WO2016024614A1 - 共重合体および成形体 - Google Patents
共重合体および成形体 Download PDFInfo
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- WO2016024614A1 WO2016024614A1 PCT/JP2015/072846 JP2015072846W WO2016024614A1 WO 2016024614 A1 WO2016024614 A1 WO 2016024614A1 JP 2015072846 W JP2015072846 W JP 2015072846W WO 2016024614 A1 WO2016024614 A1 WO 2016024614A1
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- methacrylate
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- NWAHZAIDMVNENC-UHFFFAOYSA-N CC(C(OC1C(C2)C(CCC3)C3C2C1)=O)=C Chemical compound CC(C(OC1C(C2)C(CCC3)C3C2C1)=O)=C NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- 0 CNC(C(O*)=O)=[Mn](C)=C Chemical compound CNC(C(O*)=O)=[Mn](C)=C 0.000 description 1
Classifications
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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
- 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
-
- 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
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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
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use 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; Derivatives of such polymers
- C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Definitions
- the present invention relates to a copolymer having excellent transparency and flame resistance and a high glass transition temperature, and a molded body containing such a copolymer.
- Resins with excellent transparency are used for applications such as optical materials, lighting materials, signboards, and decorative members. In these applications, flame retardancy may be required.
- a resin composition in which an inorganic compound such as basic magnesium carbonate is blended with the resin is known (see, for example, Patent Document 1).
- Patent Document 1 a resin composition in which an inorganic compound such as basic magnesium carbonate is blended with the resin.
- such a resin composition is usually not suitable for applications requiring high transparency such as optical materials because of its low transparency.
- a resin composition containing a phosphate ester or a halogen-containing condensed phosphate ester is known (see, for example, Patent Documents 2, 3, and 4).
- the blended phosphate ester or halogen-containing condensed phosphate ester may bleed out on the surface, which may cause surface whitening or reduced flame retardancy.
- a resin composition containing a halogen-containing condensed phosphate ester may generate a halogen gas having toxicity and metal corrosivity during combustion.
- An object of the present invention is to provide a copolymer having excellent transparency and flame resistance and a high glass transition temperature at a low cost.
- Structural unit (I) derived from a phosphonate monomer represented by formula (1); At least one radical polymerizable monomer selected from the group consisting of methacrylic acid, acrylic acid, a radical polymerizable monomer represented by formula (2a), and a radical polymerizable monomer represented by formula (2b) ( A structural unit (II) derived from 2); Containing a structural unit (III) derived from methyl methacrylate, and the content of phosphorus atoms derived from the phosphonate monomer represented by the formula (1) is 1.0 mass relative to the mass of the copolymer. % Or more and less than 2.0 mass%.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkylene group having 1 to 4 carbon atoms
- R 3 and R 4 each independently represents a hydrogen atom or 1 to 10 carbon atoms. Represents an alkyl group.
- R 5 represents a polycyclic aliphatic hydrocarbon group or an alkyl-substituted monocyclic aliphatic hydrocarbon group.
- R 9 represents —CH 2 CHR 10 R 11 , —CHR 10 —CHR 11 R 12 or —CR 10 R 11 R 13 , and R 10 , R 11 and R 13 each independently represents the number of carbon atoms. And represents an alkyl group having 1 to 3 and R 12 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the structural unit (II) contains at least a structural unit derived from methacrylic acid or acrylic acid, The copolymer according to [1], wherein the total content of structural units derived from methacrylic acid or acrylic acid is 1 to 12% by mass relative to the mass of the copolymer. [3] The copolymer according to [1] or [2], wherein the content of the structural unit (III) is 50% by mass to 80% by mass with respect to the mass of the copolymer. [4] The copolymer according to any one of [1] to [3], wherein the content of the structural unit (II) is 5% by mass or more and 30% by mass or less with respect to the mass of the copolymer.
- the structural unit (II) contains at least a structural unit derived from the radical polymerizable monomer represented by the formula (2a), R 5 in the formula (2a) is a norbornyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentadienyl group, an adamantyl group, or a 4-t-butylcyclohexyl group.
- the copolymer as described in any one.
- the copolymer according to any one of [1] to [5] which has a glass transition temperature of 115 ° C. or higher.
- [7] The copolymer according to any one of [1] to [6], which has a weight average molecular weight of 150,000 or more.
- the copolymer and molded body of the present invention are excellent in transparency and flame resistance and have a high glass transition temperature, and therefore can be used in fields requiring heat resistance.
- the copolymer of the present invention contains structural unit (I), structural unit (II) and structural unit (III).
- the structural unit (I) is derived from the phosphonate monomer represented by the formula (1) (hereinafter sometimes referred to as “phosphonate monomer (1)”).
- R 1 in the formula (1) represents a hydrogen atom or a methyl group.
- R 2 in the formula (1) represents an alkylene group having 1 to 4 carbon atoms.
- the alkylene group is a divalent hydrocarbon group. Examples of the alkylene group include a methylene group, an ethylene group (also known as dimethylene group), a trimethylene group, a propylene group (also known as propane-1,2-diyl group), a tetramethylene group, a butane-1,2-diyl group, And a butane-1,3-diyl group. Among these, a methylene group or an ethylene group is preferable from the viewpoint of economy.
- R 3 and R 4 in the formula (1) each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, i-pentyl group.
- the phosphonate monomer (1) include diethyl methacryloyloxymethyl phosphonate, diethyl 2-methacryloyloxyethyl phosphonate, diethyl 1-methacryloyloxyethyl phosphonate, dimethyl 3-methacryloyloxypropyl phosphonate, dimethyl 2-methacryloyloxypropyl.
- Phosphonate dimethyl 4-methacryloyloxybutyl phosphonate, dimethyl 3-methacryloyloxybutyl phosphonate, dimethyl 2-methacryloyloxybutyl phosphonate; diethyl acryloyloxymethyl phosphonate, diethyl 2-acryloyloxyethyl phosphonate, dimethyl 3-acryloyloxypropyl phosphonate, dimethyl 2 -Acryloyloxypropyl phosphonate, dimethyl Le 4- acryloyloxybutyl phosphonate, dimethyl 3-acryloyloxy-butyl phosphonate, dimethyl 2-acryloyloxy-butyl phosphonate, and the like.
- diethylmethacryloyloxymethylphosphonate and diethyl 2-methacryloyloxyethylphosphonate are preferred from the viewpoint of enhancing the flame resistance of the copolymer.
- These phosphonate monomers (1) may be used alone or in combination of two or more.
- the amount of the structural unit (I) contained in the copolymer of the present invention is preferably 3 with respect to the number of moles of all structural units contained in the copolymer, from the viewpoint of achieving both fire resistance and heat resistance.
- the amount is from 6 mol% to less than 15 mol%, more preferably from 4.0 mol% to 10 mol%.
- the content of the structural unit (I) derived from the phosphonate monomer (1) is such that two or more phosphonate monomers are used. This is the total content of structural units derived from the monomer (1).
- the phosphorus atom content derived from the phosphonate monomer (1) is preferably 1.0% by mass or more and less than 2.0% by mass with respect to the mass of the copolymer. More preferably, it is 1.20 mass% or more and 1.98 mass% or less.
- the structural unit (II) includes methacrylic acid, acrylic acid, a radical polymerizable monomer represented by the formula (2a) (hereinafter sometimes referred to as “radical polymerizable monomer (2a)”), and a formula ( At least one radically polymerizable monomer (2) selected from the group consisting of the radically polymerizable monomer represented by 2b) (hereinafter sometimes referred to as “radical polymerizable monomer (2b)”) It comes from.
