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WO2020050639A1 - Composition de résine thermoplastique - Google Patents

Composition de résine thermoplastique Download PDF

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Publication number
WO2020050639A1
WO2020050639A1 PCT/KR2019/011449 KR2019011449W WO2020050639A1 WO 2020050639 A1 WO2020050639 A1 WO 2020050639A1 KR 2019011449 W KR2019011449 W KR 2019011449W WO 2020050639 A1 WO2020050639 A1 WO 2020050639A1
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WO
WIPO (PCT)
Prior art keywords
weight
thermoplastic resin
copolymer
monomer unit
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2019/011449
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English (en)
Korean (ko)
Inventor
최정수
유근훈
이원석
이루다
이종주
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LG Chem Ltd
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LG Chem Ltd
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Publication date
Priority claimed from KR1020190108784A external-priority patent/KR102288853B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201980026447.7A priority Critical patent/CN112020537B/zh
Priority to EP19856706.7A priority patent/EP3848414B1/fr
Priority to US17/047,374 priority patent/US11299615B2/en
Priority to JP2020556909A priority patent/JP7118462B2/ja
Publication of WO2020050639A1 publication Critical patent/WO2020050639A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only 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
    • C08F279/06—Vinyl aromatic monomers and methacrylates as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition having improved transparency while maintaining basic properties.
  • ABS graft copolymer used in these parts is excellent in quality such as impact resistance, chemical resistance, processability and surface gloss, but it is an opaque material and therefore cannot be used for materials requiring transparency.
  • Commonly used transparent materials include polycarbonate (PC), polymethyl methacrylate (PMMA), polystyrene (PS), and polyacrylonitrile-styrene (SAN).
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • SAN polyacrylonitrile-styrene
  • Polycarbonate resin has excellent impact strength and transparency, but it is difficult to make complex products due to poor processability.
  • Polymethyl methacrylate has excellent transparency, but has very poor impact resistance and chemical resistance.
  • the impact resistance and chemical resistance of polystyrene (PS) and polyacrylonitrile-styrene (SAN) are very poor.
  • US Patent No. 4,767,833, Japanese Patent Publication No. Hei 11-147020, European Patent No. 703,252, and Japanese Patent Publication No. Hei 8-199008 have excellent impact resistance, chemical resistance, processability, etc.
  • -A method of imparting transparency by introducing an alkyl (meth) acrylate monomer to a styrene-based graft copolymer is disclosed.
  • the haze of most products exceeds 2.0 due to the limitation of transparency, there are limitations in use for products using PMMA, PC, SAN, etc., products that require thick injection or high transparency.
  • thermoplastic resin composition in which transparency is significantly improved while maintaining basic properties such as impact resistance and fluidity.
  • the present invention comprises A-1) a first conjugated diene polymer, an alkyl (meth) acrylate monomer unit, and an aromatic vinyl monomer unit, and the first conjugated diene polymer is average A first copolymer having a particle size of 0.05 to 0.2 ⁇ m; A-2) A second conjugated diene-based polymer, an alkyl (meth) acrylate-based monomer unit, and an aromatic vinyl-based monomer unit, wherein the second conjugated diene-based polymer has a second copolymer having an average particle diameter of 0.23 to 0.5 ⁇ m.
  • the present invention is made of the above-mentioned thermoplastic resin composition, including an impact reinforcement region and a matrix region, the impact reinforcement region being selected from the group consisting of the first conjugated diene-based polymer and the second conjugated diene-based polymer 1 It includes a species or more, and the matrix region includes the alkyl (meth) acrylate-based monomer unit and the aromatic vinyl-based monomer unit, and the impact reinforcement region and the matrix region provide a thermoplastic resin molded article having a refractive index difference of 0.01 or less.
  • thermoplastic resin composition of the present invention is not only excellent in basic physical properties such as impact resistance and fluidity, but also transparency can be remarkably improved.
  • the refractive index refers to the absolute refractive index of a material, which is recognized as the ratio of the rate of electromagnetic radiation in a free space to the rate of radiation in a material, where the radiation is visible light having a wavelength of 450 to 680 nm.
  • the refractive index can be measured using a known method, generally using an Abbe Refractometer.
