylic crosslinkable monomers such as acrylate; And at least one selected from the group consisting of vinyl-based crosslinkable monomers such as divinylbenzene, divinylnaphthalene and diallylphthalate.
  • the content of the repeating unit derived from the crosslinkable monomer included in the core may be 0.1 parts by weight to 1 part by weight based on 100 parts by weight of the total core.
  • the content of the repeating unit derived from the crosslinkable monomer may be 0.1 parts by weight to 0.8 parts by weight, 0.2 parts by weight to 0.8 parts by weight, or 0.3 parts by weight to 0.7 parts by weight, based on 100 parts by weight of the total core.
  • the polymerization productivity can be excellent within this range.
  • the particle size of the core may be 800 ⁇ to 900 ⁇ .
  • the particle size of the core may be controlled by adjusting the amount of the emulsifier and the concentration of the electrolyte during the manufacture of the core. Specifically, when the amount of emulsifier is increased during core manufacturing, the size of the core particles decreases, and when the concentration of the electrolyte is increased, the size of the core particles can be increased.In the present invention, the input amount of the emulsifier and the concentration of the electrolyte are adjusted.
  • the particle size of the core can be controlled from 800 ⁇ to 900 ⁇ , through which the impact strength, transparency, and impact strength of a molded article molded with a resin composition containing the core-shell copolymer in which the particle size of the core satisfies the above range. Thermal stability can be improved at the same time.
  • the refractive index of the core may be 1.5355 to 1.5425.
  • a material forming the core by mixing a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from an aromatic (meth)acrylate monomer, it has a refractive index within the above range, and the alkyl group contained in the aromatic ring is While being oriented, it exhibits high strength characteristics, improves heat resistance, and forms an entanglement structure due to the alkyl (meth)acrylate, thereby improving surface adhesion to the vinyl chloride resin.
  • the alkyl (meth)acrylate monomer forming the repeating unit derived from the alkyl (meth)acrylate monomer contained in the shell may be an alkyl (meth)acrylate) monomer having 1 to 8 carbon atoms. .
  • the alkyl (meth)acrylate monomer is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, and may include at least one selected from the group consisting of 2-ethylhexyl (meth) acrylate, in this case a core-shell copolymer
  • a core-shell copolymer There is an effect of excellent impact resistance of the molded article prepared from the resin composition comprising a.
  • the content of the repeating unit derived from the alkyl (meth)acrylate monomer contained in the shell is 10 parts by weight to 35 parts by weight, 10 parts by weight to 30 parts by weight, or 10 parts by weight based on the total 100 parts by weight of the core-shell copolymer. It may be from parts by weight to 20 parts by weight. Within this range, there is an effect excellent in impact resistance, surface characteristics, and heat resistance of a molded article manufactured from a resin composition containing a core-shell copolymer.
  • the description of the repeating unit derived from the aromatic vinyl monomer and the repeating unit derived from the aromatic (meth)acrylate monomer contained in the shell is for the repeating unit derived from the aromatic vinyl monomer and the repeating unit derived from the aromatic (meth)acrylate monomer contained in the core. May be the same as the description.
  • the content of the repeating unit derived from the aromatic vinyl monomer contained in the shell is 5 parts by weight to 20 parts by weight, 5 parts by weight to 18 parts by weight, or 5 parts by weight to 17 parts by weight based on the total 100 parts by weight of the core-shell copolymer. I can.
  • the content of the repeating unit derived from the aromatic (meth)acrylate monomer contained in the shell is 5 parts by weight to 20 parts by weight, 5 parts by weight to 18 parts by weight, or 5 parts by weight based on the total 100 parts by weight of the core-shell copolymer. It may be to 17 parts by weight.
  • the weight ratio of the repeating unit derived from the aromatic vinyl monomer and the repeating unit derived from the aromatic (meth)acrylate monomer contained in the shell may be 1:0.25 to 1:3.5.