- R 5 represents a polycyclic aliphatic hydrocarbon group or an alkyl-substituted monocyclic aliphatic hydrocarbon group.
- the alkyl group in the alkyl-substituted monocyclic aliphatic hydrocarbon group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an isopropyl group, or a t-butyl group.
- Examples of the polycyclic aliphatic hydrocarbon group include a norbornyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentadienyl group, an adamantyl group, a fenkyl group, and a decalin group.
- alkyl-substituted monocyclic aliphatic hydrocarbon group examples include 4-methylcyclohexyl group, 2-methylcyclohexyl group, 4-isopropylcyclohexyl group, 2-isopropylcyclohexyl group, 4-t-butylcyclohexyl group, 2-t- And a butylcyclohexyl group. Of these, 4-t-butylcyclohexyl group is preferred.
- radical polymerizable monomer (2a) examples include 4-methylcyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, 4-isopropylcyclohexyl methacrylate, 2-isopropylcyclohexyl methacrylate, 4-tert-butyl methacrylate.
- Alkyl-substituted monocyclic aliphatic hydrocarbon esters such as cyclohexyl, 2-t-butylcyclohexyl methacrylate; 2-norbornyl methacrylate, 2-methyl-2-norbornyl methacrylate, 2-ethyl-2-norbornyl methacrylate, 2-isobornyl methacrylate, 2-methyl-2-isobornyl methacrylate, 2-ethyl-2-isobornyl methacrylate, 8-tricyclo [5.2.1.0 2,6 ] decanyl methacrylate, 8-methyl methacrylate -8-G Cyclo [5.2.1.0 2, 6] decanyl, methacrylic acid 8-ethyl-8-tricyclo [5.2.1.0 2, 6] decanyl methacrylate, 2-adamantyl methacrylate, 2-methyl - 2-adamantyl, 2-ethyl-2-adamantyl methacrylate, 1-adamanty
- R 9 represents —CH 2 CHR 10 R 11 , —CHR 10 —CHR 11 R 12 or —CR 10 R 11 R 13
- R 10 , R 11 and R 13 are each independently Represents an alkyl group having 1 to 3 carbon atoms
- R 12 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
- radical polymerizable monomer (2b) examples include isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 1-methylbutyl methacrylate, 2-methylbutyl methacrylate, 1,1-dimethyl methacrylate.
- examples thereof include propyl, 1,3-dimethylbutyl methacrylate, 2-ethylbutyl methacrylate, 2-methylpentyl methacrylate and the like.
- isobutyl methacrylate, s-butyl methacrylate, and t-butyl methacrylate are preferable, and t-butyl methacrylate is more preferable.
- radical polymerizable monomers (2) may be used singly or in combination of two or more.
- the radical polymerizable monomer (2a) or (2b) is preferably a monomer that is easily converted into methacrylic acid or acrylic acid due to decomposition of the ester bond during combustion.
- Methacrylic acid or acrylic acid tends to slightly deteriorate the water absorption of the copolymer, but tends to increase the heat resistance of the copolymer.
- the radical polymerizable monomer (2a) tends to lower the water absorption of the copolymer.
- the radical polymerizable monomer (2a) tends to increase the glass transition temperature of the copolymer, and the radical polymerizable monomer (2b) tends not to decrease the glass transition temperature of the copolymer.
- methacrylic acid or acrylic acid is used in combination with the radical polymerizable monomer (2a)
- the resulting copolymer is preferred because it tends to have both low water absorption and high heat resistance.
- the lower limit amount of the structural unit (II) contained in the copolymer of the present invention is preferably 1% by mass, more preferably 5% by mass, still more preferably 10% by mass, based on the mass of the copolymer. Particularly preferably, it is 15% by mass, and the upper limit is preferably 50% by mass, more preferably 40% by mass, and further preferably 30% by mass with respect to the mass of the copolymer.
- the content of the structural unit (II) is increased, the glass transition temperature of the copolymer tends to increase.
- the content of the structural unit (II) is the structural unit derived from the two or more radical polymerizable monomers (2). Is the total content.
- the structural unit (II) contains at least a structural unit derived from methacrylic acid or acrylic acid.
- the total content of structural units derived from methacrylic acid or acrylic acid is preferably 1 to 12% by mass, more preferably 2 to 8% by mass, based on the mass of the copolymer.
- the structural unit (II) contains at least a structural unit derived from a radical polymerizable monomer represented by the formula (2a).
- R 5 in the formula (2a) is a norbornyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentadienyl group, an adamantyl group, or a 4-t-butylcyclohexyl group. preferable.
- the structural unit (III) contained in the copolymer of the present invention is derived from methyl methacrylate.
- the lower limit amount of the structural unit (III) contained in the copolymer of the present invention is preferably 50% by mass, more preferably 55% by mass, and still more preferably from the viewpoint of transparency. Is 58% by mass, most preferably 60% by mass.
- the upper limit is preferably 80% by mass, more preferably 75% by mass, and still more preferably 72% by mass with respect to the mass of the copolymer. % By weight, most preferably 70% by weight.
- the copolymer of the present invention comprises a phosphonate monomer (1), a radical polymerizable monomer (2), and a radical polymerizable monomer other than methyl methacrylate (hereinafter referred to as “radical polymerizable monomer (4). It may further have a structural unit (IV) derived from “)”.
- radical polymerizable monomer (4) examples include vinyl aromatic hydrocarbons such as styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene; vinylcyclohexane, vinylcyclopentane, vinylcyclohexene, vinylcycloheptane, Vinyl alicyclic hydrocarbons such as vinylcycloheptene and vinyl norbornene; Ethylenically unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and itaconic acid; Olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene Conjugated dienes such as butadiene, isoprene and myrcene; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride; methyl acryl
- Cyl or higher alkyl ester of lauric acid 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate; cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexane (meth) acrylate (Meth) acrylic acid unsubstituted monocyclic aliphatic hydrocarbon esters such as butyl;
- (Meth) acrylic acid aryl esters such as phenyl methacrylate and phenyl acrylate; (meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; 2-vinylfuran, 2-isopropenyl Furan, 2-vinylbenzofuran, 2-isopropenylbenzofuran, 2-vinyldibenzofuran, 2-vinylthiophene, 2-isopropenylthiophene, 2-vinyldibenzothiophene, 2-vinylpyrrole, N-vinylindole, N-vinylcarbazole, 2-vinyloxazole, 2-isopropenyloxazole, 2-vinylbenzoxazole, 3-vinylisoxazole, 3-isopropenylisoxazole, 2-vinylthiazole, 2-vinylimidazole, 4 (5) Vinylimid
- methacrylic acid alkyl esters and acrylic acid alkyl esters are preferred, and methyl methacrylate and methyl acrylate are more preferred.
- These radical polymerizable monomers (4) may be used alone or in combination of two or more.
- (Meth) acryl means “methacryl or acryl”.
- the amount of the structural unit (IV) contained in the copolymer of the present invention is preferably 15% by mass or less, more preferably 10% by mass, based on the mass of the copolymer, from the balance between heat resistance and flame resistance. Hereinafter, it is more preferably 5% by mass or less.
- the content of the structural unit (IV) is the structural unit derived from the two or more types of radical polymerizable monomers (4). Is the total content.
- the structural unit (IV) may include a structural unit (IV-1) derived from a polyfunctional polymerizable monomer.
- Polyfunctional polymerizable monomers include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di ( Polyfunctional (meth) acrylates such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylol
- ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate are preferred. These polyfunctional polymerizable monomers may be used alone or in combination of two or more. “(Meth) acrylate” means “methacrylate or acrylate”.
