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WO2014088153A1 - Copolymère (métha)acrylique et résine thermoplastique en contenant - Google Patents

Copolymère (métha)acrylique et résine thermoplastique en contenant Download PDF

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Publication number
WO2014088153A1
WO2014088153A1 PCT/KR2013/000736 KR2013000736W WO2014088153A1 WO 2014088153 A1 WO2014088153 A1 WO 2014088153A1 KR 2013000736 W KR2013000736 W KR 2013000736W WO 2014088153 A1 WO2014088153 A1 WO 2014088153A1
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WIPO (PCT)
Prior art keywords
meth
acrylic
monomer
group
acrylic copolymer
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
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PCT/KR2013/000736
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English (en)
Korean (ko)
Inventor
장주현
정진화
강용희
구자관
권기혜
김만석
김일진
박광수
김보은
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Cheil Industries Inc
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Cheil Industries Inc
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Priority claimed from KR1020120142296A external-priority patent/KR20140074086A/ko
Priority claimed from KR1020120142297A external-priority patent/KR20140074087A/ko
Application filed by Cheil Industries Inc filed Critical Cheil Industries Inc
Publication of WO2014088153A1 publication Critical patent/WO2014088153A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate

Definitions

  • the present invention relates to a (meth) acrylic copolymer and a thermoplastic resin comprising the same. More specifically, the present invention introduces a high refractive index (meth) acrylic monomer and a high refractive index phosphorus (meth) acrylic monomer to improve refractive index and have a high refractive index (meth) acrylic air having flame retardancy, transparency, scratch resistance, and environmental friendliness. It relates to a thermoplastic resin having excellent flame resistance, heat resistance, scratch resistance and eco-friendliness, including a copolymer and a (meth) acrylic copolymer and a polycarbonate resin.
  • Thermoplastic resins have a lower specific gravity than glass or metal and have excellent physical properties such as formability and impact resistance. Recently, due to the trend of low cost, large size, and light weight of electric and electronic products, plastic products using thermoplastic resins are rapidly replacing the areas where glass or metal was used, and are expanding the use area from electric and electronic products to automobile parts. Accordingly, the function of the exterior and the performance of the appearance have become important, and in particular, the demand for transparent resins is increasing due to the high thickness of electrical and electronic products and the change in design concept. Accordingly, there is an increasing demand for a functional transparent material that provides functionality such as scratch resistance and flame retardancy to existing transparent resins.
  • Polycarbonate resin is very excellent in mechanical strength and flame retardancy, excellent transparency and weather resistance, very good impact resistance, thermal stability, etc., but has a disadvantage of very poor scratch resistance.
  • PMMA polymethyl methacrylate
  • An object of the present invention is to provide a (meth) acrylic copolymer having high refractive index and excellent flame retardancy.
  • Another object of the present invention is to provide an environmentally friendly flame retardant (meth) acrylic copolymer having excellent transparency, scratch resistance and impact resistance.
  • Still another object of the present invention is to provide a thermoplastic resin excellent in flame retardancy and scratch resistance.
  • Still another object of the present invention is to provide an environmentally friendly flame retardant scratch resistant thermoplastic resin having excellent transparency and impact resistance.
  • the (meth) acrylic copolymer contains a phosphorus containing heterocyclic group and a biphenyl group.
  • the (meth) acrylic copolymer may include (A) a phosphorus-based (meth) acrylic monomer including a phosphorus-containing heterocyclic group; (B) a biphenyl group-containing (meth) acrylic monomer having a refractive index of about 1.580 to about 1.700; And (C) a monomer mixture comprising unsaturated monomers.
  • the (meth) acrylic copolymer is about 1 to about 50 wt% of the phosphorus (meth) acrylic monomer (A), about 1 to about 30 wt% of the biphenyl group-containing (meth) acrylic monomer (B) and the And about 20 to about 98 weight percent of unsaturated monomers (C).
  • the phosphorus (meth) acrylic monomer (A) may be represented by the following Chemical Formula 1:
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a hydrocarbon group of 1 to 20 carbon atoms
  • R 3 and R 4 are each independently a substituted or unsubstituted cyclic hydrocarbon group of 6 to 20 carbon atoms
  • m is an integer of 1-10
  • n is an integer of 0-5.
  • the biphenyl group-containing (meth) acrylic monomer (B) may be represented by the following Chemical Formula 2:
  • R 5 is a hydrogen atom or a methyl group
  • R 6 is a substituted or unsubstituted biphenyl group or a substituted or unsubstituted terphenyl group
  • x is an integer of 0 to 10.
  • the unsaturated monomer (C) is alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids including (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile; Allyl glycidyl ether; Glycidyl methacrylate; And styrene-based monomers.
  • the monomer mixture may further include an alicyclic or aromatic (meth) acrylic monomer having a (D) refractive index of about 1.490 to about 1.579.
  • an alicyclic or aromatic (meth) acrylic monomer having a (D) refractive index of about 1.490 to about 1.579.