  • the refractive index of the graft copolymer can be calculated according to the following formula using the refractive index and content ratio of each polymer of the graft copolymer composition:
  • Refractive index (RI) ⁇ [content of alkyl (meth) acrylate-based monomer units (% by weight)] ⁇ [refractive index of alkyl (meth) acrylate-based homopolymers] ⁇ + ⁇ [content of aromatic vinyl-based monomer units (weight %)] ⁇ [Refractive index of aromatic vinyl-based homopolymer] ⁇ + ⁇ [Content of vinyl cyan-based monomer unit (% by weight)] ⁇ [Refractive index of vinyl cyan-based homopolymer] ⁇
  • the average particle diameter of the first and second conjugated diene-based polymers can be measured using a dynamic light scattering method, and specifically, measured using Nicomp 380 equipment (product name, manufacturer: PSS). You can.
  • the average particle diameter may mean an arithmetic average particle size in the particle size distribution measured by the dynamic light scattering method, that is, the average particle size of the scattering intensity.
  • the viscosity of the plasticizer can be measured using Brookfield under the following conditions.
  • the graft ratio is 1 g of the first copolymer powder, the 2nd copolymer powder or the thermoplastic resin composition dissolved in 50 g of acetone while stirring for 24 hours, and then centrifuged (trade name: SUPRA 30 K, manufacturer: Hanil Science Industrial) And supernatant and sediment were separated by centrifugation for 4 hours under conditions of 16,000 rpm and -10 ° C, and the precipitate was dried for 12 hours with a hot air dryer at 50 ° C, and then the weight of the dried product was measured.
  • SUPRA 30 K manufacturer: Hanil Science Industrial
  • Graft ratio (%) ⁇ [(Weight of dried product)-(Weight of conjugated diene polymer)] / (Weight of conjugated diene polymer) ⁇ ⁇ 100
  • Weight of the conjugated diene-based polymer solid content weight of the first and second conjugated diene-based polymers introduced in the preparation of the first copolymer, the second copolymer, or the thermoplastic resin composition; Alternatively, the solid content weight of the first and second conjugated diene polymers measured by analyzing the first copolymer, the second copolymer, or the thermoplastic resin composition by infrared spectroscopy
  • the weight average molecular weight of the shells of the first and second copolymers is a copolymer comprising an alkyl (meth) acrylate-based monomer unit grafted to a conjugated diene-based polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit. It may mean the weight average molecular weight of the coalescence.
  • the weight average molecular weight of the shells of the first and second copolymers is dissolved in a tetrahydrofuran (THF) solution in a concentration of 1% by weight of the dried product described in the graft rate measurement method, filtered through a 1 ⁇ m filter, Gel permeation chromatography can be used to measure relative values to standard polystyrene (PS) samples.
  • THF tetrahydrofuran
  • the weight average molecular weight of the third copolymer is measured using tetrahydrofuran (THF) as the eluent, and measured relative to the standard PS (standard polystyrene) sample using gel permeation chromatography (GPC, waters breeze). can do.
  • THF tetrahydrofuran
  • PS standard polystyrene
  • Transparency in the present invention can be measured according to ASTM 1003.
  • the impact strength can be measured under 1/4 inch condition according to ASTM D256.
  • the flow index can be measured according to ASTM D1238, under 220 ° C and 10 kg conditions.
  • thermoplastic resin composition includes A-1) a first conjugated diene polymer, an alkyl (meth) acrylate monomer unit, and an aromatic vinyl monomer unit, and the first conjugated diene polymer is A first copolymer having an average particle diameter of 0.05 to 0.2 ⁇ m; A-2) A second conjugated diene-based polymer, an alkyl (meth) acrylate-based monomer unit, and an aromatic vinyl-based monomer unit, wherein the second conjugated diene-based polymer has a second copolymer having an average particle diameter of 0.23 to 0.5 ⁇ m.
  • thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
  • the first copolymer is a graft copolymer, and includes a first conjugated diene polymer, an alkyl (meth) acrylate monomer unit, and an aromatic vinyl monomer unit.
  • the first copolymer may provide excellent transparency and impact resistance to the thermoplastic resin composition in synergy with the second copolymer, and may particularly impart remarkably excellent transparency.
  • the first conjugated diene-based polymer may have an average particle size of 0.05 to 0.2 ⁇ m, and preferably 0.07 to 0.18 ⁇ m. If it is less than the above-mentioned range, excellent impact resistance cannot be achieved, and if it exceeds the above-described range, excellent transparency cannot be achieved.
