WO2015163380A1 - Copolymère fluoré ayant un groupe hydrophile, et agent de modification de surface contenant ledit copolymère - Google Patents

Copolymère fluoré ayant un groupe hydrophile, et agent de modification de surface contenant ledit copolymère Download PDF

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Publication number
WO2015163380A1
WO2015163380A1 PCT/JP2015/062296 JP2015062296W WO2015163380A1 WO 2015163380 A1 WO2015163380 A1 WO 2015163380A1 JP 2015062296 W JP2015062296 W JP 2015062296W WO 2015163380 A1 WO2015163380 A1 WO 2015163380A1
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fluorine
containing copolymer
meth
group
represented
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PCT/JP2015/062296
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English (en)
Japanese (ja)
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豊 市原
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株式会社ネオス
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Priority to CN201580020237.9A priority Critical patent/CN106232644B/zh
Priority to JP2016515188A priority patent/JP6479774B2/ja
Priority to KR1020167029335A priority patent/KR102279540B1/ko
Publication of WO2015163380A1 publication Critical patent/WO2015163380A1/fr

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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
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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

Definitions

  • the present invention is a fluorine-containing copolymer that can be used as a surface modifier that is used in the fields of glass, resins, films, optical materials, paints, etc., and that has a more hydrophilic surface and excellent surface smoothness.
  • the present invention relates to a polymer or a reactive fluorine-containing copolymer, a surface modifier containing the fluorine-containing copolymer or a reactive fluorine-containing copolymer, an active energy ray-curable coating liquid, and a cured film.
  • fluorine-containing copolymer and the reactive fluorine-containing copolymer may be collectively referred to simply as “fluorine-containing copolymer”.
  • Various additives are added to coating liquids used in the fields of resins, optical materials, paints and the like for the purpose of imparting various properties to the coating film.
  • a leveling agent which is a surfactant such as hydrocarbon, fluorine or silicone is used.
  • fluorine-based or silicone-based leveling agents have high surface smoothness and are widely used in general.
  • Fluorine-based or silicone-based surfactants have a high surface tension reducing ability, and the coating surface containing them exhibits water repellency. If an attempt is made to apply a water-soluble or water-based paint or the like on the surface of these coating films, it causes repelling, and there is a problem that post-processing is difficult due to poor coating. On the other hand, hydrocarbon-based leveling agents are unlikely to cause such coating defects but have low surface smoothness.
  • Patent Document 1 a method has been proposed in which an ionic surfactant is added to a hard coat coating solution to make the surface hydrophilic and thereby improve coating failure.
  • this method may impair basic performance such as hardness inherent in the resin composition.
  • the solvent of the hard coat coating liquid to which the ionic surfactant is added is methanol, and the surfactant is not sufficiently dissolved in the ketone-based and ester-based organic solvents generally used in the UV curing hard coat. There is a case.
  • the present invention improves the surface of glass, resin, film, optical material, paint, etc. to a more hydrophilic tendency, and at the same time, is a fluorine-containing copolymer that can be used as a surface modifier having excellent surface smoothness and surface modification.
  • the purpose is to provide a quality agent. Moreover, it aims at providing the active energy ray hardening-type coating liquid and cured film containing these.
  • the present invention provides the fluorine-containing copolymer, the reactive fluorine-containing copolymer, the surface modifier, the active energy ray-curable coating liquid, and the cured film according to items 1 to 11 below.
  • Item 1 A fluorine-containing copolymer containing at least (meth) acrylate compounds represented by general formulas A and C as monomer units, wherein the fluorine-containing copolymer is a radical polymerization reaction represented by general formula (I).
  • Fluorine-containing copolymer comprising a residue of a chain transfer agent: [Wherein Rf is a group represented by the following formula (1) or (2). R 1 is a divalent group having 2 to 50 carbon atoms. R 2 is H or a methyl group. ] [R 5 is H or a methyl group. EO is an ethylene oxide group, n is the number of repeating units, and is an integer of 2 to 20. R 6 is H or a methyl group. ] [R 7 is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms. Z represents COOH or OH, and x is an integer of 1 or 2. ].