  • the alicyclic or aromatic (meth) acrylic monomer (D) may be represented by the following Formula 3:
  • R 7 is a hydrogen atom or a methyl group
  • R 8 is a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms
  • X is an oxygen atom or Is a sulfur atom
  • y is an integer from 0 to 10
  • Z is 0 or 1;
  • the alicyclic or aromatic (meth) acrylic monomer (D) may comprise about 0 to about 30% by weight of the total (meth) acrylic copolymer.
  • the (meth) acrylic copolymer may have a weight average molecular weight of about 5,000 to about 500,000 g / mol.
  • the (meth) acrylic copolymer has a refractive index of about 1.510 to about 1.590 at a thickness of 2.5 mm, a flame retardancy measured according to UL94 of 3.2 mm thick, and is at least V2, and a specimen having a thickness of 2.5 mm ASTM D1003.
  • the total light transmittance measured according to the present invention may be about 85% or more.
  • the (meth) acrylic copolymer is a flame retardant, surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, lubricant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, inorganic additive, electrostatic It may further comprise one or more of inhibitors, pigments and dyes.
  • thermoplastic resin is (A) polycarbonate resin; And (B) the (meth) acrylic copolymer.
  • thermoplastic resin comprising about 50 to about 99% by weight of the polycarbonate resin (A), and about 1 to about 50% by weight of the (meth) acrylic copolymer (B).
  • thermoplastic resin further comprises (C) a rubber-modified vinyl-based graft copolymer resin.
  • the rubber-modified vinyl-based graft copolymer resin (C) has a structure in which a unsaturated monomer is grafted to a rubber core to form a shell, and the unsaturated monomer is an alkyl (meth) acrylate having 1 to 12 carbon atoms and an acid.
  • thermoplastic resin further comprises (D) a phosphorus-based flame retardant.
  • the thermoplastic resin may be a flame retardant, surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, lubricant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, inorganic additive, antistatic agent, pigment And at least one of dyes.
  • the thermoplastic resin has a thickness of 3.2 mm and has a flame retardancy of at least V2 measured according to UL94, and a scratch width of about 180 to about 300 by a Balltype Scratch Profile Test. It is a micrometer and a pencil hardness is 2B-3H, The thermoplastic resin characterized by the above-mentioned.
  • the present invention includes a phosphorus (meth) acrylic monomer containing a phosphorous heterocyclic group, a biphenyl group-containing (meth) acrylic monomer, and the like, and have a high refractive index and excellent flame retardancy, and have transparency and scratch resistance. And an environmentally friendly flame retardant thermoplastic (meth) acrylate copolymer having excellent impact resistance.
  • the present invention comprises a high refractive index (meth) acrylic copolymer and a polycarbonate resin prepared by applying the phosphorus-based (meth) acrylic monomer containing the phosphorus-containing heterocyclic group, excellent flame retardancy, transparency, heat resistance,
  • the invention has the effect of providing a thermoplastic resin having scratch resistance, impact resistance and environmental friendliness.
  • the (meth) acrylate copolymer and the thermoplastic resin are excellent in compatibility with the polycarbonate resin due to the high refractive index, can overcome the problems of transparency and coloring deterioration when blending, and at the same time can impart flame retardancy. It is also useful for various electric and electronic parts or automobile parts.
  • the (meth) acrylate copolymer according to the present invention contains a phosphorus-containing heterocyclic group and a biphenyl group, and in one embodiment, a phosphorus-based (meth) acryl-based compound containing a phosphorus-containing heterocyclic group.
  • a copolymer of a monomer mixture comprising a monomer, a biphenyl group-containing (meth) acrylic monomer having a refractive index of about 1.580 to about 1.700, and an unsaturated monomer.
  • (meth) acryl means that both “acryl” and “methacryl” are possible.
  • (meth) acrylate means that both “acrylate” and “methacrylate” are possible.
  • Phosphorus-based (meth) acrylic monomers containing a phosphorous heterocyclic group used in the present invention have a higher refractive index than methyl methacrylate, for example, may be represented by the following formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a hydrocarbon group having 1 to 20 carbon atoms, for example, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, C6- C20 arylene group, preferably C1-C10 linear, branched or cyclic alkylene group, C6-C10 arylene group, more preferably C1-C4 linear alkylene group.
  • R 3 and R 4 are each independently a substituted or unsubstituted cyclic hydrocarbon group having 6 to 20 carbon atoms, for example, a substituted or unsubstituted C6-C20 cycloalkyl group or an aryl group, preferably substituted or unsubstituted C6-C10 aryl group.
  • m is an integer of 1-10
  • n is an integer of 0-5.
  • n when n is 0, it represents a single bond, and the phosphorus containing heterocyclic group will form a hexagonal ring.
  • hydrocarbon group means a linear, branched or cyclic saturated or unsaturated hydrocarbon group.
  • the hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), hydroxy group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, Carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, alkyl group of C1-C20, alkenyl group of C2-C20, alkynyl group of C2-C20, C1 A substituent of an alkoxy group of C20, an aryl group of C6-C30, an aryloxy group of C6-C30, a cycloalkyl group of C3-C30, a cycl
  • phosphorus-based (meth) acrylic monomer may include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl (meth) acrylate, but are not limited thereto.