  • the first conjugated diene-based polymer is prepared by polymerizing a conjugated diene-based monomer, or a conjugated diene-based monomer and a comonomer copolymerizable with the conjugated diene-based monomer, and may have a structure in which double bonds and single bonds are arranged over one another. have.
  • the first conjugated diene-based polymer may include a conjugated diene-based polymer modified by graft polymerization of an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer on the conjugated diene-based polymer.
  • the conjugated diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, piperylene, dicyclopentadiene, ethylidene noborene, and vinyl noborene, of which 1,3-butadiene Or ethylidene novolene may be preferred.
  • the conjugated diene-based monomer and the comonomer copolymerizable may be at least one selected from the group consisting of acrylonitrile, ethylene and propylene.
  • the first conjugated diene-based polymer may include polybutadiene; A copolymer comprising 1,3-butadiene units and acrylonitrile units; And it may be at least one selected from the group consisting of a copolymer comprising an ethylidene novolene unit, an ethylene unit and a propylene unit, of which polybutadiene is preferred.
  • the first conjugated diene-based polymer may be included in 35 to 65% by weight or 40 to 60% by weight relative to the total weight of the first copolymer, and is preferably included in 40 to 60% by weight. If the above-mentioned range is satisfied, the transparency and impact resistance of the first copolymer can be further improved.
  • the alkyl (meth) acrylate-based monomer unit may impart excellent transparency to the first copolymer.
  • the alkyl (meth) acrylate monomer units are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, and la. It may be a unit derived from one or more selected from the group consisting of uryl (meth) acrylates, of which units derived from methyl methacrylate are preferred.
  • the alkyl (meth) acrylate-based monomer unit may be included in an amount of 20 to 50% by weight or 25 to 45% by weight based on the total weight of the first copolymer, and preferably 25 to 45% by weight. Do. If the above-described range is satisfied, the transparency of the first copolymer can be further improved.
  • the aromatic vinyl-based monomer unit may impart processability, rigidity, and mechanical properties of the first copolymer.
  • the aromatic vinyl monomer unit may be a unit derived from one or more selected from the group consisting of styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, and p-methyl styrene, of which units derived from styrene are preferred. .
  • the aromatic vinyl-based monomer unit may be included in 7 to 30% by weight or 10 to 25% by weight relative to the total weight of the first copolymer, and it is preferably included in 10 to 25% by weight. If the above-described range is satisfied, the processability, rigidity and mechanical properties of the first copolymer can be further improved.
  • the first copolymer may further include a vinyl cyanide monomer unit in order to improve chemical resistance.
  • the vinyl cyan monomer unit may be a unit derived from one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and ⁇ -chloroacrylonitrile, from which acrylonitrile Derived units are preferred.
  • the vinyl cyan monomer unit may be included in 0.5 to 10% by weight or 1 to 7% by weight based on the total weight of the first copolymer, and is preferably included in 1 to 7% by weight. If the above-described range is satisfied, chemical resistance can be further improved without yellowing in the first copolymer. In addition, the polymerization stability of the first copolymer may be suppressed to suppress the formation of coagulum, thereby improving the polymerization stability.
  • the first copolymer may have a graft ratio of 40 to 80%, more preferably 45 to 70%, and most preferably 50 to 60%.
  • a graft ratio of 40 to 80%, more preferably 45 to 70%, and most preferably 50 to 60%.
  • the transparency of the first copolymer may be determined by a difference between the refractive index of the first conjugated diene-based polymer and the refractive index of the shell including alkyl (meth) acrylate-based monomer units and aromatic vinyl-based monomer units. That is, in order for the first copolymer to have excellent transparency, a difference between the refractive index of the first conjugated diene polymer and the refractive index of the shell may be 0.01 or less, and it is preferable that there is no difference in refractive index.
  • the first copolymer to the third copolymer may have a difference in refractive index of 0.01 or less, respectively.
  • the difference between the refractive index of the first copolymer and the second copolymer is 0.01 or less
  • the difference between the refractive index of the first copolymer and the third copolymer is 0.01 or less
  • the second copolymer and the third copolymer The coalescence may have a difference in refractive index of 0.01 or less.
