WO2017110060A1 - コーティング剤 - Google Patents
コーティング剤 Download PDFInfo
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- WO2017110060A1 WO2017110060A1 PCT/JP2016/005129 JP2016005129W WO2017110060A1 WO 2017110060 A1 WO2017110060 A1 WO 2017110060A1 JP 2016005129 W JP2016005129 W JP 2016005129W WO 2017110060 A1 WO2017110060 A1 WO 2017110060A1
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- 0 COC(C(*)N)=O Chemical compound COC(C(*)N)=O 0.000 description 1
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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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
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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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
- C08J2433/00—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
- C08J2433/04—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
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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
- C08J2433/00—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
- C08J2433/04—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
- C08J2433/06—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
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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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
- C08J2433/00—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
- C08J2433/04—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
- C08J2433/06—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
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—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
- C08J2433/04—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
- C08J2433/14—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 halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms
Definitions
- the present invention relates to a novel coating agent, particularly a coating agent having excellent adhesion to a plastic substrate.
- R represents an acryloyl group, a methacryloyl group, an allyloxycarbonyl group, or an allyl group
- substituents Z 1 ⁇ Z 4 with the four phenyl groups are substituents respectively represented by independently represent the following formula (3), a, b, c, and d each independently 0-3 And the sum (a + b + c + d) is 1 to 4.
- Each of the four phenyl groups independently has a remaining hydrogen atom, or a part or all of the remaining hydrogen atoms are methyl groups.
- a methoxy group, a fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group, i, j, k, and l are each independently 0 or 1.
- R 1 represents a hydrogen atom or a methyl group
- Y represents a single bond, an alkylene group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms.
- An alkylene group having 1 to 12 carbon atoms having an oxygen atom at the terminal of the phenyl group, or a part or all of the hydrogen atoms having an oxygen atom at the terminal of the phenyl group is substituted with a fluorine atom
- a cured product obtained by photopolymerizing a polymerizable compound represented by the following formula: an alkylene group having 1 to 12 carbon atoms is used as an optical element. (See Patent Document 3)
- An object of the present invention is to provide a coating agent that is excellent in adhesion to a plastic substrate such as a cycloolefin resin and can form a base film having transparency and a high refractive index.
- the present inventors have formed a polymer film of the monomer represented by the formula (I) on a plastic substrate such as a cycloolefin resin with excellent adhesion. As a result, the present invention has been completed.
- the present invention (1) Formula (I) (In the formula, Ar represents a C6 to C10 aryl group which may have a substituent. Here, Ar may be the same or different.
- X represents an oxygen atom or —NR—.
- R represents a hydrogen atom or a C1-C6 alkyl group, and Y represents a polymerizable functional group.
- Formula (I) In the formula, Ar represents a C6 to C10 aryl group which may have a substituent.
- Ar may be the same or different.
- X represents an oxygen atom or —NR—.
- R represents a hydrogen atom or a C1-C6 alkyl group
- Y represents a polymerizable functional group.
- the coating agent of the present invention it is possible to form a high refractive index film (coating film) having excellent adhesion to a plastic substrate, particularly a plastic substrate such as a cycloolefin resin.
- a functional film that could not be directly formed on a plastic substrate can be laminated via the coating film of the present invention.
- the coating agent of the present invention contains a polymer having a repeating unit derived from the monomer represented by formula (I) (sometimes referred to as “polymer (I)”).
- Ar represents a C6-C10 aryl group which may have a substituent.
- the C6 to C10 aryl group include a phenyl group, a naphthyl group, and a tetrahydronaphthyl group.
- the “substituent” in “which may have a substituent” include a halogeno group, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C6 -C10 aryl group, and C6-C10 aryloxy group.
- halogeno group examples include a fluoro group, a chloro group, a bromo group, and an iodo group.
- C1-C6 alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, a t-butyl group, Examples thereof include an n-pentyl group and an n-hexyl group.
- C1-C6 alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group, a t-butoxy group, Examples thereof include an n-pentoxy group and an n-hexoxy group.
- C1-C6 alkylthio group examples include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, s-butylthio group, i-butylthio group, t-butylthio group, Examples include n-pentylthio group and n-hexylthio group.
- Specific examples of the C6 to C10 aryl group include a phenyl group and a naphthyl group.
- Specific examples of the C6-C10 aryloxy group include a phenoxy group and a naphthoxy group.
- X represents an oxygen atom or —NR—.
- R represents a hydrogen atom or a C1-C6 alkyl group, and the C1-C6 alkyl group is the same as the C1-C6 alkyl group exemplified as the “substituent” in “may have a substituent”. Groups.
- Y represents a polymerizable functional group.
- polymerizable functional groups include acryloyl group, methacryloyl group, vinyloxycarbonyl group, prop-1-en-2-yloxycarbonyl group, allyloxycarbonyl group, vinyl group, allyl group, and glycidyl group.