  • the refractive index of the phosphorus (meth) acrylic monomer may be, for example, about 1.580 to about 1.700, preferably about 1.590 to about 1.650. Within this range, a (meth) acrylic copolymer having a high refractive index can be obtained.
  • the content of the phosphorus (meth) acrylic monomer is about 1 to about 50% by weight, preferably about 5 to about 40% by weight of the total (meth) acrylic copolymer (monomer mixture). It is possible to obtain an excellent flame retardant (meth) acrylic copolymer without deteriorating heat resistance in the above range.
  • the biphenyl group-containing (meth) acrylic monomer having a refractive index of about 1.580 to about 1.700 used in the present invention has a refractive index of about 1.580 to about 1.700, and is characterized by containing a biphenyl structure.
  • the biphenyl group-containing (meth) acrylic monomer may be represented by, for example, the following Formula 2.
  • R 5 is a hydrogen atom or a methyl group
  • R 6 is a substituted or unsubstituted biphenyl group or a substituted or unsubstituted terphenyl group, for example, an oligobiphenyl group, a metabiphenyl group, a parabiphenyl group, 2 , 6-terphenyl group, alloterphenyl group, metaterphenyl group, or paraterphenyl group.
  • x is an integer of 0-10.
  • biphenyl group-containing (meth) acrylic monomers examples include allobiphenyl methacrylate, metabiphenyl methacrylate, parabiphenyl methacrylate, 2,6-terphenyl methacrylate, alloterphenyl methacrylate, Metaterphenyl methacrylate, paraterphenyl methacrylate, 4- (4-methylphenyl) phenyl methacrylate, 4- (2-methylphenyl) phenyl methacrylate, 2- (4-methylphenyl) phenyl methacrylate, 2- (2-methylphenyl) phenyl methacrylate, 4- (4-ethylphenyl) phenyl methacrylate, 4- (2-ethylphenyl) phenyl methacrylate, 2- (4-ethylphenyl) phenyl methacrylate , 2- (2-ethylphenyl) phenyl methacrylate, and the like, but are not limited thereto. These can be used
  • the content of the biphenyl group-containing (meth) acrylic monomer is about 1 to about 30% by weight, preferably about 5 to about 20% by weight of the total (meth) acrylic copolymer. Within this range, excellent high refractive index, transparency, and heat resistance physical property balance can be obtained, and it is easy to commercialize because of excellent compatibility with polycarbonate resin.
  • the unsaturated monomer used in the present invention is a monomer containing an unsaturated group, for example, alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids including (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile; Allylglycidyl ether; Glycidyl methacrylate; Styrenic monomers, mixtures thereof, and the like. These can be applied individually or in mixture of 2 or more types.
  • alkyl (meth) acrylate having 1 to 8 carbon atoms Unsaturated carboxylic acids including (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile; Allylglycidyl ether; Glycidyl meth
  • Non-limiting examples of the unsaturated monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl Acrylate, acrylic acid, methacrylic acid, maleic anhydride, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, allyl Glycidyl ether, glycidyl methacrylate, styrene, alpha-methylstyrene, etc.
  • an alkyl (meth) acrylate having 1 to 8 carbon atoms Preferably an alkyl (meth) acrylate having 1 to 4 carbon atoms can be used. In this case, better scratch resistance and transparency can be achieved.
  • the unsaturated monomer it is possible to apply a mixture of methacrylate and acrylate.
  • the ratio of methacrylate and acrylate may be about 10: 1 to about 50: 1. It may have better thermal stability and fluidity in the above range.
  • the content of the unsaturated monomer is about 20 to about 98% by weight, preferably about 40 to about 90% by weight of the total (meth) acrylic copolymer. Excellent scratch resistance, flowability, transparency and flame retardant balance of properties can be obtained in the above range.
  • the (meth) acrylic copolymer according to the present invention may further include an alicyclic or aromatic (meth) acrylic monomer having a refractive index of about 1.490 to about 1.579 as one of the monomers.
  • the alicyclic or aromatic (meth) acrylic monomer may be represented by the following formula (3).
  • R 7 is a hydrogen atom or a methyl group
  • R 8 is a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, for example, cyclohex It is a real group, a phenyl group, a methylphenyl group, methyl ethylphenyl group, a methoxyphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group, and a benzylphenyl group.
  • X is an oxygen atom or a sulfur atom
  • y is an integer of 0-10
  • Z is 0 or 1.
  • Non-limiting examples of the alicyclic or aromatic (meth) acrylic monomers include cyclohexyl methacrylate, phenoxy methacrylate, 2-ethylphenoxy methacrylate, benzyl methacrylate, phenyl methacrylate, 2-ethyl Thiophenyl methacrylate, 2-phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) Ethyl methacrylate, 2- (4-cyclohexylphenyl) ethyl methacrylate, 2-
  • the content of the cycloaliphatic or aromatic (meth) acrylic monomer is about 0 to about 30% by weight, preferably about 0 to about 25% by weight, more preferably about 5 to about 20, of the total (meth) acrylic copolymer. Weight percent. Excellent balance of refractive index and heat resistance in the above range can be obtained.