  • the first copolymer may have a refractive index of 1.5 to 1.525 or 1.51 to 1.52, of which 1.51 to 1.52 is preferred. If the above-mentioned range is satisfied, the transparency of the thermoplastic resin composition can be further improved by synergy with the second and third copolymers, which will be described later.
  • the first copolymer may have a weight average molecular weight of shell of 50,000 to 200,000 g / mol or 60,000 to 150,000 g / mol, of which 60,000 to 150,000 g / mol is preferred. If the above-mentioned range is satisfied, fluidity and impact resistance can be further improved.
  • the first copolymer may be included in 5 to 40% by weight or 10 to 35% by weight based on the total weight of the thermoplastic resin composition, and is preferably included in 10 to 35% by weight. When the above-described range is satisfied, transparency of the thermoplastic resin composition may be improved.
  • the first copolymer may be prepared by emulsion polymerization or bulk polymerization of an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer on a first conjugated diene-based polymer, of which the first copolymer has excellent transparency and impact resistance. It is preferable to prepare by emulsion polymerization so that it can be implemented.
  • the second copolymer is a graft copolymer, and includes a second conjugated diene polymer, an alkyl (meth) acrylate monomer unit, and an aromatic vinyl monomer unit.
  • the second copolymer may impart excellent impact resistance and transparency to the thermoplastic resin composition, and may particularly impart remarkably excellent impact resistance.
  • the second conjugated diene-based polymer may have an average particle diameter of 0.23 to 0.5 ⁇ m, and preferably 0.25 to 0.48 ⁇ m. If it is less than the above-mentioned range, excellent impact resistance cannot be achieved, and if it exceeds the above-described range, excellent transparency cannot be achieved.
  • the second conjugated diene-based polymer may be included in an amount of 35 to 65% by weight or 40 to 60% by weight, and preferably 40 to 60% by weight, based on the total weight of the second copolymer. If the above-mentioned range is satisfied, the impact resistance and transparency of the second copolymer can be further improved.
  • the description of the second conjugated diene-based polymer is as described above in the description of the first conjugated diene-based polymer.
  • the alkyl (meth) acrylate-based monomer unit may impart excellent transparency to the second copolymer.
  • alkyl (meth) acrylate-based monomer unit The type of the alkyl (meth) acrylate-based monomer unit is as described above.
  • the alkyl (meth) acrylate-based monomer unit may be included in an amount of 20 to 50% by weight or 25 to 45% by weight based on the total weight of the second copolymer, and preferably 25 to 45% by weight. Do. If the above-mentioned range is satisfied, the transparency of the second copolymer can be further improved.
  • the aromatic vinyl-based monomer unit may impart processability, rigidity, and mechanical properties of the second copolymer.
  • the types of the aromatic vinyl monomer units are as described above.
  • the aromatic vinyl-based monomer unit may be included in 7 to 30% by weight or 10 to 25% by weight relative to the total weight of the second copolymer, and it is preferably included in 10 to 25% by weight. If the above-described range is satisfied, the processability, rigidity and mechanical properties of the second copolymer can be further improved.
  • the second copolymer may further include a vinyl cyanide monomer unit in order to improve chemical resistance.
  • the type of the vinyl cyan monomer unit is as described above.
  • the vinyl cyan monomer unit may be included in 0.5 to 10% by weight or 1 to 7% by weight based on the total weight of the second copolymer, and is preferably included in 1 to 7% by weight. If the above-mentioned range is satisfied, chemical resistance can be further improved without yellowing in the second copolymer. In addition, the polymerization stability of the second copolymer may be suppressed to suppress the formation of coagulum, thereby improving the polymerization stability.
  • the second copolymer may be 35 to 70%, more preferably 38 to 60%, and most preferably 40 to 50%.
  • transparency of the thermoplastic resin composition may be improved. If the graft ratio is less than the above-described range, even if the refractive indexes of the first to third copolymers coincide, the transparency of the thermoplastic resin composition may be lowered. If it exceeds the above-described range, the impact strength may be lowered.
  • the transparency of the second copolymer includes the refractive index of the second conjugated diene-based polymer and the alkyl (meth) acrylate-based monomer unit and aromatic vinyl-based monomer unit, as described in the description of the first copolymer.
  • the second copolymer may have a refractive index of 1.5 to 1.525 or 1.51 to 1.52, of which 1.51 to 1.52 is preferred.