- trityl acrylate and trityl methacrylate are preferable.
- the polymer (I) used in the present invention can be used without particular limitation as long as the monomer represented by the formula (I) is polymerized.
- One obtained by polymerizing one type of monomer may be used, or one obtained by polymerizing two or more types of monomers.
- a homopolymer obtained by polymerizing one type of monomer represented by the formula (I) is preferable.
- the polymerization reaction is not particularly limited, and may be a known method for synthesizing polyacrylate, and examples thereof include radical polymerization and anionic polymerization.
- the molecular weight of the polymer (I) to be used is not limited as long as it is within the range that can be applied to the substrate, and examples thereof include polymers having a number average molecular weight within the range of 10,000 to 100,000. .
- the coating agent of the present invention can contain an organic solvent.
- organic solvents that can be used include ether-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ketone-based, and organic halide-based solvents.
- relatively inactive organic solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether can also be used.
- ester systems such as volatile acetates such as propyl acetate, butyl acetate, isoamyl acetate, heptyl acetate, ethyl butyrate, isoamyl isovalerate, etc.
- the organic solvent is preferable.
- the coating agent of the present invention can contain a condensate of an organic silane compound for the purpose of laminating an organic-inorganic composite film. Thereby, a coating film having good adhesion to the substrate can be formed.
- the condensate of the organic silane compound can be produced by using a known silanol condensation method for the organic silane compound represented by the formula (A).
- R 4 represents a C1-C30 alkyl group, a C2-C8 alkenyl group, or a C6-C10 aryl group optionally substituted with an epoxy group, a glycidyloxy group or a (meth) acryloxy group, R 3 represents a hydroxyl group or a hydrolyzable group.
- Examples of the C1-C30 alkyl group in R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group.
- neopentyl group 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, nonyl group, isononyl group, decyl group, lauryl group, tridecyl group , Myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.
- Examples of the C2-C8 alkenyl group include a vinyl group, an allyl group, and a 2-propenyl group.
- the C6 to C10 aryl group include a phenyl group and a naphthyl group.
- the hydrolyzable group of R 3 is a group that can be hydrolyzed to form a silanol group by heating at 25 ° C. to 100 ° C. under non-catalytic conditions or in the presence of excess water.
- examples of the C1-C4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group, and the like, and a C1-C6 acyloxy group.
- examples thereof include an acetyloxy group and a benzoyloxy group.
- examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.
- organic silane compound represented by the formula (A) examples include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3 -Butenyltrimethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, divinyldimethoxysilane, diallyldimethoxysilane, di-3-butenyldimethoxysilane, vinylmethyldimethoxysilane, vinylethyldiethoxysilane, methyltri (meth) acryloxysilane , Methyltris [2- (meth) acryloxyethoxy] silane, methyltriglycidyloxysilane, methyltris (3-methyl-3-oxetanemethoxy) silane, methyltrichlorosilane, methyltrime
- silanol condensation method examples include a method using a silanol condensation catalyst.
- the silanol condensation catalyst is not particularly limited as long as it hydrolyzes a hydrolyzable group in the compound represented by the formula (A) and condenses silanol to form a siloxane bond.
- a silanol condensation catalyst can be used individually by 1 type or in combination of 2 or more types.
- organic metal examples include alkyl metal compounds such as tetramethyl titanium and tetrapropyl zirconium; metal alcoholates such as tetraisopropoxy titanium and tetrabutoxy zirconium; and the like.
- the organic acid metal salt is a compound composed of a salt obtained from a metal ion and an organic acid.
- the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid and benzoic acid; and sulfur-containing organic materials such as sulfonic acid and sulfinic acid. Examples include acids, phenolic compounds, enol compounds, oxime compounds, imide compounds, aromatic sulfonamides, and the like. Specific examples include carboxylic acid metal salts, sulfonic acid metal salts, phenol metal salts, and the like.
- a metal hydroxide is a metal compound having a hydroxide ion as an anion.
- the metal complex is preferably a metal complex having a hydroxyl group or a hydrolyzable group, and more preferably a metal complex having two or more hydroxyl groups or hydrolyzable groups.
- having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.
- the hydrolyzable group include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group, and a C1-C4 alkoxy group and a C1-C4 acyloxy group are preferable.
- ⁇ -ketocarbonyl compounds ⁇ -ketoester compounds, and ⁇ -hydroxyester compounds are preferable.
- methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-acetoacetate ⁇ -ketoesters such as butyl, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane ⁇ -diketones such as 2,4-dione, nonane-2,4-dione and 5-methyl-hexane-2,4-dione; compounds coordinated with hydroxycarboxylic acids such as glycolic acid and lactic acid It is done.
- organic acid metal salts organic acid metal salts, metal hydroxides, and metal complexes, titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), germanium (Ge), indium ( In), tin (Sn), tantalum (Ta), zinc (Zn), tungsten (W), lead (Pb), and the like.