- the amount of the structural unit (IV-1) contained in the copolymer of the present invention is preferably 0.001% by mass or more and 10% by mass with respect to the mass of the copolymer from the balance between heat resistance and flame resistance.
- it is more preferably 0.01% by mass or more and 5% by mass or less, and further preferably 0.1% by mass or more and 1% by mass or less.
- the content of structural unit (IV-1) is the content of structural units derived from two or more polyfunctional polymerizable monomers. The total amount.
- the amount of each structural unit contained in the copolymer of the present invention can be quantified by 1 H-NMR measurement. Further, if it becomes difficult to quantify due to overlapping peaks in 1 H-NMR measurement, it can also be quantified using pyrolysis gas chromatography measurement.
- the copolymer examples include methyl methacrylate / methacrylic acid / diethylmethacryloyloxymethylphosphonate copolymer, methyl methacrylate / methacrylic acid / diethyl 2-methacryloyloxyethylphosphonate copolymer, methyl methacrylate / acrylic acid / Diethylmethacryloyloxymethylphosphonate copolymer, methyl methacrylate / acrylic acid / diethyl 2-methacryloyloxyethylphosphonate copolymer, methyl methacrylate / methacrylic acid 8-tricyclo [5.2.1.0 2,6 ] decanyl / Diethylmethacryloyloxymethylphosphonate copolymer, methyl methacrylate / methacrylic acid 8-tricyclo [5.2.1.0 2,6 ] decanyl / Diethylmethacryloyloxymethylphosphonate copolymer,
- the glass transition temperature of the copolymer of the present invention is preferably 110 to 180 ° C, more preferably 120 to 165 ° C. If the glass transition temperature is too low, the heat resistance of the copolymer is insufficient, and if the glass transition temperature is too high, the copolymer becomes brittle.
- the glass transition temperature is a value measured in accordance with JIS K7121. That is, the copolymer of the present invention was heated once to 230 ° C., then cooled to room temperature, and then DSC curve was measured by differential scanning calorimetry under the condition that the temperature was raised from room temperature to 230 ° C. at 10 ° C./min. And the midpoint glass transition temperature obtained from the DSC curve measured at the second temperature rise was defined as the glass transition temperature of the present invention.
- the lower limit of the weight average molecular weight of the copolymer of the present invention is preferably 100,000, more preferably 150,000, still more preferably 300,000.
- the upper limit of the weight average molecular weight is not particularly limited, but is preferably 5 million, more preferably 3 million from the viewpoint of moldability. When the weight average molecular weight is in this range, the impact resistance and toughness of the copolymer are good.
- the copolymer of the present invention has a weight average molecular weight / number average molecular weight ratio (hereinafter, this ratio may be referred to as “molecular weight distribution”), preferably 1.1 to 10.0, more preferably 1. It is 5 to 5.0, particularly preferably 1.6 to 3.0. When the molecular weight distribution is within this range, the moldability of the copolymer and the impact resistance and toughness of the molded body obtained from the copolymer are good.
- a weight average molecular weight and molecular weight distribution are the values of standard polystyrene conversion measured by GPC (gel permeation chromatography). Such weight average molecular weight and molecular weight distribution can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.
- the copolymer of the present invention comprises a phosphonate monomer (1), a radical polymerizable monomer (2) and methyl methacrylate in a proportion corresponding to the content of the structural unit, and if necessary, a radical polymerizable monomer. It can be obtained by copolymerizing the monomer (4).
- the copolymerization method is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method.
- a reactive molding method such as a cell cast polymerization method is preferable because it can reduce heat applied to the copolymer during molding and can obtain a molded product having a small yellow index.
- Copolymerization can be initiated at a predetermined temperature in the presence of a polymerization initiator. Moreover, the weight average molecular weight etc. of the copolymer obtained can be adjusted using a chain transfer agent as needed.
- the phosphonate monomer (1), radical polymerizable monomer (2), methyl methacrylate and, optionally, the radical polymerizable monomer (4), which are raw materials for obtaining the copolymer of the present invention, are:
- the yellow index at an optical path length of 3.2 mm is preferably 2 or less, and more preferably 1 or less. When the yellow index is small, coloring of the obtained copolymer can be suppressed.
- the yellow index of a test piece having a thickness of 3.2 mm of the obtained copolymer can be 2.0 or less.
- the above yellow index is a yellowness value calculated based on JIS K7373 based on a value measured based on JIS Z8722.
- the polymerization initiator used when producing the copolymer of the present invention is not particularly limited as long as it generates a reactive radical.
- t-hexyl peroxyisopropyl monocarbonate t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate soot
- t-butyl peroxypivalate T-hexylperoxypivalate
- t-butylperoxyneodecanoate t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate
- 1 1-bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, and other organic peroxides; 2,2′-azobis (2-methylpro Pion
- polymerization initiators may be used alone or in combination of two or more.
- the addition amount and addition method of the polymerization initiator are not particularly limited as long as they are appropriately set according to the purpose.
- the amount of the polymerization initiator is preferably in the range of 0.0001 to 0.2 parts by mass, more preferably in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total monomers.
- the amount of the polymerization initiator is the sum of the amounts of the two or more polymerization initiators.
- Examples of the chain transfer agent used in producing the copolymer of the present invention include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bis Thiopropionate, butanediol bisthioglycolate, butanediol bisthiopropionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris- ( ⁇ -thiopropionate), penta Alkyl mercaptans such as erythritol tetrakisthiopropionate; ⁇ -methylstyrene dimer; terpinolene and the like.
- chain transfer agents such as n-octyl mercaptan and n-dodecyl mercaptan are preferred.
- These chain transfer agents may be used alone or in combination of two or more.
- the amount of the chain transfer agent used is preferably 0.01 to 1 part by weight, more preferably 0.02 to 0.8 part by weight, still more preferably 0.03 to 0 part per 100 parts by weight of the total monomers. .6 parts by mass. Needless to say, when two or more chain transfer agents are used in combination, the amount of the chain transfer agent used is the sum of the amounts of the two or more chain transfer agents used.
- the temperature during the copolymerization is preferably 0 to 200 ° C, more preferably 20 to 180 ° C.
- the time for carrying out the copolymerization depends on the reaction scale, but is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours from the viewpoint of economy.
- the copolymerization is preferably performed in an inert gas atmosphere such as nitrogen gas.
- additives may be added to the copolymer as necessary.
- Additives include antioxidants, thermal degradation inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, impact modifiers, organic dyes, light diffusing agents, matte Agents, phosphors, antistatic agents, flame retardants, plasticizers, inorganic fillers, fibers and the like.
- the blending amount of such various additives can be appropriately determined within a range not impairing the effects of the present invention.
- the blending amount of each additive is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the copolymer and other polymers added as necessary. 1 part by mass.
- the antioxidant alone has an effect of preventing oxidative deterioration of the resin in the presence of oxygen.
- examples thereof include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. These antioxidants may be used alone or in combination of two or more. Among these, from the viewpoint of preventing the deterioration of optical properties due to coloring, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable. preferable.
- the ratio is not particularly limited, but is preferably a mass ratio of phosphorus antioxidant / hindered phenol antioxidant, preferably 1/5. ⁇ 2 / 1, more preferably 1 ⁇ 2 to 1/1.
- Examples of phosphorus antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA; trade name: ADK STAB HP-10), tris (2,4-di-t- Butylphenyl) phosphite (manufactured by BASF; trade name: IRUGAFOS168), 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3, And 9-diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: ADK STAB PEP-36).
- hindered phenol-based antioxidant pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name IRGANOX 1010), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF; trade name IRGANOX1076).