  • Item 2 Furthermore, the following general formula B: [R 3 is an optionally substituted divalent group. R 4 is H or a methyl group. ] Item 2.
  • Item 3 The fluorine-containing copolymer according to item 1 or 2, wherein the chain transfer agent is represented by the following general formula D: [R 8 is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms. Z represents COOH or OH, and x is an integer of 1 or 2. ].
  • Item 4 The fluorine-containing copolymer according to any one of Items 1 to 3, wherein the fluorine content in the copolymer is 1% to 15% by mass.
  • Item 5 The fluorine-containing copolymer according to any one of Items 2 to 4, wherein the mass ratio of the (meth) acrylate compounds represented by the general formulas B and C is a ratio of 0.2 ⁇ B / C ⁇ 2.
  • Item 6 A fluorine-containing copolymer obtained by reacting a hydroxyl group in the fluorine-containing copolymer according to any one of Items 1 to 5 with a (meth) acrylate compound having an isocyanate group represented by the following general formula E: [Wherein R 9 is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). It is. R 10 represents H or a methyl group. y is an integer of 1 or 2. ]
  • Item 7 Among the monomer units constituting the fluorine-containing copolymer, when the number of moles of the (meth) acrylate compound having a hydroxyl group is p and the number of moles of the (meth) acrylate compound represented by the general formula E is q, the mole ratio Item 7.
  • Item 8 The contact angle of water on the surface of the cured film obtained by curing the active energy ray-curable coating liquid containing the fluorine-containing copolymer is lower than the contact angle when no fluorine-containing copolymer is added.
  • Item 8 The fluorine-containing copolymer according to any one of Items 1 to 7,
  • Item 9 Item 9. A surface modifier containing the fluorine-containing copolymer according to any one of Items 1 to 8.
  • Item 10 An active energy ray-curable coating solution containing the fluorine-containing copolymer according to any one of Items 1 to 8, a polyfunctional (meth) acrylic compound, and a photopolymerization initiator.
  • Item 11 Item 11. A cured film obtained by curing the active energy ray-curable coating liquid according to Item 10.
  • the fluorine-containing copolymer of the present invention can reduce the contact angle of water on the surface of a resin, film, fiber, glass, metal, etc., and at the same time can impart smoothness. Therefore, the fluorine-containing copolymer of the present invention is useful as a surface modifier for making these surfaces hydrophilic and imparting surface smoothness.
  • (meth) acrylate means acrylate and / or methacrylate.
  • Fluorine-containing copolymer The fluorine-containing copolymer of the present invention can be obtained by radical polymerization of the general formulas A and C and, if necessary, other (meth) acrylate compounds (monomer units). Since the chain transfer agent represented by the general formula D is used in the radical polymerization reaction, the fluorine-containing copolymer of the present invention has a COOH group or an OH group at the end of the main chain.
  • (meth) acrylate compounds other than (meth) acrylate compounds represented by general formulas A and C (meth) acrylate compounds represented by general formula B, (meth) acrylate compounds represented by general formula F, Or it is preferable to use 2 or more types of those compounds.
  • the use of the (meth) acrylate compound represented by the general formula B is preferable in that hydrophilicity is improved and a functional group such as a (meth) acryloyl group can be introduced by reacting with the general formula E.
  • Use of the (meth) acrylate compound represented by the general formula F is preferable in terms of improving hydrophilicity and improving compatibility with the resin composition.
  • Use of the (meth) acrylate compound represented by the general formula E is preferable in that a group capable of reacting with the UV curable resin can be introduced.
  • a copolymer obtained by polymerizing a monomer containing at least a (meth) acrylate compound represented by general formulas A and C is referred to as a “fluorinated copolymer” in the present specification, and is represented by A, C, or the like.
  • the copolymer obtained by further reacting the copolymer obtained by polymerizing the monomer containing the (meth) acrylate compound and the (meth) acrylate compound represented by the general formula E is an acrylate-derived reactivity. In particular, it may be described as a “reactive fluorine-containing copolymer”.