  • the weight ratio of the repeating unit derived from the aromatic vinyl monomer and the repeating unit derived from the aromatic (meth)acrylate monomer contained in the shell is 1:0.27 to 1:3.5, 1:0.27 to 1:3.3 or 1:0.3 to 1 Can be :3.3.
  • the refractive index of the core-shell copolymer can be controlled to 1.5415 to 1.5440.
  • the core-shell copolymer may have a refractive index of 1.5415 to 1.5440.
  • the material forming the core and the shell by mixing a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from an aromatic (meth)acrylate monomer, it has a refractive index within the above range, and the alkyl group contained in the aromatic ring is As it is oriented in the direction, heat resistance is improved, and a structure sufficiently surrounding the core is formed due to the alkyl (meth)acrylate, thereby providing a core-shell copolymer having improved processability, transparency, thermal stability, and impact strength at the same time.
  • the particle size of the core-shell copolymer may be 900 ⁇ to 1000 ⁇ .
  • the particle size of the core-shell copolymer may be controlled according to the size of the core particle. Specifically, in the present invention, by forming the size of the core particle to 800 ⁇ to 900 ⁇ , the particle size of the core-shell copolymer can be controlled to 900 ⁇ to 1000 ⁇ , Impact strength, transparency and thermal stability can be improved at the same time.
  • the content of the core may be 40% to 95% by weight, 50% to 90% by weight, or 60% to 80% by weight based on the total content of the core-shell copolymer.
  • the content of the shell may be 5% to 60% by weight, 10% to 50% by weight, or 20% to 40% by weight based on the total content of the core-shell copolymer, within this range the core -The impact resistance of the molded article made from the resin composition containing the shell copolymer is excellent, and the balance between physical properties is excellent.
  • the core-shell copolymer manufacturing method includes the steps of preparing a core polymer by polymerizing a monomer mixture for forming a core (S10); And in the presence of the core polymer prepared in step (S10), it may include a step (S20) of preparing a core-shell copolymer by emulsion polymerization of the monomer mixture for forming a shell.
  • the polymerization of step (S10) and step (S20) is performed in the presence of a monomer mixture for forming a core and a monomer mixture for forming a shell, respectively, a peroxide-based, redox, or azo-based initiator It can be carried out by radical polymerization using, and can be carried out by an emulsion polymerization method.
  • step (S10) is a step for polymerizing a core polymer forming a core included in a core-shell copolymer, and may be carried out by emulsion polymerization of a monomer mixture for forming a core.
  • the core-forming monomer mixture may include a conjugated diene-based monomer, an aromatic vinyl monomer, and an aromatic (meth)acrylate monomer described above, and a crosslinkable monomer may be further added if necessary. It may be included, and the type and content of each monomer may be the same as the type and content of the monomer-derived repeating unit described above.
  • the emulsion polymerization in step (S10) may be carried out in the presence of an emulsifier, and in this case, the emulsifier is a group consisting of an anionic emulsifier, a cationic emulsifier, and a nonionic emulsifier.
  • One or more may be selected from, for example, sulfonate, carboxylate, succinate, sulfosuccinate and metal salts thereof, such as alkylbenzenesulfonic acid, sodium alkylbenzene sulfonate, alkylsulfonic acid, sodium Alkyl sulfonate, sodium polyoxyethylene nonylphenyl ether sulfonate, sodium stearate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate, sodium dodecyl sulfosuccinate, potassium oleate, abietic acid
  • Anionic emulsifiers generally widely used in emulsion polymerization such as salts; Cationic emulsifiers to which an amine halide, an alkyl tetraammonium salt, an alkylpyridinium salt, and the like are bound as a functional group
  • the polymerization may be performed by additionally using additives such as an initiator, a molecular weight modifier, an activator and a redox catalyst.
  • additives such as an initiator, a molecular weight modifier, an activator and a redox catalyst.
  • the initiator examples include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; Diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide , Organic peroxides such as octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutylate; And nitrogen compounds such as azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis isobutyric acid (butyric acid)
  • the molecular weight modifier examples include mercaptans such as a-methyl styrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; And sulfur-containing compounds such as tetraethyl diuram disulfide, dipentamethylene diuram disulfide, and diisopropylxanthogen disulfide.