- the thermal degradation inhibitor can prevent thermal degradation of the copolymer by scavenging polymer radicals generated when exposed to high heat in a substantially oxygen-free state.
- the thermal degradation inhibitor include 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumitizer GS) Can be mentioned.
- the ultraviolet absorber is a compound having an ability to absorb ultraviolet rays, and is mainly said to have a function of converting light energy into heat energy.
- the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like.
- benzotriazoles, triazines, or ultraviolet absorbers having a maximum molar extinction coefficient ⁇ max at a wavelength of 380 to 450 nm of 100 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less are preferable.
- Benzotriazoles are preferable as ultraviolet absorbers used when the film of the present invention is applied to optical applications because it has a high effect of suppressing deterioration of optical properties such as coloring due to ultraviolet irradiation.
- benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2- (2H- Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234), 2,2′-methylenebis [6- (2H-benzotriazole-2) -Yl) -4-t-octylphenol] (manufactured by ADEKA; LA-31) is preferred.
- an ultraviolet absorber having a maximum molar extinction coefficient ⁇ max at wavelengths of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less can suppress discoloration of the resulting film.
- ultraviolet absorbers include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan; trade name Sundebore VSU).
- benzotriazoles are preferably used from the viewpoint of suppressing resin degradation due to ultraviolet irradiation.
- a triazine UV absorber is preferably used.
- ultraviolet absorbers include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; LA-F70). Can be mentioned.
- the maximum value ⁇ max of the molar extinction coefficient of the ultraviolet absorber is measured as follows. Add 10.00 mg of UV absorber to 1 L of cyclohexane and dissolve it so that there is no undissolved material by visual observation. This solution is poured into a 1 cm ⁇ 1 cm ⁇ 3 cm quartz glass cell, and the absorbance at a wavelength of 380 to 450 nm and an optical path length of 1 cm is measured using a U-3410 type spectrophotometer manufactured by Hitachi, Ltd. The maximum value ⁇ max of the molar extinction coefficient is calculated from the molecular weight (M UV ) of the ultraviolet absorber and the maximum value (A max ) of the measured absorbance according to the following formula.
- the light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light.
- Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
- lubricant examples include stearic acid, behenic acid, stearamide acid, methylene bisstearamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hardened oil.
- the mold release agent is a compound having a function of facilitating mold release from the mold.
- the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
- the ratio is not particularly limited, but the mass ratio of higher alcohols / glycerin fatty acid monoester is preferably 2.5 / 1 to 3.5 / 1. The preferred range is 2.8 / 1 to 3.2 / 1.
- the polymer processing aid is a compound that exhibits an effect on thickness accuracy and thinning when a copolymer is formed.
- the polymer processing aid is polymer particles having a particle diameter of 0.05 to 0.5 ⁇ m, which can be usually produced by an emulsion polymerization method.
- the polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be.
- particles having a two-layer structure having a polymer layer having an intrinsic viscosity of less than 5 dl / g in the inner layer and a polymer layer having an intrinsic viscosity of 5 dl / g or more in the outer layer are preferable.
- the polymer processing aid as a whole preferably has an intrinsic viscosity of 3 to 6 dl / g.
- the impact resistance modifier examples include a core-shell type modifier containing acrylic rubber or diene rubber as a core layer component; a modifier containing a plurality of rubber particles, and the like.
- the organic dye a compound having a function of converting ultraviolet light, which is considered harmful to the copolymer, into visible light is preferably used.
- the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.
- the phosphor include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent brightener, and a fluorescent bleach.
- antistatic agent examples include stearoamidopropyldimethyl- ⁇ -hydroxyethylammonium nitrate.
- Non-halogen flame retardants such as FP800 manufactured by the company are listed.
- plasticizer examples include tricresyl phosphate, trixylenyl phosphate, triphenyl phosphate, triethylphenyl phosphate, diphenyl cresyl phosphate, monophenyl dicresyl phosphate, diphenyl monoxylenyl phosphate, Phosphoric acid triester plasticizers such as monophenyldixylenyl phosphate, tributyl phosphate, triethyl phosphate; dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-phthalate Phthalate plasticizers such as ethylhexyl, diisononyl phthalate, octyldecyl phthalate, and butylbenzyl phthalate; fatty acid monobasic esters such as butyl oleate and glycerol monooleate Plastic
- liquid paraffin white oil, JIS-K-2231
- ISO VG10 ISO VG15, ISO VG32, ISO VG68, ISO VG100, ISO VG8, ISO VG21, etc.
- polyisobutene hydrogenated polybutadiene, hydrogenated polyisoprene and the like.
- squalane, liquid paraffin and polyisobutene are preferred.
- examples of the inorganic filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.
- examples of the fiber include glass fiber and carbon fiber.
- the molded product of the present invention contains the copolymer of the present invention, and preferably contains 70% by mass or more of the copolymer of the present invention.
- the molded product of the present invention is not particularly limited in its production method.
- a T-die method laminate method, coextrusion method, etc.
- an inflation method coextrusion method, etc.
- a compression molding method a blow molding method
- a calendar molding method a molding method
- the copolymer of the present invention can be obtained by molding by melt molding method such as vacuum molding method, injection molding method (insert method, two-color method, pressing method, core back method, sandwich method, etc.) and solution casting method. it can.
- the molded article of the present invention can be obtained by simultaneously performing a reaction molding method such as a cell cast polymerization method, that is, a polymerization reaction and molding of a monomer mixture.
- a reaction molding method such as a cell cast polymerization method, that is, a polymerization reaction and molding of a monomer mixture.
- these molding methods the T-die method, the inflation method, the injection molding method, and the cell cast polymerization method are preferable from the viewpoint of high productivity and cost.
- the thing of thickness of 2 mm or more can be obtained by the above-mentioned method, for example.
- the molding may be performed a plurality of times.
- the pellet-shaped molded body can be further molded to obtain a molded body having a desired shape.
- another copolymer may be mixed with the copolymer of the present invention within a range not impairing the effects of the present invention.
- examples of such other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, and high impact polystyrene.
- the laminate may be a laminate of only the molded article of the present invention, or may be a laminate of the molded article of the present invention and another material.
- the method for producing the laminate is not particularly limited. For example, a method of extruding two or more polymers at the same time (coextrusion method); a method of fusing two or more molded products with heat, ultrasonic waves, high frequency, etc. (fusion method); Method of bonding with ultraviolet curable adhesive, thermosetting adhesive, radiation curable adhesive, etc.
- the surface to be fused or the surface to be bonded may be surface-treated with a known primer, or subjected to corona discharge treatment or plasma treatment before fusing or bonding. Also good.
- Other materials to be laminated with the molded body of the present invention are not particularly limited, and can be appropriately selected according to the use of the laminated body.
- Other materials in the case where the laminate is used as an optical component are not particularly limited.
- hard coating materials, antireflection materials, liquid crystals, cyclic olefin-based ring-opening polymers or hydrogenated products thereof, and cyclic olefin-based addition polymers are not particularly limited.
- hard coating materials for example, antireflection materials, liquid crystals, cyclic olefin-based ring-opening polymers or hydrogenated products thereof, and cyclic olefin-based addition polymers.
- Aliphatic olefin resin acrylic polymer, polycarbonate resin, liquid crystal polymer, soda glass, quartz glass and the like.
- the surface of the molded body of the present invention or a laminate including the molded body can be printed, or the surface can be shaped by cutting or embossing. After printing or shaping, if it is laminated with other materials by insert molding, etc., the characters, patterns, irregularities, etc. formed by printing or shaping are enclosed between the molded body of the present invention and other materials. . Since the molded article of the present invention is excellent in transparency, encapsulated characters, patterns, irregularities and the like can be clearly observed.