- titanium (Ti), zirconium (Zr), aluminum (Al), Tin (Sn) is preferred, and titanium (Ti) is particularly preferred. These may be used alone or in combination of two or more.
- acids include organic acids and mineral acids.
- organic acids include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid.
- mineral acids include hydrochloric acid. , Nitric acid, boric acid, borohydrofluoric acid and the like.
- a photoacid generator that generates an acid by light irradiation, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like are also included in the acid.
- the base examples include strong bases such as tetramethylguanidine and tetramethylguanidylpropyltrimethoxysilane; organic amines, carboxylic acid neutralized salts of organic amines, quaternary ammonium salts, and the like.
- the compounding ratio of the silanol condensation catalyst is 1:99 to 99: 1, preferably 1:99 to 50:50 with respect to the mass of the organosilane compound.
- Metal compounds, etc. A metal compound can be added to the coating agent of the present invention for the purpose of increasing the refractive index and hardness of the coating film to be formed.
- the metal compound include the organic silane compounds described above, and organic metals exemplified as silanol condensation catalysts, organic acid metal salts, metal hydroxides, and metal chelate compounds.
- Other metal compounds include metal oxides. Specific examples include silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide (zirconia), cobalt oxide metal oxide particles, and the like. Zirconium oxide is particularly preferable.
- colloidal metal oxide particles can also be used as the metal oxide particles of the present invention. Specific examples include colloidal silica and colloidal zirconium, and water-dispersed colloidal or organic solvent-dispersed colloidal metal oxide particles such as methanol or isopropanol.
- a filler may be added and dispersed separately in order to exhibit various properties such as coloring of the coating film, thickening, prevention of UV transmission to the base, provision of corrosion resistance, and heat resistance.
- fillers include water-insoluble pigments such as organic pigments and inorganic pigments, and particulate, fibrous or scale-like metals and alloys other than pigments, and oxides, hydroxides, carbides, nitrides and sulfides thereof. Etc.
- dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium coupling agents, dyes, dispersants, thickeners, leveling agents, etc. These additives can also be added.
- the coating agent of the present invention may contain a copolymerizable compound in addition to the polymer (I).
- the copolymerizable compound may be appropriately selected according to the purpose of adjustment such as the melting point, viscosity, or refractive index, and is not particularly limited, but specific examples include the following.
- the ratio of the polymer (I) to the total amount of the copolymerizable compound other than the polymer (I) contained in the coating agent of the present invention is preferably 30% by mass or more, and more preferably 50% by mass or more.
- the coating agent of this invention may contain the polymerization initiator.
- the polymerization reaction include a photopolymerization reaction and a thermal polymerization reaction, and a photopolymerization reaction that does not have a thermal influence on the plastic substrate is preferable.
- Examples of light used for the photopolymerization reaction include ultraviolet light and visible light, and ultraviolet light having a high polymerization rate is preferable.
- Examples of the photopolymerization initiator include (a) a compound that generates cationic species by light irradiation, and (b) a compound that generates active radical species by light irradiation.
- Examples of the compound that generates a cationic species by light irradiation include, for example, a cation moiety having sulfonium, iodonium, diazonium, ammonium, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe cation.
- the anion moiety is BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , [BX 4 ] ⁇ (X represents a phenyl group substituted with at least two fluorine or trifluoromethyl groups).
- the onium salt comprised is mentioned.
- sulfonium salts include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenyl).
- iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium Examples include hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, and bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate.
- diazonium salt examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate, and the like.
- ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium Tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium And tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate, and the like.
- (2,4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe salt includes (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe.
- compounds that generate active radical species upon irradiation with light include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, Fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl Ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Xanthone, diethylthioxanthone, 2-isopropylthioxan
- the thermal polymerization initiator refers to a compound that generates radicals upon heating, and examples thereof include organic peroxides, azo compounds, and redox initiators.
- the blending amount of the polymerization initiator used in the present invention is preferably 0.01 to 20% by mass, and preferably 0.1 to 10% by mass with respect to the total amount of all copolymerizable compounds other than the polymer (I). Is more preferable.
- a sensitizer can be added as necessary.
- the coating agent of the present invention can contain additional components such as ultraviolet absorbers, dyes, rust preventives, preservatives, etc., as long as the purpose of the present invention is not impaired. .
- the coating agent in the present invention is usually prepared by mixing, in addition to the polymer (I), an organic silane compound condensate, a photopolymerization initiator, a metal compound, and the like in an organic solvent.
- the solid content in the coating agent of the present invention is preferably 1 to 90% by mass, and more preferably 5 to 60% by mass.
- Molded body The molded body of the present invention is obtained by directly providing a film (coating film) obtained by applying the coating agent containing the polymer (I) on a plastic substrate and curing the coating agent.
- the base material on which the coating agent of the present invention can be used is preferably a plastic base material, and examples thereof include cycloolefin resin, polycarbonate resin, acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin, and polyether sulfone.