  • (meth) acrylic copolymers according to the present invention if necessary, flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, commercialization Agents may further include one or more additives such as inorganic additives, antistatic agents, pigments and dyes. These additives may be added in the polymerization process, or may be added to the pelletization process (extrusion process, etc.) to be included in the copolymer, but the method and the addition amount thereof are not particularly limited.
  • Non-limiting examples of such antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydrophenyl) propionate, triethylene glycol-bis-3 (3-tertary-butyl-4 -Hydroxy-5-methylphenyl) propionate, 2,6-di-tert-butyl-4-methyl phenol, 2,2'-methylenebis (4-methyl-6-tert-butylbutyl phenol), tri ( 2,4-di-tert-butylphenyl) phosphite, normal-octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, disterylthiol dipropio Nate, lauthiol
  • the (meth) acrylic copolymer of the present invention may be prepared by conventional polymerization methods known in the copolymer production field, for example, bulk polymerization, emulsion polymerization, suspension polymerization, and the like. It may be prepared through a manufacturing method including the step of polymerizing.
  • the polymerization initiator is a radical polymerization initiator
  • the polymerization may be a suspension polymerization in consideration of the refractive index, etc.
  • the suspension polymerization may be carried out in the presence of a suspension stabilizer and a chain transfer agent. That is, a radical polymerization initiator and a chain transfer agent are added to the monomer to prepare a reaction mixture, and the prepared reaction mixture is added to an aqueous solution in which a suspension stabilizer is dissolved to prepare a (meth) acrylic copolymer of the present invention (suspension polymerization). Can be.
  • the additive may be further added.
  • the polymerization initiator may be a conventional radical polymerization initiator known in the polymerization art, for example, octanoyl peroxide, decanyl peroxide, lauroyl peroxide, benzoyl peroxide, monochlorobenzoyl peroxide, dichloro Benzoyl peroxide, p-methylbenzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile, azobis- (2,4-dimethyl) -valeronitrile, and the like, but are not limited thereto. . These can be used individually or in mixture of 2 or more types.
  • the polymerization initiator may be included in an amount of about 0.01 to about 10 parts by weight, preferably about 0.02 to about 5 parts by weight, based on 100 parts by weight of the monomer mixture.
  • the chain transfer agent may be used to control the weight average molecular weight of the (meth) acrylate copolymer and to improve thermal stability.
  • the weight average molecular weight can be controlled by the content of the polymerization initiator contained in the monomer.
  • the end of the chain becomes the second carbon structure. This is stronger in bond strength than the ends of the chain with double bonds produced when no chain transfer agent is used. Therefore, the addition of the chain transfer agent can improve the thermal stability, and eventually improve the optical properties of the (meth) acrylate copolymer.
  • chain transfer agent conventional chain transfer agents known in the polymerization art may be used.
  • chain transfer agent conventional chain transfer agents known in the polymerization art may be used.
  • the amount of the chain transfer agent varies depending on the type, but about 0.01 to about 10 parts by weight, preferably about 0.02 to about 5 parts by weight, based on 100 parts by weight of the monomer mixture may be used. In the above range, it may have excellent heat resistance, prevents the molecular weight of the polymer from being lowered too much and is excellent in mechanical properties.
  • organic suspension stabilizers such as polyalkyl acrylate-acrylic acid, polyolefin-maleic acid, polyvinyl alcohol, cellulose, and inorganic suspension stabilizers such as tricalcium phosphate may be used, but are not limited thereto.
  • suspension stability aid disodium hydrogen phosphate, sodium dihydrogen phosphate, or the like may be used, and sodium sulfate or the like may be added to control solubility characteristics of the water-soluble polymer or monomer.
  • the said polymerization temperature and polymerization time can be adjusted suitably. For example, it may be reacted for about 2 to about 8 hours at a polymerization temperature of about 65 to about 125 ° C, preferably about 70 to about 120 ° C.
  • the (meth) acrylic copolymer of the present invention may have a weight average molecular weight of about 5,000 to about 500,000 g / mol, preferably about 10,000 to about 250,000 g / mol, more preferably about 20,000 to about 200,000. It may have excellent impact resistance and flame resistance in the above range.
  • the (meth) acrylic copolymer may have a refractive index of about 1.510 to about 1.590, preferably about 1.520 to about 1.560 at a thickness of 2.5 mm, and a flame retardancy measured according to the UL94 evaluation method with a specimen of 3.2 mm, at least V2, eg For example, it may be V2 to V0.
  • the (meth) acrylic copolymer may have a total light transmittance of about 85% or more, preferably about 90% or more, measured in accordance with ASTM D1003 as a specimen having a thickness of 2.5 mm.
  • thermoplastic resin according to the present invention comprises a polycarbonate resin and a resin containing a phosphorus-containing heterocyclic group, and in one embodiment, the thermoplastic resin is (A) a polycarbonate resin, and (B) the phosphorus-containing hetero It is characterized by including a (meth) acrylic copolymer containing a cyclic group.
  • thermoplastic resin according to the present invention may further include (C) rubber-modified vinyl-based graft copolymer resin and / or (D) phosphorus-based flame retardant as necessary.