- the molded product of the present invention is preferably a film or a sheet.
- a film refers to a planar molded body having a thickness of 0.005 mm or more and 0.25 mm or less
- a sheet refers to a planar molded body having a thickness of more than 0.25 mm.
- the molded body of the present invention has a thickness of preferably 0.1 mm or more and less than 100 mm, more preferably 0.5 mm or more and less than 50 mm, further preferably 0.8 mm or more and less than 30 mm, and most preferably 1 mm or more and less than 10 mm. .
- the copolymer and molded product of the present invention are excellent in transparency, flame resistance and heat resistance, they can be used in various fields such as the optical field, food field, medical field, automobile field, and electric / electronic field.
- various optical members for optical devices microwaves, binoculars, cameras, etc.) (finders, filters, prisms, Fresnel lenses, etc.)
- various optical members for display devices TVs, touch panels, personal computers, portable terminals, etc.
- optical switch optical connector
- Optical member such as; useful like lighting member such as a lighting cover.
- house parts (roofs, windows, gutters, walls, etc.), retroreflective films / sheets, agricultural films / sheets, signs (gas station signs, display boards, store signs, etc.), decorative parts, soundproof walls, etc. Useful for applications used outdoors. Furthermore, it is useful for signboards and building materials for stations, buildings, houses, etc.
- the present invention will be described more specifically with reference to examples and comparative examples.
- this invention is not restrict
- the present invention includes all aspects that are obtained by arbitrarily combining the above-described items representing technical characteristics such as characteristic values, forms, manufacturing methods, and uses.
- the physical properties of the copolymer and the molded body were measured by the following methods.
- Total light transmittance The resin pellets were hot press molded at 230 ° C. to obtain a sheet-like molded body having a thickness of 3.2 mm.
- the total light transmittance at an optical path length of 3.2 mm was measured using HR-100 (product number) manufactured by Murakami Color Research Laboratory according to JIS K7361-1.
- haze (H) at an optical path length of 3.2 mm was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) in accordance with JISK7136.
- Glass-transition temperature In accordance with JIS K7121, the resin pellet is heated once to 230 ° C., then cooled to room temperature, and then the temperature is raised from room temperature to 230 ° C. at a rate of 10 ° C./minute by differential scanning calorimetry. DSC curve was measured. The midpoint glass transition temperature obtained from the DSC curve measured at the second temperature increase was adopted as the glass transition temperature in the present invention.
- DSC-50 product number manufactured by Shimadzu Corporation was used as a measuring apparatus.
- DEMMPO diethyl methacryloyloxymethyl phosphonate
- B diethyl 2-methacryloyloxyethyl phosphonate
- radical polymerizable monomer (2) examples include methacrylic acid (hereinafter referred to as “MAA”), t-butyl methacrylate (hereinafter referred to as “tBMA”), and 8-tricyclo [5] methacrylate. .2.1.0 2,6 ] decanyl (see formula (C), hereinafter referred to as “TCDMA”) and 2-isobornyl methacrylate (see formula (D), hereinafter referred to as “IBMA”) Prepared).
- MAA methacrylic acid
- tBMA t-butyl methacrylate
- IBMA 2-isobornyl methacrylate
- MMA methyl methacrylate
- Examples of the radical polymerizable monomer (4) include methyl acrylate (hereinafter referred to as “MA”), styrene (hereinafter referred to as “St”), and 5-methyl-3-methylidene dihydrofuran. -2 (3H) -one (see Formula (E), hereinafter referred to as “MMBL”) was prepared. MMBL was synthesized by the method described in Non-Patent Document 5.
- Example 1 15 parts by mass of DEMMPO, 15 parts by mass of TCDMA, 6 parts by mass of MAA, 62 parts by mass of MMA, and 2 parts by mass of MA were mixed to obtain a monomer mixture.
- a polymerization initiator (2,2′-azobis (2-methylpropionitrile), hydrogen abstraction capacity: 1%, half hour temperature: 83 ° C.
- the raw material liquid was obtained by dissolving. This raw material liquid was poured into a glass cell composed of two glass plates (thickness 10 mm, 30 cm square) treated with water repellency and a vinyl chloride resin gasket, and deaerated at 10 mmHg for 3 minutes. The glass cell was held at 70 ° C.
- the obtained sheet-like molded article was composed of a very high molecular weight polymer, and therefore did not dissolve in the solvent, but only swelled. Therefore, the molecular weight cannot be measured by GPC.
- the estimated weight average molecular weight is 1 million g / mol or more.
- the structural unit (mol%) derived from DEMMPO, which is the phosphonate monomer (1), and the phosphorus atom content (mass%) were calculated by 1 H-NMR measurement in a swollen state. The results are shown in Table 1.
- Example 2 A sheet-like molded body having a thickness of 3.2 mm was obtained by the same method as in Example 1 except that the formulation shown in Table 1 or 2 was used. These test pieces were evaluated in the same manner as in Example 1. The results are shown in Table 1 or Table 2.
- Example 3 10 parts by weight of DEMMPO, 15 parts by weight of TCDMA, 6 parts by weight of MAA, and 69 parts by weight of MMA were mixed to obtain a monomer mixture.
- 0.1 parts by mass of a polymerization initiator (2,2′-azobis (2-methylpropionitrile), hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.) and 1 part by mass of a chain transfer agent (n-octyl mercaptan) was added and dissolved to obtain a raw material liquid.
- 100 parts by mass of ion-exchanged water, 0.03 parts by mass of sodium sulfate, and 0.46 parts by mass of a suspension dispersant were mixed to obtain a mixed solution.
- the obtained copolymer was supplied to a twin screw extruder controlled at 230 ° C. to separate and remove volatile components such as unreacted monomers, and then the resin component was extruded to form a strand.
- the strands were cut with a pelletizer to form pellets.
- the glass transition temperature of the obtained pellet-shaped molded body was measured. Moreover, this pellet-shaped molded object was hot press molded at 230 degreeC, and the sheet-shaped molded object of thickness 3.2mm was obtained. A test piece having a length of 127 mm, a width of 13 mm, and a thickness of 3.2 mm was cut out from the obtained sheet-like molded body, and evaluated for flame resistance, transparency, and water absorption. The results are shown in Table 1.
- Example 4 A pellet-shaped molded body was obtained in the same manner as in Example 3 except that the formulation shown in Table 1 was changed. Measurement of various physical properties of these pellet-shaped molded bodies and evaluation of test pieces were carried out in the same manner as in Example 1. The results are shown in Table 1. The results are shown in Table 1.
- the copolymer of the present invention has excellent transparency and flame resistance, and a high glass transition temperature.