- a cycloolefin resin is particularly preferably used.
- the coating film of the present invention can be formed by applying the above-described coating agent on a substrate, drying, and heating as necessary.
- light containing ultraviolet rays It can form by passing through the process of irradiating, photopolymerizing, and hardening a coating agent.
- heat polymerization may be performed by heating instead of irradiating light in the step (B).
- the condensate of the organosilane compound represented by Formula (A) the carbon atom content of the surface part of the coating film to be formed is within the coating film (near the joint with the substrate). The composition is smaller than the carbon atom content, and a condensed layer of a condensate of an organosilane compound can be formed on the surface of the coating film.
- the coating method of the coating agent As a coating method of the coating agent, a known coating method can be used. A dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, an ink jet method. Etc. Further, the thickness of the coating film to be formed is not particularly limited, and is about 0.1 to 200 ⁇ m.
- the coating film is preferably dried at 40 to 200 ° C. for about 0.5 to 120 minutes, more preferably at 60 to 120 ° C. for about 1 to 60 minutes.
- Irradiation with ultraviolet rays can be performed using a known apparatus such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp.
- a functional film can be further provided on the coating film of the present invention. Since the coating film of the present invention has very good adhesion to a plastic substrate, the coating film of the present invention can be used as an adhesive layer or an intermediate layer. Conventionally, a functional film that could not be directly formed on a plastic substrate can be laminated via the coating film of the present invention. A plurality of layers can be laminated, and the coating agent of the present invention can be further applied on the plurality of layers and further laminated.
- the functional film examples include a transparent conductive film and a gas barrier film.
- a transparent conductive film indium oxide film doped with tin (ITO film), tin oxide film doped with fluorine (FTO film), zinc oxide film doped with antimony, zinc oxide film doped with indium, etc. Is mentioned.
- the gas barrier film is not particularly limited as long as it has gas barrier properties such as oxygen and water vapor, but is preferably a thin film of an inorganic compound, in particular, titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, A thin film of a metal oxide, metal nitride, metal carbide or a composite thereof having a metal element selected from the group consisting of tungsten and lead is preferred.
- the thickness of these functional films is usually 10 to 300 nm, preferably 10 to 200 nm, more preferably 10 to 100 nm.
- a method of forming a transparent conductive film or gas barrier film made of an inorganic compound on the coating film of the present invention can be formed by a known method, such as a sputtering method, a vacuum deposition method, an ion plating method, etc. Or a chemical method such as a spray method, a dipping method, a thermal CVD method, or a plasma CVD method.
- a film made of silicon oxide can be formed by using a silicon compound sintered in the presence of oxygen gas as a target, and metal silicon can be used as a target in the presence of oxygen.
- a film can also be formed by reactive sputtering.
- a film made of silicon oxynitride can be formed on a substrate by supplying silane gas together with oxygen gas and nitrogen gas into a chamber in which plasma is generated and reacting them.
- a film made of silicon oxide can be formed by using an organic solvent solution containing a silicon compound as an evaporant.
- the functional film by sputtering, vacuum deposition, ion plating, or plasma CVD.
- the surface of the coating film of the present invention may be subjected to plasma treatment or UV ozone treatment in advance as necessary.
- Example 1 Synthesis of trityl methacrylate A 300 mL four-necked flask purged with nitrogen was charged with trityl chloride (20.00 g, 0.072 mol), triethylamine (12.34 g, 0.122 mol), and super-dehydrated tetrahydrofuran (168.89 g). The reaction solution was cooled to 10 ° C. or lower with an ice bath, methacrylic acid chloride (9.88 g, 0.115 mol) was slowly added dropwise, and the reaction solution was warmed to room temperature and reacted for 24 hours.
- trityl chloride 20.00 g, 0.072 mol
- triethylamine (12.34 g, 0.122 mol
- super-dehydrated tetrahydrofuran 168.89 g
- Example 2 Synthesis of tris (4-methylphenyl) methyl methacrylate A nitrogen-substituted 100 mL four-necked flask was charged with chlorotris (4-methylphenyl) methane (2.00 g, 0.006 mol), triethylamine (1.07 g, 0.011 mol), And ultra-dehydrated tetrahydrofuran (15.74 g) were charged. The reaction solution was cooled to 10 ° C. or lower with an ice bath, methacrylic acid chloride (0.86 g, 0.010 mol) was slowly added dropwise, and the reaction solution was warmed to room temperature and reacted for 24 hours.
- Example 3 Synthesis of tris (4-chlorophenyl) methyl methacrylate Into a nitrogen-substituted 100 mL four-necked flask, chlorotris (4-chlorophenyl) methane (5.00 g, 0.013 mol), triethylamine (2.26 g, 0.022 mol) and ultra-dehydration Tetrahydrofuran (36.30 g) was charged. The reaction solution was cooled to 10 ° C. or lower with an ice bath, methacrylic acid chloride (1.81 g, 0.021 mol) was slowly added dropwise, and the reaction solution was warmed to room temperature and reacted for 24 hours.