  • the fluorine content in the copolymer is preferably 1% to 15% by mass, more preferably 2 to 14%, still more preferably 3 to 13%, and even more preferably 4 to 12%. Practically, it can be used in a narrower range of 1 to 10%, and more narrow range of 2 to 8%.
  • the fluorine content of the fluorinated copolymer is represented by ((fluorine atom weight ⁇ number of fluorine atoms in the entire copolymer) ⁇ 100 / mass of the entire copolymer). If the fluorine content is too large, water and oil repellency is exhibited due to the effect of fluorine, which is not suitable because hydrophilicity is not exhibited.
  • the (meth) acrylate compound represented by the general formula A (sometimes referred to as “compound A”) is represented by the following formula.
  • Rf is a group represented by the following formula (1) or (2).
  • R 1 is a divalent group having 2 to 50 carbon atoms, preferably 2 to 10 carbon atoms.
  • R 2 is H or a methyl group.
  • X is preferably 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, particularly preferably 1,4-phenylene.
  • Y is preferably —CO—O—.
  • R 2 is H or a methyl group, preferably a methyl group.
  • the (meth) acrylate compound represented by the general formula A can be produced by a known method.
  • the content of Compound A is 2 to 30% by mass of the total (meth) acrylate compound, preferably 4 to 18% by mass.
  • the (meth) acrylate compound represented by general formula C (sometimes referred to as “compound C”) in the fluorine-containing copolymer of the present invention is represented by the following formula.
  • R 5 is H or a methyl group.
  • EO is an ethylene oxide group
  • n is the number of repeating units and is 2 to 20.
  • R 6 is H or a methyl group.
  • (EO) n represents an ethylene oxide group having 2 to 20 repeating units, and the number of repeating units of the ethylene oxide group is preferably 4 to 15.
  • the compound represented by the general formula C can be produced by a known method, or can be obtained as a commercial product.
  • commercial products of the compound represented by the general formula C Blemmer AE-90 manufactured by NOF Corporation, Blemmer AE-200 manufactured by NOF Corporation, Blemmer AE-400 manufactured by NOF Corporation, Japan Examples include Blemmer AME-90 manufactured by Oil Co., Ltd., Blemmer AME-200 manufactured by NOF Corporation, Blemmer AME-400 manufactured by NOF Corporation, Blemmer PE-350 manufactured by NOF Corporation, and the like. .
  • R 5 in the (meth) acrylate compound represented by the general formula C is H
  • a compound in which R 5 in the (meth) acrylate compound represented by the general formula C is methyl can be used in combination.
  • the compound in which R 5 is methyl can be used in the same amount or less than the compound in which R 5 is H.
  • the compound in which R 5 in the (meth) acrylate compound represented by the general formula C is H is used as the (meth) acrylate compound represented by the general formula C
  • the (meth) represented by the general formula E Acrylate compounds can be used.
  • the amount of compound C used is 2 to 8 parts by mass with respect to the amount of compound A used by 1 part by mass.
  • (meth) acrylate compounds represented by general formulas B and F other than general formulas A and C and a mixture of two or more thereof can be used as a copolymerization component.
  • the (meth) acrylate compound represented by the general formula B (sometimes referred to as “compound B”) is represented by the following formula.
  • R 3 is a divalent group which may be substituted.
  • R 4 is H or a methyl group.
  • examples of the divalent group having 2 to 50 carbon atoms represented by R 3 include the divalent groups exemplified for the above R 3 .
  • the divalent group preferably has 2 to 30 carbon atoms.
  • the compound represented by the general formula B can be produced by a known method, or can be obtained as a commercial product.
  • Commercially available products of the compound represented by the general formula B include 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester HO-250), 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester). HOA), 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., 4-HBA) and the like.
  • the mass ratio of the (meth) acrylate compound represented by the general formulas B and C is a ratio of 0.2 ⁇ B / C ⁇ 2, particularly Preferably 0.4 ⁇ B / C ⁇ 1.
  • the (meth) acrylate compound represented by the general formula F (sometimes referred to as “compound F”) is represented by the following formula.
  • R 11 is H or a group having 1 to 20 carbon atoms.
  • R 12 is H or a methyl group.