  • the transparency of the thermoplastic resin composition can be further improved by synergistically working with the first and third copolymers.
  • the second copolymer may have a weight average molecular weight of shell of 50,000 to 200,000 g / mol or 70,000 to 150,000 g / mol, of which 70,000 to 150,000 g / mol is preferred. If the above-mentioned range is satisfied, fluidity and impact resistance can be further improved.
  • the second copolymer based on the total weight of the thermoplastic resin composition, may be included in 10 to 40% by weight or 13 to 35% by weight, preferably 13 to 35% by weight. If the above-mentioned range is satisfied, impact resistance of the thermoplastic resin composition may be further improved.
  • the second copolymer may be prepared by emulsion polymerization or bulk polymerization of an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer on a second conjugated diene-based polymer, of which the second copolymer has excellent impact resistance and transparency. It is preferable to prepare by emulsion polymerization so that it can be realized.
  • the third copolymer is a matrix copolymer, and includes an alkyl (meth) acrylate monomer unit and a vinyl cyan monomer unit.
  • the third copolymer provides excellent transparency and processability to the thermoplastic resin composition.
  • the third copolymer may include the alkyl (meth) acrylate-based monomer unit and the aromatic vinyl-based monomer unit in a weight ratio of 30:70 to 80:20 or 40:60 to 75:25, of which 40: It is preferred to include in a weight ratio of 60 to 75:25. If the above-described range is satisfied, transparency and processability of the thermoplastic resin composition can be further improved.
  • alkyl (meth) acrylate-based monomer units The types of the alkyl (meth) acrylate-based monomer units and the types of aromatic vinyl-based monomer units are as described above.
  • the third copolymer may further include a vinyl cyanide monomer unit in order to improve chemical resistance.
  • the type of the vinyl cyan monomer unit is as described above.
  • the third copolymer further comprises a vinyl cyan-based monomer unit
  • the third copolymer is 60 to 80% by weight of the alkyl (meth) acrylate monomer unit relative to the total weight of the third copolymer; 15 to 35% by weight of the aromatic vinyl monomer unit; And 0.5 to 10% by weight of the vinyl cyan monomer unit, preferably 65 to 75% by weight of the alkyl (meth) acrylate monomer unit; 20 to 30% by weight of the aromatic vinyl monomer unit; And 1 to 10% by weight of the vinyl cyan monomer unit. If the above-described range is satisfied, chemical resistance can be further improved without causing yellowing in the third copolymer.
  • a difference in refractive index between each of the first copolymer and the second copolymer may be 0.01 or less, and it is preferable that there is no difference in refractive index between them.
  • the third copolymer may have a refractive index of 1.5 to 1.525 or 1.51 to 1.52, of which 1.5 to 1.52 is preferred. If the above-mentioned range is satisfied, the transparency of the thermoplastic resin composition can be further improved by synergy with the first and second copolymers.
  • the third copolymer may have a weight average molecular weight of 50,000 to 200,000 g / mol or 60,000 to 150,000 g / mol, of which 60,000 to 150,000 g / mol is preferred. If the above-described range is satisfied, fluidity and impact resistance may be more excellent.
  • the third copolymer based on the total weight of the thermoplastic resin composition, may be included in 20 to 75% by weight or 30 to 70% by weight, preferably 30 to 70% by weight. When the above-described range is satisfied, transparency and processability of the thermoplastic resin composition may be further improved.
  • the third copolymer may be prepared by suspension polymerization or bulk polymerization of an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer, and among them, a bulk polymerization capable of manufacturing a copolymer with high purity and cost reduction, In particular, it is preferable to manufacture by continuous bulk polymerization.
  • the plasticizer has a viscosity of 700 to 10,000 cP, and the plasticizer may impart excellent processability to the thermoplastic resin composition.
  • the plasticizer may have a viscosity of preferably 1,000 to 90,000 cP, more preferably 1,200 to 5,000 cP. If it is less than the above-mentioned range, the migration phenomenon of the plasticizer occurs in the thermoplastic resin composition. In addition, gas and mold deposits may occur during injection molding. When the above-mentioned range is exceeded, the workability of the thermoplastic resin composition decreases.
  • the plasticizer may be included in an amount of 0.3 to 5% by weight, preferably 0.5 to 4% by weight, and more preferably 1 to 4% by weight, based on the total weight of the thermoplastic resin composition.