Abstract
Description
樹脂の難燃性を高める方法として、樹脂に塩基性炭酸マグネシウムなどの無機化合物を配合した樹脂組成物が知られている(例えば特許文献1参照)。しかしながら、かかる樹脂組成物は、通常、透明性が低いため、光学材料などの高い透明性を求められる用途には適さない。
メタクリル酸、アクリル酸、式(2a)で示されるラジカル重合性単量体、および式(2b)で示されるラジカル重合性単量体からなる群より選ばれる少なくとも一つのラジカル重合性単量体(2)に由来する構造単位(II)と、
メタクリル酸メチルに由来する構造単位(III)とを含有し、且つ
式(1)で示されるホスホネート系単量体に由来するリン原子の含有量が共重合体の質量に対して1.0質量%以上2.0質量%未満である、共重合体。
メタクリル酸またはアクリル酸に由来する構造単位の合計含有量が共重合体の質量に対して1~12質量%である〔1〕に記載の共重合体。
〔3〕構造単位(III)の含有量が共重合体の質量に対して50質量%以上80質量%以下である〔1〕または〔2〕に記載の共重合体。
〔4〕構造単位(II)の含有量が共重合体の質量に対して5質量%以上30質量%以下である〔1〕~〔3〕のいずれかひとつに記載の共重合体。
式(2a)中のR5が、ノルボルニル基、イソボルニル基、トリシクロデカニル基、ジシクロペンタジエニル基、アダマンチル基、または4-t-ブチルシクロヘキシル基である〔1〕~〔4〕のいずれかひとつに記載の共重合体。
〔6〕ガラス転移温度が115℃以上である〔1〕~〔5〕のいずれかひとつに記載の共重合体。
〔7〕重量平均分子量が15万以上である〔1〕~〔6〕のいずれかひとつに記載の共重合体。
〔9〕2mm以上の厚さを有する〔8〕に記載の成形体。
式(1)中のR1は、水素原子またはメチル基を表す。
式(1)中のR2は、炭素数1~4のアルキレン基を表す。アルキレン基は2価の炭化水素基である。アルキレン基としては、例えば、メチレン基、エチレン基(別名:ジメチレン基)、トリメチレン基、プロピレン基(別名:プロパン-1,2-ジイル基)、テトラメチレン基、ブタン-1,2-ジイル基、ブタン-1,3-ジイル基などが挙げられる。これらのうち経済性の観点からメチレン基またはエチレン基が好ましい。
多環脂肪族炭化水素基としては、例えば、ノルボルニル基、イソボルニル基、トリシクロデカニル基、ジシクロペンタジエニル基、アダマンチル基、フェンキル基、デカリン基などが挙げられる。これらのうち、ノルボルニル基、イソボルニル基、トリシクロデカニル基、ジシクロペンタジエニル基、アダマンチル基が好ましい。
アルキル置換単環脂肪族炭化水素基としては、例えば、4-メチルシクロヘキシル基、2-メチルシクロヘキシル基、4-イソプロピルシクロヘキシル基、2-イソプロピルシクロヘキシル基、4-t-ブチルシクロヘキシル基、2-t-ブチルシクロヘキシル基などが挙げられる。これらのうち4-t-ブチルシクロヘキシル基が好ましい。
本発明の共重合体に含まれる構造単位(III)は、透明性の観点からその下限量が、共重合体の質量に対して、好ましくは50質量%、より好ましくは55質量%、さらに好ましくは58質量%、最も好ましくは60質量%であり、耐燃性の観点からその上限量が、共重合体の質量に対して、好ましくは80質量%、より好ましくは75質量%、さらに好ましくは72質量%、最も好ましくは70質量%である。
これらラジカル重合性単量体(4)は、1種単独でまたは2種以上を組み合わせて用いてもよい。なお、「(メタ)アクリル」は「メタクリルまたはアクリル」を意味する。
なお、重量平均分子量および分子量分布は、GPC(ゲルパーミエーションクロマトグラフィ)で測定した標準ポリスチレン換算の値である。
かかる重量平均分子量および分子量分布は、重合開始剤および連鎖移動剤の種類や量などを調整することによって制御できる。
なお、上記したイエロインデックスは、JIS Z8722に準拠して測定した値を元にJIS K7373に準拠して算出した黄色度の値である。
リン系酸化防止剤とヒンダードフェノール系酸化防止剤とを併用する場合、その割合は特に制限されないが、リン系酸化防止剤/ヒンダードフェノール系酸化防止剤の質量比で、好ましくは1/5~2/1、より好ましくは1/2~1/1である。
該熱劣化防止剤としては、2-t-ブチル-6-(3’-t-ブチル-5’-メチル-ヒドロキシベンジル)-4-メチルフェニルアクリレート(住友化学社製;商品名スミライザーGM)、2,4-ジ-t-アミル-6-(3’,5’-ジ-t-アミル-2’-ヒドロキシ-α-メチルベンジル)フェニルアクリレート(住友化学社製;商品名スミライザーGS)などが挙げられる。
紫外線吸収剤としては、ベンゾフェノン類、ベンゾトリアゾール類、トリアジン類、ベンゾエート類、サリシレート類、シアノアクリレート類、蓚酸アニリド類、マロン酸エステル類、ホルムアミジン類などが挙げられる。これらの中でも、ベンゾトリアゾール類、トリアジン類、または波長380~450nmにおけるモル吸光係数の最大値εmaxが100dm3・mol-1cm-1以下である紫外線吸収剤が好ましい。
これら紫外線吸収剤の中、紫外線被照による樹脂劣化が抑えられるという観点からベンゾトリアゾール類が好ましく用いられる。
該重合体粒子は、単一組成比および単一極限粘度の重合体からなる単層粒子であってもよいし、また組成比または極限粘度の異なる2種以上の重合体からなる多層粒子であってもよい。この中でも、内層に5dl/g未満の極限粘度を有する重合体層を有し、外層に5dl/g以上の極限粘度を有する重合体層を有する2層構造の粒子が好ましいものとして挙げられる。高分子加工助剤は、それ全体として、極限粘度が3~6dl/gであることが好ましい。
光拡散剤や艶消し剤としては、ガラス微粒子、ポリシロキサン系架橋微粒子、架橋ポリマー微粒子、タルク、炭酸カルシウム、硫酸バリウムなどが挙げられる。
蛍光体として、蛍光顔料、蛍光染料、蛍光白色染料、蛍光増白剤、蛍光漂白剤などが挙げられる。
繊維としては、ガラス繊維、カーボン繊維などが挙げられる。
積層体の作製法は、特に制限されない。例えば、2種以上の重合体を同時に押出成形する方法(共押出法);2以上の成形体を熱、超音波、高周波などで融着させる方法(融着法);2以上の成形体を紫外線硬化性接着剤、熱硬化性接着剤、放射線硬化性接着剤などで接着する方法(接着法);シートやフィルムなどを金型内にセットしそこに溶融した重合体を流し込んで成形する方法(インサート成形法);他の基材を化学蒸着または物理蒸着によって堆積させる方法(蒸着法);他の基材を含む塗料を塗布して膜を形成する方法(塗布法)等が挙げられる。また、融着法または接着法においては、融着させる面もしくは接着する面を、融着または接着の前に、公知のプライマーで表面処理してもよいし、コロナ放電処理、プラズマ処理などしてもよい。
装置:核磁気共鳴装置(Bruker社製 ULTRA SHIELD 400 PLUS)
溶媒: 重クロロホルム
測定核種: 1H
測定温度: 室温
積算回数: 64回
ゲルパーミエーションクロマトグラフィー(GPC)による測定に基づき、ポリスチレン換算値で共重合体の重量平均分子量および分子量分布を決定した。ここでは、GPC装置として、東ソー株式会社製のHLC-8320(品番)を用い、カラムとして、東ソー株式会社製のTSKgel SuperMultipore HZM-Mの2本とSuperHZ4000の1本を直列に繋いだものを用いた。
溶離剤: テトラヒドロフラン
溶離剤流量: 0.35ml/分
カラム温度: 40℃
検量線: 標準ポリスチレン10点を用いて作成
樹脂ペレットを、230℃にて熱プレス成形し、厚さ3.2mmのシート状の成形体を得た。JIS K7361-1に準じて、村上色彩研究所製、HR-100(品番)を用いて、光路長3.2mmにおける全光線透過率を測定した。
厚さ3.2mmの試験片を用いて、JISK7136に準拠して、ヘイズメータ(村上色彩研究所製、HM-150)を用いて光路長3.2mmにおけるヘイズ(H)を測定した。
厚さ3.2mmの試験片を用いて、日本電色工業株式会社製の測色色差計ZE-2000を用い、JIS Z8722に準拠して光路長3.2mmで測定した値を元にJIS K7373に準拠して算出した黄色度の値をイエロインデックス(YI)とした。
樹脂ペレットを、JIS K7121に準拠して、230℃まで一度昇温し、次いで室温まで冷却し、その後室温から230℃までを10℃/分で昇温させる条件にて示差走査熱量測定法にてDSC曲線を測定した。2回目の昇温時に測定されるDSC曲線から求められる中間点ガラス転移温度を本発明におけるガラス転移温度として採用した。ここでは、測定装置として島津製作所製DSC-50(品番)を用いた。
長さ50mm×幅50mm×厚さ3.2mmの試験片を、50℃、667Pa(5mmHg)の環境下において3日間、乾燥させて、絶乾試験片を得た。絶乾試験片の質量W0を測定した。その後、絶乾試験片を温度23℃の水の中に浸漬させ2ヶ月間放置した。水から引き上げ後、試験片の質量W1を測定した。下式により飽和吸水率(%)を算出した。