  • thermoplastic resin means both the thermoplastic resin itself, as well as a blend of two or more thermoplastic resins and other additives (thermoplastic resin composition), and the like.
  • the polycarbonate resin (A) used in the present invention can be produced by reacting a dihydric phenol compound and a phosgene in the presence of a molecular weight modifier and a catalyst according to a conventional production method.
  • the polycarbonate resin (A) may be prepared using an ester interchange reaction of a dihydric phenol compound and a carbonate precursor such as diphenyl carbonate.
  • a bisphenol compound may be used as the dihydric phenol compound, and preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) may be used.
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • the bisphenol A may be partially or wholly replaced by another type of dihydric phenol compound.
  • dihydric phenolic compounds examples include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl) cyclo Hexane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Halogenated bisphenols such as sulfoxide, bis (4-hydroxyphenyl) ketone or bis (4-hydroxyphenyl) ether, and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane Can be mentioned.
  • the type of dihydric phenol compound that can be used for the production of the polycarbonate resin (A) is not limited thereto, and the polycarbonate resin may be manufactured using any dihydric phenol compound.
  • the polycarbonate resin (A) may be a homopolymer using one type of dihydric phenol compound, a copolymer using two or more types of dihydric phenol compounds, or a mixture thereof.
  • the polycarbonate resin may have a form such as a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin.
  • the polycarbonate resin (A) included in the thermoplastic resin of the present invention is not limited to a specific form, and any of these linear polycarbonate resins, branched polycarbonate resins, polyester carbonate copolymer resins, and the like can be used.
  • linear polycarbonate resin bisphenol-A polycarbonate resin
  • branched polycarbonate resin polyfunctional aromatic compounds, such as trimellitic anhydride or trimellitic acid, May be prepared by reacting with a dihydric phenol compound and a carbonate precursor.
  • polyester carbonate copolymer resin for example, one produced by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor can be used.
  • conventional linear polycarbonate resins, branched polycarbonate resins or polyestercarbonate copolymer resins can be used without limitation.
  • the polycarbonate resin (A) may be used alone or in combination of two or more kinds having different molecular weights.
  • the content of the polycarbonate resin (A) is about 50 to about 99% by weight, preferably about 55 to about 95% by weight of the resin containing (A) + (B), more preferably about 60 to about 90 wt%. It can have a good balance of mechanical properties and scratch resistance in the above range.
  • the content of the (meth) acrylate copolymer (B) is about 1 to about 50% by weight, preferably about 5 to, of the resin containing (A) + (B). About 45% by weight, more preferably about 10 to about 40% by weight. In the above range, scratch resistance can be sufficiently improved, and impact and mechanical property deterioration can be prevented.
  • the rubber-modified vinyl graft copolymer (C) used in the present invention has a core-shell graft copolymer structure which is a structure in which an unsaturated monomer is grafted to a rubber core structure to form a shell, and thus impacts in a thermoplastic resin. It acts as an adjuvant.
  • the rubber it is preferable to use a polymer prepared by polymerizing one or more rubber monomers of a diene rubber, an acrylate rubber, and a silicone rubber having 4 to 6 carbon atoms, and in terms of structural stability, a silicone rubber is used alone. It is more preferable to use a silicone rubber and an acrylate rubber in combination.
  • acrylate type rubber methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (Meth) acrylate monomers, such as (meth) acrylate, can be used, At this time, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 3- butylene glycol di (meth) acrylate And curing agents such as 1,4-butylene glycol di (meth) acrylate, allyl (meth) acrylate, and triallyl cyanurate.
  • the silicone rubber is prepared from cyclosiloxane, and specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, and tetramethyltetraphenyl. It may be prepared from one or more selected from cyclotetrosiloxane, and octaphenylcyclotetrasiloxane. At this time, curing agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane and tetraethoxysilane can be further used.
  • the rubber may be included in about 50 to about 95 parts by weight, preferably about 60 to about 90 parts by weight, and more preferably about 70 to about 85 parts by weight of the rubber-modified vinyl graft copolymer (C). . It is excellent in compatibility with the resin in the above range, as a result can exhibit an excellent impact reinforcing effect.
  • the average particle diameter of the rubber may be about 0.1 to about 1 ⁇ m, preferably about 0.4 to about 0.9 ⁇ m. It may be more preferable to maintain the impact resistance and colorability balance in the above range.
  • Examples of the unsaturated monomer grafted to the rubber include at least one unsaturated compound of alkyl (meth) acrylate, (meth) acrylate, acid anhydride, and alkyl or phenyl nucleosubstituted maleimide having 1 to 12 carbon atoms. Can be used.
  • alkyl (meth) acrylate may include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and the like, of which methyl methacrylate may be preferably used.
  • Carboxylic anhydrides such as maleic anhydride and itaconic anhydride, can be used as said acid anhydride.
  • the grafted unsaturated monomer is about 5 to about 50 parts by weight, preferably about 10 to about 40 parts by weight, more preferably about 15 to about 30 parts by weight, in the rubber-modified vinyl-based graft copolymer (C). May be included as a wealth. It is excellent in compatibility with the resin in the above range, it can exhibit an excellent impact reinforcing effect.