  • preferred compounds in general formula F include Methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, lauryl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, acrylic acid, methacrylic acid, benzyl methacrylate, etc., preferably methacrylic acid, tetrahydrofurfuryl methacrylate, etc., more preferably Methacrylic acid is mentioned.
  • Compound F is used in an amount of 1 to 4 parts by mass with respect to 1 part by mass of Compound A.
  • the fluorine-containing copolymer of the present invention uses a thiol compound represented by the general formula D (sometimes referred to as “compound D”) as a chain transfer agent in the copolymerization reaction, and the thiol compound is represented by the following formula. Is done.
  • R 8 is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms.
  • Z represents COOH or OH, and x is an integer of 1 or 2.
  • the thiol compound represented by the general formula D is not particularly limited as long as it causes chain transfer.
  • R 8 is divalent, R 8 is preferably an alkanediyl group, where x is 1.
  • R 8 is trivalent, R 8 is preferably an alkanetriyl group, where x is 2.
  • Specific examples of the compound represented by the general formula D include, for example, thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercapto-2-methylpropionic acid, 4-mercaptobutanoic acid, 3-mercapto.
  • the compound represented by the general formula D can be produced by a known method, or can be obtained as a commercial product.
  • Particularly preferred compounds include mercaptopropionic acid, 3-mercapto-1,2-propanediol, and particularly mercaptopropionic acid.
  • COOH or an OH group can be introduced into the main chain terminal of the copolymer of the present invention.
  • the amount of the compound D is 0.5 to 4.5 parts by mass, preferably 0.5 to 4.0 parts by mass, when the total amount of the (meth) acrylate compound is 100 parts by mass.
  • a reactive fluorine-containing copolymer can be obtained by reacting a hydroxyl group in the fluorine-containing copolymer with a (meth) acrylate compound having an isocyanate group at the terminal represented by the general formula E. .
  • R 9 is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). is there.
  • R 10 represents H or a methyl group, preferably H.
  • y is an integer of 1 or 2.
  • Examples of the divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10, preferably 2 to 4 carbon atoms represented by R 9 include the following groups, and the corresponding ( A meth) acrylate compound is also shown together.
  • the mole ratio is 0.
  • the ratio is 01 ⁇ q / p ⁇ 0.8.
  • a ratio of 0.05 ⁇ q / p ⁇ 0.5 is particularly preferable.
  • (meth) acrylate for obtaining a fluorinated copolymer As a polymerization method of (meth) acrylate for obtaining a fluorinated copolymer, a known polymerization method can be used, but a raw material monomer, a polymerization initiator and a chain transfer agent are used as a polymerization solvent. It is preferable to perform radical copolymerization in a dissolved state. Specifically, (meth) acrylates A, B, C and F are mixed at a desired ratio, D is added as an appropriate amount of a polymerization initiator and a chain transfer agent, and the temperature is from room temperature to about 100 ° C. in the presence of an organic solvent. The reaction is carried out for about 1 to 24 hours. As a result, the reaction proceeds quantitatively.
  • the mixing order of (meth) acrylates A, B, C and F is not particularly limited.
  • the polymerization initiator examples include the following photopolymerization initiators.
  • azobisisobutyronitrile, benzoyl peroxide, and the like can be preferably used.
  • the organic solvent is not particularly limited as long as the above reaction proceeds, and examples thereof include an aprotic solvent.
  • Preferred examples of the aprotic solvent include dimethoxyethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, toluene, and propylene glycol monomethyl ether acetate.
  • the organic solvent may be used alone or in combination of two or more.
  • the repeating unit may not be positioned as shown in the chemical formula, and the hydroxyl group-containing copolymer is a random polymer or block copolymer of (meth) acrylates A, B, C, and F. It may be.
  • the reaction between the fluorine-containing copolymer and the isocyanate group-containing (meth) acrylate E is performed by mixing (meth) acrylate E in a predetermined ratio with the obtained hydroxyl group-containing copolymer solution, and -20 ° C to 100 ° C. It can be achieved by stirring for 1 to 48 hours at ° C, preferably 20 ° C to 90 ° C.