- chlorotris (4-chlorophenyl) methane 5.00 g, 0.013 mol
- triethylamine 2.26 g, 0.022 mol
- ultra-dehydration Tetrahydrofuran 36.30 g
- Example 4 Synthesis of tris (3,5-dimethylphenyl) methyl methacrylate Into a nitrogen-substituted 100 mL four-necked flask, chlorotris (3,5-dimethylphenyl) methane (5.00 g, 0.01381 mol), triethylamine (2.37 g, 0 0.0347 mol) and ultra-dehydrated tetrahydrofuran (37.11 g) were charged. The reaction solution was cooled to 10 ° C. or lower with an ice bath, methacrylic acid chloride (1.90 g, 0.02209 mol) was slowly added dropwise, and the reaction solution was warmed to room temperature and reacted for 24 hours.
- chlorotris (3,5-dimethylphenyl) methane 5.00 g, 0.01381 mol
- triethylamine (2.37 g, 0 0.0347 mol
- ultra-dehydrated tetrahydrofuran 37.11
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Abstract
Description
本願は、2015年12月21日に出願された日本国特許出願第2015-248224号に対し優先権を主張し、その内容をここに援用する。
また下記式(2)
一方、シクロオレフィン樹脂は、光学レンズ、光学部品、又は医療用として広く使用されているが、その表面改質を行うための密着性に優れたプライマー層は知られていなかった。
本発明は、シクロオレフィン樹脂等のプラスチック基材との密着性に優れ、透明性と高屈折率を有する下地膜を形成することができるコーティング剤を提供することを課題とする。
(1)式(I)
(2)式(I)
(3)式(I)中、Yがアクリロイル基又はメタクリロイル基である(1)又は(2)に記載のコーティング剤、
(4)コーティング剤が、プラスチック基材上へのコーティング剤である(1)~(3)のいずれかに記載のコーティング剤、及び
(5)プラスチック基材が、ポリオレフィン樹脂基材である(4)に記載のコーティング剤に関する。
〔式(I)で表されるモノマー〕
本発明のコーティング剤は、式(I)で表されるモノマー由来の繰り返し単位を有するポリマー(「ポリマー(I)」と言うことがある。)を含有する。
C6~C10のアリール基としては、具体的には、フェニル基、ナフチル基、テトラヒドロナフチル基等が挙げられる。
「置換基を有してもよい」における「置換基」としては、具体的には、ハロゲノ基、水酸基、C1~C6のアルキル基、C1~C6のアルコキシ基、C1~C6のアルキルチオ基、C6~C10のアリール基、及びC6~C10のアリールオキシ基が挙げられる。
C1~C6のアルキル基としては、具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、s-ブチル基、i-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基等が挙げられる。
C1~C6のアルコキシ基としては、具体的には、メトキシ基、エトキシ基、n-プロポキシ基、i-プロポキシ基、n-ブトキシ基、s-ブトキシ基、i-ブトキシ基、t-ブトキシ基、n-ペントキシ基、n-ヘキソキシ基等が挙げられる。
C1~C6のアルキルチオ基としては、具体的には、メチルチオ基、エチルチオ基、n-プロピルチオ基、i-プロピルチオ基、n-ブチルチオ基、s-ブチルチオ基、i-ブチルチオ基、t-ブチルチオ基、n-ペンチルチオ基、n-ヘキシルチオ基等が挙げられる。
C6~C10のアリール基としては、具体的には、フェニル基、ナフチル基等が挙げられる。
C6~C10のアリールオキシ基としては、具体的には、フェノキシ基、ナフトキシ基等が挙げられる。
本発明に用いるポリマー(I)は、式(I)で表されるモノマーを重合したものであれば、特に制限なく使用することができる。1種類のモノマーを重合したものでよいし、2種類以上のモノマーを重合したものでもよい。特には、式(I)で表される1種類のモノマーを重合したホモポリマーであることが好ましい。重合反応は、特に制限されず、ポリアクリレートを合成する公知の方法であってもよく、例えば、ラジカル重合、アニオン重合等を挙げることができる。用いるポリマー(I)の分子量は、基材上への塗布可能な範囲内であれば、制限はなく、例えば、10,000~100,000の範囲内の数平均分子量のポリマーを挙げることができる。