  • the content of the rubber-modified vinyl graft copolymer resin (C) is about 0 to about 30 parts by weight, preferably about 3 to about 100 parts by weight of the base resin including the (A) + (B). About 20 parts by weight. In the above range, not only the impact reinforcing effect can be obtained, but also the mechanical strength such as tensile strength, flexural strength, flexural modulus, etc. can be improved.
  • Phosphorus-based flame retardant (D) used in the present invention is added to further secure flame retardancy, for example, phosphate (Phosphate), phosphonate (Phosphonate), phosphinate (Phosphinate), phosphine oxide ( Conventional phosphorus-containing flame retardants such as Phosphine Oxide, Phosphene and metal salts thereof can be used without limitation.
  • phosphorus-based flame retardant (D) may be used that represented by the following formula (4).
  • R 9 , R 10 , R 12, and R 13 are each independently an aryl group having 6 to 20 carbon atoms, or a C 1 -C 10 alkyl substituted C 6 -C 20 aryl group, and R 11 Is one derived from dialcohol of resorcinol, hydroquinol, bisphenol-A, or bisphenol-S, and p is an integer from 0 to 10.
  • p is specifically illustrated when 0, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trigylyl phosphate, tri (2,4,6-trimethylphenyl) phosphate, Tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, and the like, and ii) the case where p is 1 is concretely exemplified by resorcinol bis (diphenylphosphate).
  • the phosphorus-based flame retardant (D) may be used represented by the formula (5).
  • R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , and R 23 each independently represent an alkyl group having 1 to 6 carbon atoms. , C 6 -C 20 aryl, C 1 -C 6 alkyl substituted C 6 -C 20 aryl, C 6 -C 20 aralkyl group, C 1 -C 6 alkoxy group, C 6 -C 20 aryloxy group, amino group or hydroxy group A substituent, R 24 is a C6-C30 deoxyaryl group or a C6-C30 deoxyaryl group derivative substituted with an alkyl group, q is a number average polymerization degree, and the average value of q is 0.3 to 3, and k and j are It is an integer of 0-10.
  • the alkoxy group or the aryloxy group of Formula 5 may be substituted with an alkyl group, an aryl group, an amino group,
  • the phosphorous flame retardant (D) may be included in an amount of about 0 to about 20 parts by weight based on 100 parts by weight of the base resin including the (A) + (B), but is not limited thereto.
  • Thermoplastic resins according to the present invention if necessary, flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, electrostatic Additives such as inhibitors, pigments, and dyes may be further included.
  • the additives may be applied alone or by mixing two or more kinds. These additives may be added during the polymerization process of the (meth) acrylic copolymer (B), may be included in the (meth) acrylic copolymer (B) in the thermoplastic resin, and may be added to the usual pelletization process (extrusion process) of the thermoplastic resin.
  • thermoplastic resin It may be included in the thermoplastic resin as a whole, but the method is not particularly limited.
  • the additive may be included in an amount of about 0.001 to about 20 parts by weight based on 100 parts by weight of the resin (A) + (B), but is not limited thereto.
  • Non-limiting examples of such antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydrophenyl) propionate, triethylene glycol-bis-3 (3-tertary-butyl-4 -Hydroxy-5-methylphenyl) propionate, 2,6-di-tert-butyl-4-methyl phenol, 2,2'-methylenebis (4-methyl-6-tert-butylbutyl phenol), tri ( 2,4-di-tert-butylphenyl) phosphite, normal-octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, disterylthiol dipropio Nate, lauthiol
  • Thermoplastic resin of the present invention is a specimen having a thickness of 3.2mm
  • the flame retardancy measured according to UL94 may be V2 or more, for example, V2 to V0
  • the scratch width according to the Balltype Scratch Profile Test. ) May be, for example, about 180 to about 350 ⁇ m
  • pencil hardness may be in the range of 2B to 3H, for example.
  • thermoplastic resin according to the present invention can be produced by a known thermoplastic resin manufacturing method.
  • the components of the present invention and other additives may be simultaneously mixed and then melt-extruded in an extruder to produce pellets, and the pellets may be used to produce plastic injection and compression molded articles.
  • the (meth) acrylic copolymer and the thermoplastic resin according to the present invention may form a molded article.
  • a molding method for manufacturing the molded article extrusion, injection, casting, etc. may be applied, but is not limited thereto.
  • Such molding methods are well known to those skilled in the art.
  • the (meth) acrylic copolymer or the thermoplastic resin and, if necessary, the additives are mixed and then melt-extruded in an extruder to produce pellets, and the injection and compression molded articles are manufactured using the pellets. It can manufacture.
  • 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer 10% by weight, 15% by weight of allobiphenyl methacrylate monomer, 75% by weight of methyl methacrylate monomer 0.5 parts by weight of n-octyl mercaptan was mixed with respect to 100 parts by weight of the monomer mixture and the monomer mixture.
  • a stainless steel high pressure reactor equipped with a stirrer 130 parts by weight of ion-exchanged water, 0.2 parts by weight of polyethylacrylate-methylacrylic acid (weight average molecular weight: 1 million or more), as a suspension stabilizer, based on 100 parts by weight of the monomer mixture.