飽和吸水率={(W1-W0)/W0}×100
JIS K6911(1995) 5.24 耐燃性 A法に準拠して、耐燃性の評価を行った。樹脂ペレットを、長さ約127mm、幅及び厚さそれぞれ12.7±0.5mmに成形して試験片を用意する。試験片の一端(自由端)から25mm及び100mmの箇所に標線を付けた。バーナーを傾斜角30度の支持台に載せ、鉛直線に対し30度傾斜した状態に保持した。空気の流れを感じない室内で、試験片の長さ方向が水平に、幅方向が水平に対して45°の角度に、試験片下端がバーナー青色炎の先端高さとなるように、一方の端をつかみ具を具備した実験用スタンドに保持した。試験片の自由端の下端に、バーナー青色炎の先端を30度の角度を保持して30秒間接触させ、炎を取り去ると同時にストップウオッチを始動させた。炎は試験片から450mm以上離しておき、試験片の炎が消えたときストップウオッチを止め、その時間を秒単位で読み取り、燃焼時間とした。このとき、試験片の炎が180秒間以上消えない場合は「可燃性」とした。消火後、試験片の燃焼した長さを下端で測り、燃焼距離をミリメートル(mm)単位で測定した。燃焼距離が25mm以下の場合は「不燃性」、25mmを超え100mm以下の場合は「自消性」とした。
15質量部のDEMMPO、15質量部のTCDMA、6質量部のMAA、62質量部のMMA、および2質量部のMAを混合して単量体混合物を得た。この単量体混合物に0.1質量部の重合開始剤(2,2’-アゾビス(2-メチルプロピオニトリル)、水素引抜能:1%、1時間半減期温度:83℃)を加え、溶解させて原料液を得た。
かかる原料液を、撥水処理したガラス板(厚さ10mm、30cm角)2枚と塩化ビニル樹脂製ガスケットより構成されるガラスセルに注入し、10mmHgにて3分間脱気した。このガラスセルを70℃にて2時間、次いで120℃にて2時間保持して単量体混合物を重合させた。次いでガラス板を取り除き、厚さ3.2mmのシート状成形体を得た。得られたシート状成形体から長さ127mm×幅13mm×厚さ3.2mmの試験片を切り出して、耐燃性、透明性および吸水性の評価を行った。
得られたシート状成形体は、非常に高い分子量の重合体で構成されているため溶媒に溶解せず、膨潤するのみであった。そのため、GPCによる分子量の測定はできなかった。推定重量平均分子量は100万g/mol以上である。ホスホネート系単量体(1)であるDEMMPO由来の構造単位(mol%)およびリン原子の含有量(質量%)は、膨潤した状態で1H-NMR測定することにより算出した。結果を表1に示す。
表1または2に示す処方に変えた以外は実施例1と同じ手法によって、厚さ3.2mmのシート状の成形体を得た。これらの試験片の評価を実施例1と同じ手法で実施した。結果を表1または表2に示す。
10質量部のDEMMPO、15質量部のTCDMA、6質量部のMAA、および69質量部のMMAを混合して単量体混合物を得た。この単量体混合物に0.1質量部の重合開始剤(2,2’-アゾビス(2-メチルプロピオニトリル)、水素引抜能:1%、1時間半減期温度:83℃)および0.1質量部の連鎖移動剤(n-オクチルメルカプタン)を加え、溶解させて原料液を得た。
100質量部のイオン交換水、0.03質量部の硫酸ナトリウムおよび0.46質量部の懸濁分散剤を混ぜ合わせて混合液を得た。
耐圧重合槽に、420質量部の前記混合液と210質量部の前記原料液を仕込み、窒素雰囲気下で撹拌しながら、温度を70℃にして重合反応を開始させた。重合反応開始後、3時間経過時に、温度を90℃に上げ、撹拌を引き続き1時間行って、ビーズ状の微粒子が分散した分散液を得た。
得られた分散液を濾過し、微粒子をイオン交換水で洗浄したのち、80℃で4時間、100Paで減圧乾燥し、ビーズ状の共重合体を得た。
得られた共重合体を230℃に制御された二軸押出機に供給して、未反応単量体などの揮発成分を分離除去し、次いで樹脂成分を押出成形してストランドにした。該ストランドをペレタイザーでカットし、ペレット状の成形体とした。
表1に示す処方に変えた以外は実施例3と同じ手法によって、ペレット状の成形体を得た。これらのペレット状の成形体の各種物性測定および試験片の評価を実施例1と同じ手法で実施した。結果を表1に示す。結果を表1に示す。
Claims (10)
- 式(1)で示されるホスホネート系単量体に由来する構造単位(I)と、
メタクリル酸、アクリル酸、式(2a)で示されるラジカル重合性単量体、および式(2b)で示されるラジカル重合性単量体からなる群より選ばれる少なくとも一つのラジカル重合性単量体(2)に由来する構造単位(II)と、
メタクリル酸メチルに由来する構造単位(III)とを含有し、且つ
式(1)で示されるホスホネート系単量体に由来するリン原子の含有量が共重合体の質量に対して1.0質量%以上2.0質量%未満である、共重合体。
(式(1)中、R1は水素原子またはメチル基を表し、R2は炭素数1~4のアルキレン基を表し、R3およびR4はそれぞれ独立に水素原子または炭素数1~10のアルキル基を表す。)
(式(2a)中、R5は、多環脂肪族炭化水素基またはアルキル置換単環脂肪族炭化水素基を表す。)
(式(2b)中、R9は-CH2CHR10R11、-CHR10-CHR11R12または-CR10R11R13表わし、R10、R11およびR13はそれぞれ独立に炭素数1~3のアルキル基を表し、R12は水素原子または炭素数1~3のアルキル基を表わす。) - 構造単位(II)が少なくともメタクリル酸またはアクリル酸に由来する構造単位を含有しており、 メタクリル酸またはアクリル酸に由来する構造単位の合計含有量が共重合体の質量に対して1~12質量%である請求項1に記載の共重合体。
- 構造単位(III)の含有量が共重合体の質量に対して50質量%以上80質量%以下である請求項1または請求項2に記載の共重合体。
- 構造単位(II)の含有量が共重合体の質量に対して5質量%以上30質量%以下である請求項1~3のいずれかひとつに記載の共重合体。
- 構造単位(II)が少なくとも式(2a)で示されるラジカル重合性単量体に由来する構造単位を含有しており、 式(2a)中のR5が、ノルボルニル基、イソボルニル基、トリシクロデカニル基、ジシクロペンタジエニル基、アダマンチル基、または4-t-ブチルシクロヘキシル基である請求項1~4のいずれかひとつに記載の共重合体。
- ガラス転移温度が115℃以上である請求項1~5のいずれかひとつに記載の共重合体。
- 重量平均分子量が15万以上である請求項1~6のいずれかひとつに記載の共重合体。
- 請求項1~7のいずれかひとつに記載の共重合体を含有する成形体。
- 2mm以上の厚さを有する請求項8に記載の成形体。
- 0.1mm以上100mm未満の厚さを有する請求項8に記載の成形体。
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Cited By (4)
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---|---|---|---|---|
JP2017196609A (ja) * | 2016-04-30 | 2017-11-02 | 順造 玉利 | 硫黄や不純物、付着、劣化、を防止する手段 |
WO2018062475A1 (ja) | 2016-09-30 | 2018-04-05 | 株式会社クラレ | ホスホネート基を有する共重合体組成物 |
CN109265598A (zh) * | 2017-07-19 | 2019-01-25 | 上海广大有机玻璃有限公司 | 一种阻燃有机玻璃及其制备方法 |
JP2019217754A (ja) * | 2018-11-09 | 2019-12-26 | 順造 玉利 | 硫黄や不純物、付着、劣化、を防止する手段 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015105050A1 (en) * | 2014-01-07 | 2015-07-16 | Toyo Gosei Co., Ltd. | A composition and a method for manufacturing a component |
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WO2020209263A1 (ja) * | 2019-04-11 | 2020-10-15 | デンカ株式会社 | 共重合体、分散剤、及び樹脂組成物 |
CN112708009A (zh) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | 含磷酸甲酯阻燃聚丙烯腈及其制备方法和应用 |