  • the molecular weight modifier may be used in an amount of 0.1 to 3 parts by weight, based on 100 parts by weight of the total core-shell copolymer.
  • the activator is, for example, sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium linolenic acid, and sodium sulfate to select one or more selected from among I can.
  • the activator may be used in an amount of 0.01 parts by weight to 0.15 parts by weight based on 100 parts by weight of the total core-shell copolymer.
  • the redox catalyst may be, for example, sodium formaldehyde sulfoxylate, ferrous sulfate, disodium ethylenediaminetetraacetate, and second copper sulfate.
  • the redox catalyst may be used in an amount of 0.01 parts by weight to 0.1 parts by weight based on a total of 100 parts by weight of the core-shell copolymer.
  • the polymerization of the step (S10) and the step (S20) may be carried out at a temperature of 50 °C to 150 °C, or 50 °C to 130 °C, and to perform the polymerization of each step. It may be carried out in the presence of various solvents and additives that are commonly used for this purpose.
  • the core polymer and core-shell copolymer prepared in the (S10) and (S20) steps are obtained in the form of latex in which the polymer and the copolymer are dispersed in a solvent, respectively.
  • a core-shell copolymer latex containing a core-shell copolymer in the form of powder after the core-shell copolymer latex is prepared in the step (S20) agglomeration, aging, dehydration and drying, etc. The process of can be carried out.
  • a resin composition comprising the core-shell copolymer as an impact modifier.
  • the resin composition may include the core-shell copolymer and a vinyl chloride polymer. That is, the resin composition may be a vinyl chloride resin composition.
  • the vinyl chloride polymer may be used without limitation as long as it is a vinyl chloride polymer containing a repeating unit derived from a vinyl chloride monomer, and the resin composition is based on 100 parts by weight of the vinyl chloride polymer, and the core -A shell copolymer (based on solid content) may be included in an amount of 1 to 10 parts by weight, or 3 to 8 parts by weight, and within this range, the impact strength of the molded article manufactured from the resin composition is improved, and thermal stability And there is an effect of improving the transparency characteristics.
  • the resin composition according to the present invention in addition to the core-shell copolymer and the vinyl chloride polymer, if necessary, within a range that does not deteriorate its physical properties, stabilizers, processing aids, thermal stabilizers, lubricants, pigments, dyes, antioxidants It may further include additives such as.
  • the particle size was measured for the weight average particle size using a Nicomp instrument. Specifically, 1 g of the latex composition was sampled using Nicomp 380, and the sample was diluted and proceeded for 5 minutes at an intensity of 300 KHz, and then the stabilized particle size was measured.
  • the refractive index was determined by using an Abbe Mark III refractometer (Reichert) to pin 1 g of core latex or core-shell copolymer latex to a thickness of 0.1 mm on a Saale, and then dry it at 55° C. for 4 hours to form a film. It was measured after making it.
  • Abbe Mark III refractometer Reichert
  • the core-shell copolymer powders prepared in Examples 1 to 7 and Comparative Examples 1 to 9 were added in 7 parts by weight, respectively, and a two-roll at 195°C was used to have a thickness of 0.6 mm. A sheet of was prepared.
  • Swell index weight of swelling in toluene/weight after drying toluene
  • Izod impact strength was measured according to ASTM D256 for the prepared resin composition specimen.
  • the prepared resin composition specimen having a thickness of 0.6 mm was cut into a size of 10 cm (horizontal) X 14 cm (vertical), and the transmittance and haze were measured using a haze meter (Suga company).
  • ⁇ YI YI value of 10-minute machined specimen-YI value of 3-minute machined specimen
  • the resin composition containing the core-shell copolymers of Examples 1 to 7 prepared according to the present invention as an impact modifier does not use both alphamethylstyrene and biphenylmethyl acrylate. It was confirmed that transparency, thermal stability, and impact strength were improved compared to Comparative Example 1.