(有機溶媒)
本発明のコーティング剤には、有機溶媒を含むことができる。使用可能な代表的有機溶媒としては、エーテル系、エステル系、脂肪族炭化水素系、芳香族炭化水素系、ケトン系、有機ハロゲン化物系等が挙げられる。
エーテル系の有機溶媒としてはジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、ジアミルエーテル;エステル系の有機溶媒としてはエチルアセテート、プロピルアセテート、ブチルアセテート、アミルアセテート、ヘプチルアセテート、エチルブチレート、イソアミルイソバリレート;脂肪族系炭化水素系の有機溶媒としてはノルマルヘキサン、ノルマルヘプタン、シクロヘキサン;芳香族系の有機溶媒としてはトルエン、キシレン;ケトン系の有機溶媒としてはメチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン;有機ハロゲン化物系の有機溶媒としてはトリクロロエタン、トリクロロエチレン;等が挙げられる。さらには、プロピレングリコールモノメチルエーテルやプロピレングリコールモノエチルエーテルなどの比較的非活性な有機溶媒も使用可能である。
中でも、本発明が自然環境下の開放系で用いられることが多いことを考慮すると、揮発性を有するプロピルアセテート、ブチルアセテート、イソアミルアセテート、ヘプチルアセテート、エチルブチレート、イソアミルイソバリレートなどのエステル系の有機溶媒が好ましい。
本発明のコーティング剤には、有機無機複合膜を積層することを目的として、有機シラン化合物の縮合物を含有することができる。これによって、基材と接着性のよいコーティング膜を形成することができる。
R4Si(R3)3 (A)
C2~C8のアルケニル基としては、ビニル基、アリル基、2-プロペニル基等が挙げられる。
C6~C10のアリール基としては、フェニル基、ナフチル基等が挙げられる。
ここで、光照射によって酸を発生する光酸発生剤、具体的には、ジフェニルヨードニウムヘキサフルオロホスフェート、トリフェニルホスホニウムヘキサフルオロホスフェート等も酸に包含される。
本発明のコーティング剤には、形成されるコーティング膜の屈折率や硬度を上げることを目的として、金属化合物を添加することができる。金属化合物としては、前述の有機シラン化合物や、シラノール縮合触媒として例示された有機金属、有機酸金属塩、金属水酸化物、金属キレート化合物が挙げられるが、それら以外の金属化合物としては、金属酸化物が挙げられ、具体的には、二酸化ケイ素、酸化チタン、酸化アルミニウム、酸化クロム、酸化マンガン、酸化鉄、酸化ジルコニウム(ジルコニア)、酸化コバルトの金属酸化物粒子等が挙げられる。特に酸化ジルコニウムが好ましい。
粒子の形状としては、球状、多孔質粉末、鱗片状、繊維状等が挙げられるが、多孔質粉末状であることがより好ましい。
また、本発明の金属酸化物粒子としては、コロイド状金属酸化物粒子も使用できる。具体的には、コロイド状シリカ、コロイド状ジルコニウムを挙げることができ、水分散コロイド状、あるいはメタノール若しくはイソプロパノールなどの有機溶媒分散コロイド状の金属酸化物粒子を挙げることができる。
その他、オルトギ酸メチル、オルト酢酸メチル、テトラエトキシシランなどの公知の脱水剤、各種界面活性剤、前記以外のシランカップリング剤、チタンカップリング剤、染料、分散剤、増粘剤、レベリング剤などの添加剤を添加することもできる。
本発明のコーティング剤は、ポリマー(I)以外に、共重合性化合物を含んでいてもよい。
また、本発明のコーティング剤は、重合開始剤を含んでいてもよい。ここで、重合反応としては、光重合反応や熱重合反応等が挙げられるが、プラスチック基材への熱的影響がない光重合反応が好ましい。光重合反応に用いる光線としては、紫外線又は可視光線が挙げられるが、重合速度が速い紫外線が好ましい。
本発明におけるコーティング剤は、通常、有機溶媒中に前記ポリマー(I)のほか、必要に応じて、前記有機シラン化合物の縮合物、光重合開始剤、金属化合物等を混合して調製される。本発明のコーティング剤中の固形分は、1~90質量%であることが好ましく、5~60質量%であることがより好ましい。
本発明の成形体は、上記ポリマー(I)を含有するコーティング剤を、プラスチック基材上に塗布し、前記コーティング剤を硬化させた膜(コーティング膜)を直接設けたものである。
本発明のコーティング剤が使用できる基材としては、プラスチック基材が好ましく、例えば、シクロオレフィン樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリイミド樹脂、ポリエステル樹脂、エポキシ樹脂、液晶ポリマー樹脂、ポリエーテルスルフォンが挙げられるが、特に、シクロオレフィン樹脂が好適に用いられる。