  • the hydroxyl group derived from the (meth) acrylate B or C component in the hydroxyl group-containing copolymer and the isocyanate group of (meth) acrylate E react to form a urethane bond, and the reactive fluorine-containing oligomer of the present invention Is obtained.
  • the mixed (meth) acrylate E reacts quantitatively.
  • an alkaline catalyst may be used.
  • the alkaline catalyst is not particularly limited as long as the above reaction proceeds.
  • examples of preferable alkaline catalysts include organic alkaline catalysts such as triethylamine, tributylamine, pyridine, 1,4-diazabicyclo [2.2.2] octane. Is mentioned.
  • the alkaline catalyst is particularly preferably 1,4-diazabicyclo [2.2.2] octane.
  • the alkaline catalyst may be used alone or in combination of two or more.
  • the weight average molecular weight of the fluorine-containing copolymer or fluorine-containing reactive copolymer of the present invention is usually 2000 to 50000, preferably 3000 to 20000.
  • the weight average molecular weight may be measured by a conventionally known method such as gel filtration chromatography, viscosity method, or light scattering method.
  • the fluorine-containing copolymer and the reactive fluorine-containing copolymer of the present invention can be used as a solution, but are usually mixed with additives such as a resin component, a solvent component, a polymerization initiator component, and a filler component. And used as a resin composition.
  • examples of the solvent include toluene, xylene, diethyl ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonitrile, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, ethanol, isopropanol, tetrahydrofuran, 1, 4 -An organic solvent such as dioxane may be mentioned, and methyl isobutyl ketone is preferred.
  • a solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. When used as a solution, the concentration is preferably 0.01% by mass to 5% by mass.
  • the cured film surface obtained by curing the active energy ray-curable coating liquid to which the fluorine-containing copolymer and / or photopolymerization initiator of the present invention has been added has a lower water contact angle than when it is not added. Become. If an overcoat layer is formed on the hard coat surface with a water contact angle exceeding 60 °, it may cause repellency and unevenness.
  • the fluorine-containing copolymer of the present invention is used for the purpose of, for example, setting the contact angle of water on the hard coat surface to 60 ° or less and suppressing repelling and unevenness of the overcoat layer.
  • the water contact angle on the coating surface is 45 ° to 60 °. It becomes a range and becomes a moderate hydrophilic surface. If the contact angle of water is within this range, it is preferable because repelling is unlikely to occur when a water-soluble paint or the like is overcoated.
  • the curable resin composition included in the present invention is prepared as a coating liquid for application to a substrate.
  • a fluorine-containing copolymer and / or a reactive fluorine-containing copolymer as a component that exhibits antifouling properties and leveling properties energy beam curability that mainly functions as a resin film
  • a resin monomer or resin oligomer, other polymerization initiator, solvent, and the like are blended.
  • no solvent is blended in the case of a solvent-free coating solution, and no polymerization initiator is required in the case of radiation curing.
  • the content of the fluorine-containing copolymer and / or reactive fluorine-containing copolymer in the total amount of the curable resin composition of the present invention is usually The amount is about 0.001 to 10% by mass, preferably about 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass.
  • the curable resin composition of the present invention is an energy that forms a cured resin film by reacting with the fluorine-containing copolymer and / or reactive fluorine-containing copolymer.
  • a linear curable resin monomer and / or a resin oligomer (hereinafter sometimes referred to as a resin monomer or a resin oligomer) are included.
  • Such a resin monomer and resin oligomer are not particularly limited as long as they form a cured film by reacting with a fluorine-containing copolymer and / or a reactive fluorine-containing copolymer, and usually a hard coat film or a reflective film.
  • the energy ray-curable resin monomer and / or resin oligomer used for the prevention coating film can be arbitrarily used.
  • the resin monomer and resin oligomer include reactive compounds such as acrylics such as various acrylates and acrylic urethanes, urethanes, and epoxies, and acrylic resins are preferably used.
  • the curable resin composition of the present invention is cured and used in the form of a film, it is preferable to use a resin monomer and / or a resin oligomer having a bifunctional or higher functional group.