  • a suspension aid stabilizer As a suspension aid stabilizer, a small amount such as disodium hydrogen phosphate and sodium sulfate was added and stirred. The monomer mixture containing n-octyl mercaptan was added to the aqueous solution in which the suspension stabilizer and the like were dissolved, followed by stirring, and the inside of the reactor was filled with an inert gas such as nitrogen, followed by 3 hours at 70 ° C and 2 hours at 110 ° C. After the polymerization, the reaction was terminated. After the reaction was terminated, the (meth) acrylic copolymer particles were obtained through washing, dehydration and drying. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.
  • Example 1 instead of the monomer mixture of Example 1 above, 30% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 20% by weight of allobiphenyl methacrylate monomer, And a monomer mixture including 50% by weight of methyl methacrylate monomer, and 0.2 parts by weight of n-octyl mercaptan is mixed with respect to 100 parts by weight of the monomer mixture in the same manner as in Example 1 ( Meta) acrylic copolymer particles were obtained. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.
  • Example 1 instead of the monomer mixture of Example 1 above, 30% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 15% by weight of parabiphenyl methacrylate monomer, And a monomer mixture comprising 55% by weight of methyl methacrylate monomer, and 0.3 parts by weight of n-octyl mercaptan is mixed with respect to 100 parts by weight of the monomer mixture in the same manner as in Example 1 above ( Meta) acrylic copolymer particles were obtained. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.
  • n-octyl mercaptan 0.3 (Meta) acrylic copolymer particles were obtained in the same manner as in Example 1 except that the parts by weight were mixed. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 2.
  • Example 2 instead of the monomer mixture of Example 1, using a monomer mixture comprising 20% by weight of the allobiphenyl methacrylate monomer, 77.5% by weight of methyl methacrylate monomer and 2.5% by weight of methyl acrylate monomer, and the monomer mixture 100 (Meta) acrylic copolymer particles were obtained in the same manner as in Example 1, except that 0.3 parts by weight of n-octyl mercaptan was mixed with respect to parts by weight. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 2.
  • Example 2 a monomer mixture comprising 20% by weight of parabiphenyl methacrylate monomer and 80% by weight of methyl methacrylate monomer was used, and based on 100 parts by weight of the monomer mixture, n- (Meta) acrylic copolymer particles were obtained in the same manner as in Example 1, except that 0.5 parts by weight of octyl mercaptan was mixed. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 2.
  • Example 2 instead of the monomer mixture of Example 1, using a monomer mixture comprising 30% by weight phenyl methacrylate monomer, 67.5% by weight methyl methacrylate monomer and 2.5% by weight methyl acrylate monomer, 100 parts by weight of the monomer mixture (Meth) acrylic copolymer particles were obtained in the same manner as in Example 1, except that 0.5 parts by weight of n-octyl mercaptan was mixed. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 2.
  • Refractive index It measured at 20 degreeC using the "DR-A1" refractor made by ATAGO company, and the thickness of the specimen was 2.5 mm.
  • a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer
  • b-1 oxobiphenyl methacrylate monomer
  • b-2 parabiphenyl methacrylate
  • c-1 methyl methacrylate monomer
  • c-2 methyl acrylate monomer
  • c-3 phenyl methacrylate monomer
  • a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer
  • b-1 oxobiphenyl methacrylate monomer
  • b-2 parabiphenyl methacrylate
  • c-1 methyl methacrylate monomer
  • c-2 methyl acrylate monomer
  • c-3 phenyl methacrylate monomer
  • the (meth) acrylic copolymers (Examples 1 to 7) using the phosphorus-based (meth) acrylic monomers containing the phosphorus-containing heterocyclic group of the present invention are excellent in transparency and have a refractive index of 1.5238. It is higher than the above, it can be seen that the flame retardancy is excellent than V2. On the other hand, in Comparative Examples 1 to 4 without using the phosphorus (meth) acrylic monomer, the refractive index is 1.5194 or less, it can be seen that does not have a flame retardancy.
  • PANLITE L-1250WP of TEIJIN, Japan which is a bisphenol-A type linear polycarbonate resin, having a weight average molecular weight of 25,000 g / mol, was used.
  • Resorcinolbis (diphenyl phosphate) was used.
  • L84 of LG MMA a polymethyl methacrylate resin having a weight average molecular weight of 92,000 g / mol, was used.
  • 30 wt% of the phenyl methacrylate monomer having a refractive index of 1.570 was prepared by a conventional suspension polymerization method using 70 wt% of methyl methacrylate monomer, and the weight average molecular weight of the prepared copolymer was 40,000 g / mol.
  • thermoplastic resin The transparency of the thermoplastic resin is evaluated by Haze of the appearance of the injection molded article and the total light transmittance (transmitted light), and the improved compatibility can be evaluated by the flow mark of the appearance.
  • VST Heat resistance
  • MI Flow index
  • Flame retardant A specimen having a thickness of 3.2 mm was prepared and flame retardant was measured by a UL94 vertical test method.