FR3109780A1 (fr) * | 2020-04-30 | 2021-11-05 | Arkema France | Composition comprenant un copolymère comprenant des monomères de méthacrylate de méthyle et d’acide méthacrylique, son utilisation et objet moulé |
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US11879042B2 (en) | 2021-08-02 | 2024-01-23 | B/E Aerospace, Inc. | Fire resistant thermoplastic-based resin for fiber-reinforced composites |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59179608A (ja) * | 1983-03-31 | 1984-10-12 | Nitto Electric Ind Co Ltd | 光硬化性ヒドロゾル組成物の製造法 |
JPS59179612A (ja) * | 1983-03-31 | 1984-10-12 | Nitto Electric Ind Co Ltd | 光硬化性ヒドロゾル |
JPH08170036A (ja) * | 1994-12-20 | 1996-07-02 | Toray Ind Inc | 艶消し電着塗料組成物 |
EP1479746A2 (de) * | 2003-05-21 | 2004-11-24 | tesa AG | Flammfeste und Hitze-aktivierbare Haftklebemassen |
CN103073963A (zh) * | 2011-10-26 | 2013-05-01 | 比亚迪股份有限公司 | 一种阻燃型反射隔热涂料及其制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5941349A (ja) | 1982-09-01 | 1984-03-07 | Mitsubishi Rayon Co Ltd | 難燃性アクリル系樹脂組成物およびその製造方法 |
JPS61141759A (ja) | 1984-12-14 | 1986-06-28 | Tokuyama Soda Co Ltd | アクリル樹脂材料組成物 |
FR2740775B1 (fr) | 1995-11-06 | 1997-12-05 | Atohaas Holding Cv | Composition pour plaques coulees ignifuges en polymeres (meth)acryliques et plaques obtenues a partir de cette composition |
JPH09302191A (ja) | 1996-05-14 | 1997-11-25 | Mitsubishi Rayon Co Ltd | メタクリル系樹脂組成物 |
JP3577172B2 (ja) | 1996-09-02 | 2004-10-13 | 積水化学工業株式会社 | 難燃性光重合性組成物及びこれを用いた難燃性粘着テープ |
JPH10114848A (ja) | 1996-10-11 | 1998-05-06 | Sumitomo Chem Co Ltd | 近赤外吸収樹脂組成物及び材料 |
JP2003137915A (ja) | 2001-11-05 | 2003-05-14 | Sumitomo Chem Co Ltd | メタクリル酸メチル系樹脂 |
KR20110077881A (ko) * | 2009-12-30 | 2011-07-07 | 제일모직주식회사 | 투명성 및 난연성이 우수한 인계 아크릴계 공중합체 수지 및 그 조성물 |
KR101293787B1 (ko) * | 2010-07-28 | 2013-08-06 | 제일모직주식회사 | 난연성 및 내열성이 우수한 투명 열가소성 수지 조성물 |
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2015
- 2015-08-12 TW TW104126203A patent/TWI691516B/zh not_active IP Right Cessation
- 2015-08-12 KR KR1020177001006A patent/KR20170042554A/ko not_active Application Discontinuation
- 2015-08-12 EP EP15832518.3A patent/EP3181602A4/en not_active Withdrawn
- 2015-08-12 CN CN201580043163.0A patent/CN106574020B/zh not_active Expired - Fee Related
- 2015-08-12 JP JP2016542604A patent/JP6576931B2/ja active Active
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59179608A (ja) * | 1983-03-31 | 1984-10-12 | Nitto Electric Ind Co Ltd | 光硬化性ヒドロゾル組成物の製造法 |
JPS59179612A (ja) * | 1983-03-31 | 1984-10-12 | Nitto Electric Ind Co Ltd | 光硬化性ヒドロゾル |
JPH08170036A (ja) * | 1994-12-20 | 1996-07-02 | Toray Ind Inc | 艶消し電着塗料組成物 |
EP1479746A2 (de) * | 2003-05-21 | 2004-11-24 | tesa AG | Flammfeste und Hitze-aktivierbare Haftklebemassen |
CN103073963A (zh) * | 2011-10-26 | 2013-05-01 | 比亚迪股份有限公司 | 一种阻燃型反射隔热涂料及其制备方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3181602A4 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2017196609A (ja) * | 2016-04-30 | 2017-11-02 | 順造 玉利 | 硫黄や不純物、付着、劣化、を防止する手段 |
WO2018062475A1 (ja) | 2016-09-30 | 2018-04-05 | 株式会社クラレ | ホスホネート基を有する共重合体組成物 |
JPWO2018062475A1 (ja) * | 2016-09-30 | 2019-07-18 | 株式会社クラレ | ホスホネート基を有する共重合体組成物 |
EP3521364A4 (en) * | 2016-09-30 | 2020-03-25 | Kuraray Co., Ltd. | COPOLYMER COMPOSITION COMPRISING A PHOSPHONATE GROUP |
CN109265598A (zh) * | 2017-07-19 | 2019-01-25 | 上海广大有机玻璃有限公司 | 一种阻燃有机玻璃及其制备方法 |
JP2019217754A (ja) * | 2018-11-09 | 2019-12-26 | 順造 玉利 | 硫黄や不純物、付着、劣化、を防止する手段 |
Also Published As
Publication number | Publication date |
---|---|
CN106574020B (zh) | 2019-03-19 |
TWI691516B (zh) | 2020-04-21 |
TW201615676A (zh) | 2016-05-01 |
US20170226249A1 (en) | 2017-08-10 |
KR20170042554A (ko) | 2017-04-19 |
CN106574020A (zh) | 2017-04-19 |
JPWO2016024614A1 (ja) | 2017-06-01 |
JP6576931B2 (ja) | 2019-09-18 |
US10407524B2 (en) | 2019-09-10 |
EP3181602A1 (en) | 2017-06-21 |
EP3181602A4 (en) | 2018-01-17 |
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