  • the above-described range is satisfied, transparency and processability of the thermoplastic resin composition can be further improved, and the migration phenomenon of the plasticizer can be prevented.
  • transparency and processability of the thermoplastic resin composition deteriorate.
  • the transparency and impact strength of the thermoplastic resin composition is lowered. In addition, the phenomenon of plasticizer migration occurs.
  • the plasticizer may have a refractive index of 1.45 or more, 1.45 to 1.6 or 1.45 to 1.52, of which 1.45 to 1.52 is preferred. When the above-described conditions are satisfied, the transparency of the manufactured thermoplastic resin molded article may be more excellent.
  • the plasticizer may include an aliphatic dicarboxylic acid-based monomer unit and an aliphatic dihydroxy-based monomer unit.
  • the aliphatic dicarboxylic acid-based monomer unit may be a unit derived from one or more selected from the group consisting of adipic acid, succinic acid and glutaric acid, and among these, a unit derived from adipic acid is preferred.
  • the aliphatic dihydroxy-based monomer unit is 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1, It may be a unit derived from one or more selected from the group consisting of 6-hexanediol, 1,4-hexanediol, 2-2-dimethyl-1,3-propanediol, of which 1,3-butanediol, 1 Preferred is a unit derived from one or more selected from the group consisting of, 2-propanediol, and 2-2-dimethyl-1,3-propanediol.
  • the plasticizer may further include an aliphatic ester-based monomer unit and an acetate-based monomer unit, and the aliphatic ester-based monomer unit is derived from at least one selected from the group consisting of 2-ethylhexyl ester, octyl ester, and isononyl ester. May be a unit.
  • the acetate-based monomer unit may be a unit derived from acetate.
  • the plasticizer is polydi (2-ethylhexyl) glycol adipate (CAS NO. 73018-26-5); 2,2'-methylenebis [6- (2H-benzotrizol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (CAS NO. 103597-45-1); Hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, isononyl ester (Hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2 -propanediol, isononyl ester, CAS NO.
  • Hexanedioic acid polymer with 1,2-propanediol, n-octyl ester, CAS NO. 82904-80-1; And Hexanedioic acid, polymer with 1,2-propanediol, acetate (Hexanedioic acid, polymer with 1,2-propanediol, acetate, CAS NO.
  • 55799-38-7) may be one or more selected from the group consisting of, Among them, polydi (2-ethylhexyl) glycol adipate; 2,2'-methylenebis [6- (2H-benzotrizol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol]; And hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, and isononyl ester.
  • SONGCIZER TM P-2600 (trade name, manufacturer: Songwon Industry)
  • SONGCIZER TM P-3600 (trade name, manufacturer: Songwon Industry)
  • Palamoll ® 632 (trade name, manufacturer: BASF)
  • Palamoll ® 638 Trade name, manufacturer: BASF
  • Palamoll ® 652 (trade name, manufacturer: BASF)
  • Admex TM 760 Polymeric Plasticizer (trade name, manufacturer: EASTMAN)
  • EDENOL ® 1225 (trade name, manufacturer: EMERYOLECHEMICALS).
  • SONGCIZER TM P-2600 (trade name, manufacturer: Songwon Industries), Palamoll ® 638 (trade name, manufacturer: BASF), Palamoll ® 652 (trade name, manufacturer: BASF), and EDENOL ® 1225 (trade name, Manufacturer: EMERYOLECHEMICALS) is preferably one or more selected from the group consisting of.
  • the plasticizer is not a phthalate-based plasticizer that causes environmental problems.
  • thermoplastic resin composition in the total weight of the thermoplastic resin composition, the first conjugated diene-based polymer 3 to 20% by weight; 3 to 20% by weight of the second conjugated diene-based polymer; 45 to 65% by weight of the alkyl (meth) acrylate monomer unit; 10 to 30% by weight of the aromatic vinyl monomer unit; And 0.3 to 5% by weight of the plasticizer, preferably 5 to 15% by weight of the first conjugated diene-based polymer; 5 to 15% by weight of the second conjugated diene-based polymer; 50 to 65% by weight of the alkyl (meth) acrylate monomer unit; 15 to 25% by weight of the aromatic vinyl monomer unit; And 0.5 to 4% by weight of the plasticizer.