本発明のコーティング膜は、共重合性化合物の重合を必要としない場合は、上述したコーティング剤を基材上に塗布し、乾燥、必要に応じて加熱する工程を経ることにより形成できる。
さらに、式(A)で表わされる有機シラン化合物の縮合物を含有する場合は、形成されるコーティング膜の表面部の炭素原子含有量が、コーティング膜の内部(基材との接合部付近)の炭素原子含有量に比して少ない構成となり、コーティング膜の表面に有機シラン化合物の縮合物の濃縮層を形成することができる。
必要に応じて、本発明のコーティング膜の上に、さらに機能性膜を設けることができる。
本発明のコーティング膜は、非常にプラスチック基材と密着性がよいため、本発明のコーティング膜を接着層又は中間層として用いることができる。従来、プラスチック基材に直接形成することができなかった機能性膜を、本発明のコーティング膜を介して積層させることができる。複数層を積層することができ、また、本発明のコーティング剤を複数層上にさらに塗布し、さらに積層することもできる。
透明導電膜としては、スズがドープされた酸化インジウム膜(ITO膜)、フッ素がドープされた酸化スズ膜(FTO膜)、アンチモンがドープされた酸化亜鉛膜やインジウムがドープされた酸化亜鉛膜等が挙げられる。
ガスバリア膜は、酸素、水蒸気等のガスバリア性を有する限り特に制限はないが、好ましくは、無機化合物の薄膜であり、特に、チタン、ジルコニウム、アルミニウム、ケイ素、ゲルマニウム、インジウム、スズ、タンタル、亜鉛、タングステン及び鉛から成る群より選ばれた金属元素を有する金属酸化物、金属窒化物、金属炭化物又はそれらの複合物の薄膜が好ましい。
1.トリチルメタクリレートの合成
窒素置換した300mL四ツ口フラスコに、トリチルクロライド(20.00g、0.072mol)、トリエチルアミン(12.34g、0.122mol)、及び超脱水テトラヒドロフラン(168.89g)を仕込んだ。反応溶液を氷浴で10℃以下に冷却し、メタクリル酸クロライド(9.88g、0.115mol)をゆっくり滴下し、さらに反応液を室温まで昇温し、24時間反応を行った。反応終了後、反応溶液を飽和重曹水で水洗し、有機層中のTHFをエバポレーターで留去した。その後、ヘキサンで再結晶する事で、トリチルメタクリレート19.34g(収率82%)を得た。
得られたトリチルメタクリレートのNMRデータを以下に示す。
1H NMR(アセトン-d6、500 MH、300K、TMS):7.2-7.5, 6.2, 5.7, 1.9-2.0 ppm
ポリマーは、アゾビスイソブチロニトリル(AIBN)を開始剤としたラジカル重合反応で作製した。
実施例1で合成したトリチルメタクリレート(2.00g、0.006mol)と、AIBN(20mg、0.12mmol)を、50mLシュレンク管に仕込んだ。撹拌子を入れ、三方コックで密閉した後、窒素入りのガス採取袋を設置した。真空ポンプで系中の脱気を行った後、窒素置換した。続いて、脱酸素トルエン(8.00mL)を加え、65℃のオイルバスで24時間加熱することで、ラジカル重合反応を行った。反応終了後、反応液をメタノール中に加えることで再沈殿を行った。これを、ベンゼン/ヘキサン混合溶媒で分別してオリゴマーを取り除き、不溶分としてポリマーを得た。
GPCからポリマーの数平均分子量(Mn)は、39631Daであった。
ポリ(トリチルメタクリレート)(0.1g)を、THF/シクロヘキサノン=5/5(v/v)(9.9g)に加熱溶解させることで、固形分濃度1wt%のコーティング剤(A-1)を得た。
厚さ188μmのシクロオレフィンポリマー(COP)フィルム(製品名「ZEONOR Film ZF-16」、日本ゼオン社製)を50mm×50mmにカットし、コーティング剤(A-1)をバーコートで成膜した。コートしたフィルムを、オーブン内で乾燥(120℃、3分間)することで、成形体(A-2)を得た。
1.トリス(4-メチルフェニル)メチルメタクリレートの合成
窒素置換した100mL四ツ口フラスコに、クロロトリス(4-メチルフェニル)メタン(2.00g、0.006mol)、トリエチルアミン(1.07g、0.011mol)、及び超脱水テトラヒドロフラン(15.74g)を仕込んだ。反応溶液を氷浴で10℃以下に冷却し、メタクリル酸クロライド(0.86g、0.010mol)をゆっくり滴下し、さらに反応液を室温まで昇温し、24時間反応を行った。反応終了後、反応溶液を飽和重曹水で水洗し、有機層中のTHFをエバポレーターで留去した。その後、ヘキサンで再結晶することで、トリス(4-メチルフェニル)メチルメタクリレート(1.805g、収率78%)を得た。
得られたトリス(4-メチルフェニル)メチルメタクリレートのNMRデータを以下に示す。
1H NMR(アセトン-d6、500 MH、300K、TMS):7.2-7.3, 7.1-7.15, 6.15-6.2, 5.6-5.7, 2.3, 1.9-2.0 ppm。