  • resin monomers and resin oligomers having a bifunctional or higher reactive functional group examples include tricyclodecane dimethylol diacrylate, bisphenol F EO-modified diacrylate, bisphenol A EO-modified diacrylate, isocyanuric acid EO-modified diacrylate, and polypropylene.
  • Glycol diacrylate polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane PO-modified triacrylate, glycerin PO-added triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane EO-modified trimethacrylate , Isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, ⁇ - Prolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, various urethane acrylate oligomers Shigumi series manufactured by company, Art
  • Examples of energy rays for curing resin monomers and resin oligomers include radiation, electron beams, ultraviolet rays, and visible rays. Since the energy of electromagnetic waves is high in curing with radiation and electron beam, polymerization is possible only with a polymerizable double bond. When ultraviolet rays and visible rays are used as energy sources, it is preferable to blend a polymerization initiator component described later.
  • the content of the resin monomer and resin oligomer in the total amount of the curable resin composition of the present invention is usually about 55 to 99.9% by mass, preferably Is about 60 to 99.5% by mass, and more preferably about 70 to 99% by mass.
  • the resin monomer and the resin oligomer and the fluorine-containing copolymer and / or the reactive fluorine-containing copolymer is used in an amount of 100 parts by mass of the resin monomer and the resin oligomer, and the fluorine-containing copolymer and / or The reactive fluorine-containing copolymer is usually used in an amount of about 0.001 to 10 parts by mass, preferably about 0.01 to 5 parts by mass, more preferably about 0.1 to 2 parts by mass.
  • Polymerization initiator component In the curable resin composition of the present invention, in addition to the fluorine-containing copolymer and / or reactive fluorine-containing copolymer, resin monomer and / or resin oligomer, if necessary, polymerization is initiated.
  • An agent component may be included.
  • a conventionally well-known thing can be used for a polymerization initiator component,
  • a photoinitiator can be used.
  • photopolymerization initiators are known and may be appropriately selected and used.
  • the addition amount of the polymerization initiator component is based on 100 parts by mass of the polymerizable resin component (total amount of the fluorine-containing copolymer and / or reactive fluorine-containing copolymer, the resin monomer and / or the resin oligomer). Usually, the amount is about 0.1 to 50 parts by mass, preferably about 0.5 to 30 parts by mass, more preferably about 1 to 10 parts by mass.
  • Solvent component The curable resin composition of the present invention need not contain a solvent component, but may contain a solvent component as necessary.
  • solvent component conventionally known solvent components may be used, for example, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, toluene, xylene, etc.
  • aromatic hydrocarbons such as diethyl ether, alkylene glycol monoethers such as diethylene glycol monoethyl ether, alkylene glycol diethers such as diethylene glycol diethyl ether, tetrahydrofuran, and 1,4-dioxane.
  • alkylene glycol monoethers such as diethylene glycol monoethyl ether
  • alkylene glycol diethers such as diethylene glycol diethyl ether
  • tetrahydrofuran 1,4-dioxane.
  • the amount of the solvent component used in the curable resin composition of the present invention is the polymerizable resin component (the fluorine-containing copolymer and / or the reactive fluorine-containing copolymer, the resin monomer and
  • the total amount of the resin oligomer is usually about 25 to 5000 parts by mass, preferably about 40 to 2000 parts by mass, more preferably about 60 to 1000 parts by mass with respect to 100 parts by mass.
  • the curable resin composition of the present invention may contain fine particles, fillers and the like as necessary in order to provide a shape on the surface of the cured film and to provide other desired functions.
  • the curable resin composition of the present invention is used as a coating liquid, and after the coating liquid is applied to a substrate, a cured film can be formed by light irradiation or the like.
  • the procedure for obtaining the cured film of the present invention includes a fluorine-containing copolymer and / or a reactive fluorine-containing copolymer, a resin monomer and / or a resin oligomer, and, if necessary, a polymerization initiator component and a solvent.
  • Components, fine particles, fillers and the like are mixed and dissolved at an appropriate blending ratio to prepare the curable resin composition of the present invention as a coating liquid.