  • the above-described range is satisfied, transparency, processability, and impact resistance of the thermoplastic resin composition may be further improved.
  • thermoplastic resin composition according to an embodiment of the present invention further comprises a vinyl cyanide monomer unit
  • it may include 0.5 to 10% by weight or 1 to 7% by weight relative to the total weight of the thermoplastic resin composition, It is preferable to include 1 to 7% by weight.
  • thermoplastic resin composition according to an embodiment of the present invention has a graft ratio of 35 to 65% or 40 to 60%, and preferably 40 to 60%. When the above-described range is satisfied, transparency of the thermoplastic resin composition may be improved.
  • thermoplastic resin molded article according to another embodiment of the present invention is made of a thermoplastic resin composition according to an embodiment of the present invention, and the impact-reinforced region comprising the first conjugated diene-based polymer and the second conjugated diene-based polymer;
  • the difference in refractive index between the matrix region including the alkyl (meth) acrylate-based monomer unit and the aromatic vinyl-based monomer unit is 0.01 or less.
  • the transparency of the thermoplastic resin molded article can be further improved.
  • the thermoplastic resin molded article may have a haze of 1.3 or less, an impact strength of 7 kg.cm/cm or more, a transparency of 1.2 or less, and an impact strength of 9 kg.cm/cm or more. When the above conditions are satisfied, the transparency and impact resistance of the thermoplastic resin molded article may be further improved.
  • Polybutadiene latex (polymerization method: emulsion polymerization, gel content: 90%, average particle diameter: 0.12 ⁇ m) 50 parts by weight, 50 parts by weight of ion-exchanged water, 8.8 parts by weight of methyl methacrylate, 3 parts by weight of styrene, acrylonitrile 0.8 parts by weight, 0.1 parts by weight of divinylbenzene as a crosslinking agent, 0.2 parts by weight of cumene hydroperoxide as an initiator, 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzene sulfonate) as an emulsifier, mixed for 5 hours, and then methyl 26.2 parts by weight of methacrylate, 9 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of ethylene
  • the temperature was raised to 80 ° C, aged for 1 hour, and polymerization was terminated to obtain a graft copolymer latex.
  • 2 parts by weight of magnesium sulfate was added to the graft copolymer latex as a coagulant to agglomerate, followed by dehydration and drying to obtain a graft copolymer powder.
  • the obtained graft copolymer powder had a refractive index of 1.516 and a graft ratio of 55%.
  • Polybutadiene latex (polymerization method: emulsion polymerization, gel content: 70%, average particle size: 0.3 ⁇ m) 50 parts by weight, 50 parts by weight of ion-exchanged water, 8.8 parts by weight of methyl methacrylate, 3 parts by weight of styrene, acrylonitrile 0.8 parts by weight, 0.1 parts by weight of divinylbenzene as a crosslinking agent, 0.2 parts by weight of cumene hydroperoxide as an initiator, 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzene sulfonate) as an emulsifier, and mixed for 3 hours, 26.2 parts by weight of methyl methacrylate, 9 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of oxidation
  • the temperature was raised to 80 ° C, aged for 1 hour, and polymerization was terminated to obtain a graft copolymer latex.
  • 2 parts by weight of magnesium sulfate was added to the graft copolymer latex as a coagulant to agglomerate, followed by dehydration and drying to obtain a graft copolymer powder.
  • the obtained graft copolymer powder had a refractive index of 1.516 and a graft ratio of 45%.
  • Polybutadiene latex (polymerization method: emulsion polymerization, gel content: 70%, average particle diameter: 0.3 ⁇ m) 50 parts by weight, 50 parts by weight of ion-exchanged water, 7.5 parts by weight of methyl methacrylate, 4.8 parts by weight of styrene, acrylonitrile 0.8 parts by weight, 0.1 parts by weight of divinylbenzene as a crosslinking agent, 0.2 parts by weight of cumene hydroperoxide as an initiator, 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzene sulfonate) as an emulsifier, and mixed for 3 hours, 22.3 parts by weight of methyl methacrylate, 14.4 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of
  • graft copolymer powder had a refractive index of 1.53 and a graft ratio of 47%.
  • the polymerization solution discharged from the reaction tank was heated in a preliminary heating tank, unreacted monomer was volatilized in a volatilization tank, and the polymer temperature was maintained at 210 ° C to obtain a pelletized MSAN copolymer using a polymer transfer pump extrusion processor.