  • Scratch resistance measured by BSP (Ball-type Scratch Profile) test. Scratch lengths of 10 to 20 mm were applied to a L90 mm ⁇ W50 mm ⁇ t2.5 mm specimen surface using a 0.7 mm diameter spherical metal tip with a load of 1000 g and a scratch speed of 75 mm / min. Scratch width ( ⁇ m), which is a measure of scratch resistance, was measured by surface scanning of the applied scratch using Ambios' contact surface profile analyzer (XP-1) with a metal stylus tip of 2 ⁇ m in diameter. At this time, the scratch resistance increases as the measured scratch width decreases.
  • BSP All-type Scratch Profile
  • Pencil hardness After leaving the specimen horizontal and vertical 100mm x 100mm at 23 °C, 50% relative humidity for 48 hours, pencil hardness was measured according to JIS K 5401 standard. The scratch resistance is evaluated as 3B, 2B, B, HB, F, H, 2H, 3H, etc. according to the pencil hardness result. The higher the H value, the better the scratch resistance, and the higher the B value, the scratch resistance. This means that it is degraded.
  • thermoplastic resins (Examples 8 to 16) of the present invention have excellent impact strength and scratch resistance, and are compatible with (Flow mark), compared to the thermoplastic resins of Comparative Examples 5 to 12. It can be seen that transparency and transparency are excellent, and that flame retardancy is excellent at V2 or higher even without including a phosphorus-based flame retardant.

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Abstract

Le copolymère (métha)acrylique de la présente invention contient un groupe hétérocyclique contenant du phosphore et un groupe biphényle. Le copolymère (méth)acrylique de la présente invention est un copolymère à base d'un mélange de monomères comprenant : (A) un monomère (métha)acrylique phosphorique comportant un groupe hétérocyclique contenant du phosphore ; (B) un monomère (métha)acrylique contenant un groupe biphényle et présentant un indice de réfraction variant d'environ 1 580 à environ 1 700 ; et (C) un monomère insaturé. Ledit copolymère (métha)acrylique comprend ledit monomère (métha)acrylique à fort indice de réfraction et ledit monomère (métha)acrylique phosphorique à fort indice de réfraction, ce qui permet une amélioration de l'indice de réfraction et l'obtention de propriétés intéressantes en matière de capacité ignifuge, de transparence, de résistance aux rayures et de respect de l'environnement.
PCT/KR2013/000736 2012-12-07 2013-01-30 Copolymère (métha)acrylique et résine thermoplastique en contenant Ceased WO2014088153A1 (fr)

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KR10-2012-0142297 2012-12-07
KR1020120142296A KR20140074086A (ko) 2012-12-07 2012-12-07 (메타)아크릴계 공중합체, 그 제조방법 및 이를 포함하는 성형품
KR1020120142297A KR20140074087A (ko) 2012-12-07 2012-12-07 열가소성 수지 및 이를 포함하는 성형품
KR10-2012-0142296 2012-12-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116438280A (zh) * 2020-11-20 2023-07-14 株式会社可乐丽 聚合物、阻燃性组合物和聚合物的制造方法

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US3030347A (en) * 1960-04-25 1962-04-17 Rohm & Haas Dialkylphosphonoalkyl acrylate and methacrylate copolymers
JP2001151855A (ja) * 1999-11-25 2001-06-05 Matsushita Electric Works Ltd リン含有ビニルエステルの製造方法及びこのビニルエステルを用いたラジカル重合性樹脂組成物の製造方法
US20070173549A1 (en) * 2004-02-24 2007-07-26 Uni-Chemical., Ltd. Phosphorus-acid-group-containing (meth) acrylamide, its polymer and use thereof, and their production methods
JP2007238738A (ja) * 2006-03-08 2007-09-20 Showa Highpolymer Co Ltd ラジカル重合性難燃樹脂組成物
WO2012086867A1 (fr) * 2010-12-23 2012-06-28 제일모직 주식회사 Composition de résine copolymère acrylique

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Publication number Priority date Publication date Assignee Title
US3030347A (en) * 1960-04-25 1962-04-17 Rohm & Haas Dialkylphosphonoalkyl acrylate and methacrylate copolymers
JP2001151855A (ja) * 1999-11-25 2001-06-05 Matsushita Electric Works Ltd リン含有ビニルエステルの製造方法及びこのビニルエステルを用いたラジカル重合性樹脂組成物の製造方法
US20070173549A1 (en) * 2004-02-24 2007-07-26 Uni-Chemical., Ltd. Phosphorus-acid-group-containing (meth) acrylamide, its polymer and use thereof, and their production methods
JP2007238738A (ja) * 2006-03-08 2007-09-20 Showa Highpolymer Co Ltd ラジカル重合性難燃樹脂組成物
WO2012086867A1 (fr) * 2010-12-23 2012-06-28 제일모직 주식회사 Composition de résine copolymère acrylique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116438280A (zh) * 2020-11-20 2023-07-14 株式会社可乐丽 聚合物、阻燃性组合物和聚合物的制造方法
EP4249528A4 (fr) * 2020-11-20 2024-11-06 Kuraray Co., Ltd. Polymère, composition ignifuge et procédé de production de polymère

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