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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)

Abstract

La présente invention concerne un copolymère cœur-écorce. Plus particulièrement, la présente invention concerne un copolymère cœur-écorce comprenant un cœur et une écorce entourant le cœur, le cœur comprenant un motif de répétition dérivé d'un monomère à base de diène conjugué, un motif de répétition dérivé d'un monomère de vinyle aromatique, et un motif de répétition dérivé d'un monomère (méth)acrylate aromatique, l'écorce comprenant un motif de répétition dérivé d'un monomère à base de (méth)acrylate d'alkyle, un motif de répétition dérivé d'un monomère de vinyle aromatique, et un motif de répétition dérivé d'un monomère (méth)acrylate aromatique, la taille de particule du cœur étant de 800 à 900 Å, la taille de particule du copolymère cœur-écorce étant de 900 à 1 000 Å, l'indice de réfraction du cœur étant de 1,5355 à 1,5425, et l'indice de réfraction du copolymère cœur-écorce étant de 1,5415 à 1,5440.
PCT/KR2020/010947 2019-09-26 2020-08-18 Copolymère cœur-écorce et composition de résine le contenant WO2021060709A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/423,360 US11746173B2 (en) 2019-09-26 2020-08-18 Core-shell copolymer and resin composition containing same
JP2021539850A JP7205985B2 (ja) 2019-09-26 2020-08-18 コア－シェル共重合体およびそれを含む樹脂組成物
EP20869461.2A EP3892657B1 (fr) 2019-09-26 2020-08-18 Copolymère coeur-écorce et composition de résine le contenant
CN202080009226.1A CN113302218B (zh) 2019-09-26 2020-08-18 核-壳共聚物和包含该核-壳共聚物的树脂组合物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2019-0118625 2019-09-26
KR20190118625 2019-09-26
KR10-2020-0085311 2020-07-10
KR1020200085311A KR102532948B1 (ko) 2019-09-26 2020-07-10 코어-쉘 공중합체 및 이를 포함하는 수지 조성물

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Publication number Priority date Publication date Assignee Title
JP2002256037A (ja) * 2001-02-27 2002-09-11 Kuraray Co Ltd コア・シェル構造重合体粒子および該粒子を含有するポリエチレンテレフタレート系樹脂組成物
KR100815995B1 (ko) * 2006-06-08 2008-03-21 제일모직주식회사 저온 및 상온 내충격성과 착색성 및 내후성이 우수한ａｓａ 그라프트 공중합체 및 이를 포함한 열가소성 수지조성물
KR20080068037A (ko) * 2005-09-30 2008-07-22 바스프 에스이 개선된 광학 성질을 갖는 열가소성 플라스틱 성형 조성물
KR20160081497A (ko) * 2014-12-31 2016-07-08 삼성에스디아이 주식회사 그라프트 공중합체 및 이를 포함하는 열가소성 수지 조성물
KR20190084549A (ko) * 2018-01-08 2019-07-17 주식회사 엘지화학 코어-쉘 공중합체, 이의 제조방법 및 이를 포함하는 수지 조성물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002256037A (ja) * 2001-02-27 2002-09-11 Kuraray Co Ltd コア・シェル構造重合体粒子および該粒子を含有するポリエチレンテレフタレート系樹脂組成物
KR20080068037A (ko) * 2005-09-30 2008-07-22 바스프 에스이 개선된 광학 성질을 갖는 열가소성 플라스틱 성형 조성물
KR100815995B1 (ko) * 2006-06-08 2008-03-21 제일모직주식회사 저온 및 상온 내충격성과 착색성 및 내후성이 우수한ａｓａ 그라프트 공중합체 및 이를 포함한 열가소성 수지조성물
KR20160081497A (ko) * 2014-12-31 2016-07-08 삼성에스디아이 주식회사 그라프트 공중합체 및 이를 포함하는 열가소성 수지 조성물
KR20190084549A (ko) * 2018-01-08 2019-07-17 주식회사 엘지화학 코어-쉘 공중합체, 이의 제조방법 및 이를 포함하는 수지 조성물

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