  • the coating liquid is applied on the substrate so as to have a certain film thickness, and after removing the solvent component by hot air drying, vacuum drying, etc., irradiation with energy rays such as radiation, electron beams, ultraviolet rays, and visible rays is performed.
  • energy rays such as radiation, electron beams, ultraviolet rays, and visible rays
  • the coating method of the coating liquid is not particularly limited, but for example, it is applied by wet coating, and as its method, for example, gravure method, bar coating method, wire bar method, spin coating method, doctor blade method, dip coating method, slit coating method Etc.
  • the substrate for producing the cured film is not particularly limited as long as the cured film can be supported, but for example, a transparent sheet is desirable when used as a hard coat for optical applications.
  • a transparent sheet is desirable when used as a hard coat for optical applications.
  • the material for the transparent sheet include glass and plastic, and a plastic sheet is particularly preferable.
  • thermoplastic resins, thermosetting resins and the like can be used, for example, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, cellulose resins such as triacetyl cellulose and butyl cellulose, polystyrene resins, polyurethane resins, Examples thereof include polyvinyl alcohol, polyvinyl chloride, acrylic resin, polycarbonate resin, polyacrylonitrile, cycloolefin polymer, and polyethersulfone. These sheets may be subjected to an easy attachment process such as a binder process, a corona process, a plasma process, or a flame process, if necessary.
  • polyolefin resins such as polyethylene and polypropylene
  • polyester resins such as polyethylene terephthalate
  • cellulose resins such as triacetyl cellulose and butyl cellulose
  • polystyrene resins polyurethane resins
  • polyurethane resins examples thereof
  • the thickness of the cured film of the present invention is not particularly limited, and may be appropriately selected depending on the application. Usually, it can be about 100 nm to 30 ⁇ m.
  • the fluorine-containing (meth) acrylate (A-1) used in the synthesis examples was synthesized by a known synthesis method (for example, the synthesis method described in JP-A-2010-47680).
  • Synthesis example 1 In a three-necked flask (50 mL) equipped with a condenser tube, 1.00 g of fluorine-containing acrylate (A-1), 4.00 g of methoxypolyethylene glycol monoacrylate (C-1: AME-400 manufactured by NOF Corporation), 4.00 g of 4-hydroxybutyl acrylate (B-1), 18.00 g of methyl isobutyl ketone, 0.065 g of 2,2′-azobisisobutyronitrile and 0.2 g of mercaptopropionic acid were added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C.
  • the target fluorine-containing oligomer was obtained quantitatively (33% by mass methyl isobutyl ketone solution).
  • the resulting fluorine-containing copolymer was prepared by adding methyl isobutyl ketone so that the solid content concentration was 30% by mass.
  • the weight average molecular weight (Mw) of the obtained reduced fluoropolymer was measured using the following apparatus under the following conditions.
  • the weight average molecular weight of the fluoropolymer obtained in Synthesis Example 1 was 6700.
  • Synthesis Examples 2 to 6, and 10 to 12, 14, 17 to 18 A fluorine-containing copolymer was synthesized by changing the ratio of monomers A, B, C, F and compound D in the same procedure as in Synthesis Example 1.
  • the monomer ratio and the monomer type are as shown in Table 1.
  • the numbers in parentheses represent mass ratios (except for the monomer E column).
  • the numbers in parentheses of the monomer E represent the equivalent ratio of the monomer E to the hydroxyl group in the fluorine-containing copolymer.
  • Synthesis example 7 The fluorine-containing copolymer obtained in Synthesis Example 1 was mixed with 0.2 equivalent of 2- (isocyanatoethyl) acrylate (E-1) and 0.01 equivalent with respect to the hydroxyl group-containing acrylate compound (B-1). Of 1,4-diazabicyclo [2.2.2] octane was added and stirring of the reaction solution was continued at 50 ° C. for 20 hours. The completion of the reaction was confirmed by disappearance of —N ⁇ C ⁇ O absorption (2275-2250 cm ⁇ 1 ) using FT-IR. The target reactive fluorine-containing oligomer was obtained quantitatively (30% by mass methyl isobutyl ketone solution).