  • the prepared MSAN copolymer had a refractive index of 1.516.
  • thermoplastic resin composition A graft copolymer, a matrix copolymer and a plasticizer were mixed at the contents shown in the table below to prepare a thermoplastic resin composition.
  • antioxidant trade name: Irganox 1010, manufacturer: BASF
  • the physical properties of the pellets were measured in the following manner, and are listed in the following table.
  • Notched Izod Impact Strength (1/4 INCH, kg ⁇ cm / cm): Notched Izod impact strength was measured at 23 ° C. according to ASTM245 D256.
  • C-3 EDENOL ® 1225 (brand name, manufacturer: EMERYOLECHEMICALS, viscosity: 1,200 cP, refractive index: 1.463)
  • C-4 Palamoll ® 638 (trade name, manufacturer: BASF, viscosity: 8,000 cP, refractive index: 1.468, substance name: hexanedioic acid, polymer with 1,2-propanediol, n-octyl ester, CAS NO. 82904-80-1)
  • Examples 1 to 5 containing a plasticizer having a viscosity of 2,200 cP at 0.3 to 4 wt% had a high flow index and low haze, so that processability and transparency were improved.
  • Comparative Example 1 without plasticizer has a low flow index and high haze compared to Examples 1 to 5, so that the processability and You can see that the transparency decreases.
  • Examples 6 to 10 including plasticizers having a viscosity of 2,200 cP, 2,000 cP, 1,200 cP, and 8,000 cP, respectively, implement excellent flow index, haze, impact strength, and performance.
  • Comparative Example 4 including a plasticizer having a viscosity of 60 cP and Comparative Example 5 containing a plasticizer having a viscosity of 150 cP have high haze and deteriorate transparency.
  • Comparative Example 6 by containing the graft copolymer having an average particle diameter of polybutadiene of 0.12 ⁇ m in an excessive amount compared to Comparative Example 1, haze was lowered and excellent transparency could be realized. However, since it does not contain a plasticizer, it can be confirmed that the flow index is lowered and workability is significantly lowered.
  • Comparative Example 8 which does not contain a plasticizer and has an average particle diameter of polybutadiene of 0.3 ⁇ m and a refractive index of 1.53
  • Comparative Example 8 is an excess of a graft copolymer having an average particle diameter of polybutadiene of 0.12 ⁇ m. By including, it was possible to lower haze, but it was difficult to realize excellent transparency. In addition, since it does not contain a plasticizer, it was confirmed that the flow index was lowered and the workability was significantly reduced.

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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne une composition de résine thermoplastique dont la transparence, la résistance au choc et la fluidité sont excellentes, et qui comprend : A-1) un premier copolymère comprenant un premier polymère de diène conjugué ayant une granulométrie moyenne de 0,05 à 0,2 µm, un motif (méth)acrylate d'alkyle monomère et un motif monomère vinylaromatique ; A-2) un deuxième copolymère comprenant un second polymère de diène conjugué ayant une granulométrie moyenne de 0,23 à 0,5 µm, un motif (méth)acrylate d'alkyle monomère et un motif monomère vinylaromatique ; B) un troisième copolymère comprenant un motif (méth)acrylate d'alkyle monomère et un motif monomère vinylaromatique ; C) 0,3 à 5 % en poids d'un plastifiant ayant une viscosité de 700 à 10 000 cP.
PCT/KR2019/011449 2018-09-05 2019-09-05 Composition de résine thermoplastique Ceased WO2020050639A1 (fr)

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CN201980026447.7A CN112020537B (zh) 2018-09-05 2019-09-05 热塑性树脂组合物
EP19856706.7A EP3848414B1 (fr) 2018-09-05 2019-09-05 Composition de résine thermoplastique
US17/047,374 US11299615B2 (en) 2018-09-05 2019-09-05 Thermoplastic resin composition
JP2020556909A JP7118462B2 (ja) 2018-09-05 2019-09-05 熱可塑性樹脂組成物

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Cited By (1)

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US20210355313A1 (en) * 2019-06-13 2021-11-18 Lg Chem, Ltd. Thermoplastic resin composition

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US11898029B2 (en) * 2019-06-13 2024-02-13 Lg Chem, Ltd. Thermoplastic resin composition

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