ポリマーは、トリス(4-メチルフェニル)メチルメタクリレート(2.00g、0.005 mol)、AIBN(5.9mg、0. 04mmol)を使用する以外は、実施例1と同様の手法で作製した。
GPCからポリマーの数平均分子量(Mn)は、42301Daであった。
ポリ{トリス(4-メチルフェニル)メチルメタクリレート}(0.1g)、THF/シクロヘキサノン =5/5 (v/v)(9.9g)に加熱溶解させることで、固形分濃度1wt%のコーティング剤(B-1)を得た。
コーティング剤に(B-1)を使用する以外は、実施例1と同様の操作で行い、成形体(B-2)を得た。
1.トリス(4-クロロフェニル)メチルメタクリレートの合成
窒素置換した100mL四ツ口フラスコに、クロロトリス(4-クロロフェニル)メタン(5.00g、0.013mol)、トリエチルアミン(2.26g、0.022mol)そして超脱水テトラヒドロフラン(36.30g)を仕込んだ。反応溶液を氷浴で10℃以下に冷却し、メタクリル酸クロライド(1.81 g、0.021mol)をゆっくり滴下し、さらに反応液を室温まで昇温し、24時間反応を行った。反応終了後、反応溶液を飽和重曹水で水洗し、有機層中のTHFをエバポレーターで留去した。その後、ヘキサンで再結晶することで、トリス(4-クロロフェニル)メチルメタクリレート(4.58g、収率81%)を得た。
得られたトリス(4-クロロフェニル)メチルメタクリレートのNMRデータを以下に示す。
1H NMR(アセトン-d6、500 MH、300K、TMS): 7.25-7.4, 6.08, 5.61, 1.90 ppm。
ポリマーは、トリス(4-クロロフェニル)メチルメタクリレート(2.00g、0.005mol)、AIBN(5.1mg、0. 03mmol)を使用する以外は、実施例1と同様の手法で作製した。
GPCからポリマーの数平均分子量(Mn)は、47011Daであった。
ポリ{トリス(4-クロロフェニル)メチルメタクリレート}(0.1g)をTHF/シクロヘキサノン=5/5 (v/v) (9.9 g)に加熱溶解させることで、固形分濃度1wt%のコーティング剤(C-1)を得た。
コーティング剤に(C-1)を使用する以外は、実施例1と同様の操作で行い、成形体(C-2)を得た。
1.トリス(3,5-ジメチルフェニル)メチルメタクリレートの合成
窒素置換した100mL四ツ口フラスコに、クロロトリス(3,5-ジメチルフェニル)メタン(5.00g、0.01381mol)、トリエチルアミン(2.37g、0.02347mol)、そして超脱水テトラヒドロフラン(37.11g)を仕込んだ。反応溶液を氷浴で10℃以下に冷却し、メタクリル酸クロライド(1.90g、0.02209mol)をゆっくり滴下し、さらに反応液を室温まで昇温し、24時間反応を行った。反応終了後、反応溶液を飽和重曹水で水洗し、有機層中のTHFをエバポレーターで留去した。その後、ヘキサンで再結晶することで、トリス(3,5-ジメチルフェニル)メチルメタクリレート(4.50g、収率79%)を得た。
得られたトリス(3,5-ジメチルフェニル)メチルメタクリレートのNMRデータを以下に示す。
1H NMR(アセトン-d6、500 MH、300K、TMS): 7.03, 6.75, 6.0, 5.6, 2.2, 1.9 ppm。
2.ポリ{トリス(3,5-ジメチルフェニル)メチルメタクリレート}の作製
ポリマーは、トリス(3,5-ジメチルフェニル)メチルメタクリレート(2.00g、0.00485mol)、AIBN(4.0mg、0.024mmol)を使用する以外は、実施例1と同様の手法で作製した。GPCからポリマーの数平均分子量(Mn)は、48231Daであった。
3.コーティング剤の調製
ポリ{トリス(3,5-ジメチルフェニル)メチルメタクリレート}0.1gをTHF/シクロヘキサノン =5/5(v/v)(9.9g)に加熱溶解させることで、固形分濃度 1wt%のコーティング剤(D-1)を得た。
4.コーティング膜の形成
コーティング剤に(D-1)を使用する以外は、実施例1と同様の操作で行い、成形体(D-2)を得た。
上記の実施例で得られた成形体(A-2)、(B-2)、(C-2)、及び成形体(D-2)について、碁盤目剥離試験をJIS K-5400(1999年)に記載された碁盤目テープ剥離試験法に準じて行った。
それぞれの成形体上のコーティング膜を1mm×1mmの碁盤目状にクロスカットし、透明粘着テープを用いて剥離試験を行なった。結果を表1に示す。
いずれのコーティング膜ともCOPフィルム上からの剥離は見られなかった。
Claims (5)
- 式(I)中、Yがアクリロイル基又はメタクリロイル基である請求項1又は2に記載のコーティング剤。
- コーティング剤が、プラスチック基材上へのコーティング剤である請求項1~3のいずれかに記載のコーティング剤。
- プラスチック基材が、ポリオレフィン樹脂基材である請求項4に記載のコーティング剤。
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