  • Synthesis Example 8 A reactive fluorine-containing copolymer was synthesized in the same procedure as in Synthesis Example 7 except that the ratios of monomers B and C were changed.
  • Synthesis Example 9 A reactive fluorine-containing copolymer was synthesized in the same procedure as in Synthesis Example 7 except that the ratio of the monomer E was changed.
  • Synthesis Example 13 A reactive fluorine-containing copolymer was synthesized in the same procedure as in Synthesis Example 7 except that the ratios of monomers B and C were changed.
  • Synthesis Example 15 A reactive fluorine-containing copolymer was synthesized in the same procedure as in Synthesis Example 1 except that the ratios of monomers B and C were changed. The weight average molecular weight of the fluoropolymer obtained in Synthesis Example 15 was 12000.
  • Synthesis Example 16 A reactive fluorine-containing copolymer was synthesized in the same procedure as in Synthesis Example 7 except that the copolymer obtained in Synthesis Example 15 was used. The weight average molecular weight of the fluoropolymer obtained in Synthesis Example 16 was 12000.
  • Synthesis Example 19 A reactive fluorine-containing copolymer was synthesized in the same procedure as in Synthesis Example 7 except that the ratio of the monomers B and C was changed and the compound D was changed. The weight average molecular weight of the fluoropolymer obtained in Synthesis Example 19 was 19000.
  • Pencil hardness In accordance with JIS K 5600-5-4, a pencil core is applied at an angle of about 45 ° to the test coating plate surface, and pressed against the test coating plate surface with a load of 750 g. Moved 10 mm or more. The hardness symbol of the hardest pencil with no scratches, dents or tears on the coating film was defined as the coating film hardness.
  • the fluorine-containing copolymer according to the present invention is useful as a surface modifier that makes the surface used in the fields of glass, fiber, metal, resin, film, optical material, paint, etc., hydrophilic, for example. It is useful as a compound that can impart moderate hydrophilicity and smoothness to the surface. Since the curable composition containing the fluorine-containing copolymer of the present invention is also excellent in transparency, it can be used in fields requiring transparency, such as optical applications.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un nouveau copolymère fluoré qui peut satisfaire aux exigences d'hydrophilie et de lissé appropriées dans le domaine des agents de traitement de surface, des agents de modification de surface, etc., pour des résines, des films, des fibres, du verre, des métaux, etc. Ce copolymère fluoré contient un composé (méth)acrylate représenté par les formules générales A et C en tant que motif monomère, et est caractérisé en ce que le composé fluoré contient le résidu d'un agent de transfert de chaîne dans la réaction de polymérisation radicalaire, représenté par la formule générale (I). Rf représente un groupe fluoré spécifique.
PCT/JP2015/062296 2014-04-25 2015-04-22 Copolymère fluoré ayant un groupe hydrophile, et agent de modification de surface contenant ledit copolymère WO2015163380A1 (fr)

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JP2019031592A (ja) * 2017-08-04 2019-02-28 中国塗料株式会社 光硬化性樹脂組成物、該組成物から形成される硬化被膜およびその製造方法、ならびに、被膜付き基材およびその製造方法

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CN109929066A (zh) * 2017-12-15 2019-06-25 上海飞凯光电材料股份有限公司 一种紫外光固化树脂、制备方法、涂料
CN112480296B (zh) * 2019-09-12 2023-10-27 浙江省化工研究院有限公司 一种亲水改性的乙烯-三氟氯乙烯共聚物、其制备方法及应用
CN112409915A (zh) * 2020-12-21 2021-02-26 广州市奈森化工有限公司 亲水疏油防雾光固化涂料及其制备方法

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JPS5962611A (ja) * 1982-10-02 1984-04-10 Daikin Ind Ltd フルオロアルキルアクリレ−ト重合体
JP2004346231A (ja) * 2003-05-23 2004-12-09 Daikin Ind Ltd コーティング組成物
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JP2019031592A (ja) * 2017-08-04 2019-02-28 中国塗料株式会社 光硬化性樹脂組成物、該組成物から形成される硬化被膜およびその製造方法、ならびに、被膜付き基材およびその製造方法
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CN106232644A (zh) 2016-12-14
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