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WO2018163837A1 - Composition durcissable par rayonnement d'énergie active, produit durci et film - Google Patents

Composition durcissable par rayonnement d'énergie active, produit durci et film Download PDF

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Publication number
WO2018163837A1
WO2018163837A1 PCT/JP2018/006389 JP2018006389W WO2018163837A1 WO 2018163837 A1 WO2018163837 A1 WO 2018163837A1 JP 2018006389 W JP2018006389 W JP 2018006389W WO 2018163837 A1 WO2018163837 A1 WO 2018163837A1
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Prior art keywords
meth
acrylate
energy ray
active energy
mass
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Ceased
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PCT/JP2018/006389
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English (en)
Japanese (ja)
Inventor
茂年 西澤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Publication date
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Priority to CN201880016681.7A priority Critical patent/CN110402258B/zh
Priority to JP2018526604A priority patent/JP6388189B1/ja
Priority to KR1020197024169A priority patent/KR102405075B1/ko
Publication of WO2018163837A1 publication Critical patent/WO2018163837A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • 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
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to an active energy ray-curable composition, a cured product thereof, and a film.
  • Antireflective (LR) films used on the surface of flat panel displays (FPD) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), plasma displays (PDPs), etc. have a large refractive index difference on the film substrate
  • FPD flat panel displays
  • LCDs liquid crystal displays
  • OLEDs organic EL displays
  • PDPs plasma displays
  • LR refractive index difference
  • This is realized by a multilayer structure in which two layers are formed (base material / high refractive index layer / low refractive index layer).
  • base material high refractive index layer / low refractive index layer
  • Each of these layers is required to have high scratch resistance in order to prevent scratches in the production process of the antireflection film, and also to have high antistatic properties in order to prevent contamination and blocking of the film.
  • an antireflection film is an optical film, each layer is also required to have high transparency.
  • the problem to be solved by the present invention is an active energy ray capable of forming a hard coat layer having excellent antistatic properties and having excellent water resistance that does not become cloudy even when water is mixed and does not cause poor appearance. It is to provide a curable composition.
  • the present invention comprises an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide.
  • An active energy ray-curable composition is provided.
  • this invention provides the cured
  • the active energy ray-curable composition of the present invention is excellent in continuous productivity by providing a composition having water resistance that is not easily clouded even when water is mixed during coating, and excellent in the film surface after curing.
  • a hard coat layer having antistatic properties can be formed.
  • the film which has a hard-coat layer which consists of a cured coating film of the active energy ray curable composition of this invention is flat panel displays, such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP) ( It can be suitably used as an optical film used for FPD). Furthermore, since it has excellent antistatic properties when used in these applications, adhesion of dust and the like can be suppressed. Furthermore, when this film is used for a liquid crystal display or the like, malfunction of the display due to generated static electricity can be prevented.
  • LCD liquid crystal display
  • OLED organic electroluminescent display
  • PDP plasma display
  • the active energy ray-curable composition of the present invention comprises an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide. It contains.
  • Examples of the active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1), urethane (meth) acrylate (A2), and a high refractive index polymerizable monomer having a refractive index of 1.55 or more.
  • Examples thereof include body (A3), epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. These may be used alone or in combination of two or more.
  • a polyfunctional (meth) acrylate (A1) is obtained from the viewpoint that a more excellent scratch resistance, hard coat property, water resistance, and transparency of a cured coating film can be obtained.
  • a combination of (meth) acrylate (A1) and urethane (meth) acrylate (A2) or a combination of polyfunctional (meth) acrylate (A1) and high refractive index polymerizable monomer (A3) is more preferable.
  • (meth) acrylate refers to one or both of acrylate and methacrylate
  • (meth) acryloyl refers to one or both of acryloyl and methacryloyl.
  • the polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acryloyl groups in one molecule.
  • Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol.
  • polyfunctional (meth) acrylates (A1) can be used alone or in combination of two or more.
  • these polyfunctional (meth) acrylates (A1) since the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention is improved, dipentaerythritol hexa (meth) acrylate, di It is preferable to use at least one compound selected from the group consisting of pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Is more preferable.
  • urethane (meth) acrylate (A2) a reaction product of polyisocyanate (a2-1) and (meth) acrylate (a2-2) having a hydroxyl group can be used.
  • polyisocyanate (a2-1) examples include aliphatic polyisocyanates and aromatic polyisocyanates. Since the coloring of the cured coating film of the active energy ray-curable composition of the present invention can be reduced, Isocyanates are preferred.
  • the aliphatic polyisocyanate is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon.
  • Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanato).
  • cycloaliphatic polyisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane.
  • a trimerized product obtained by trimming the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate.
  • these aliphatic polyisocyanates can be used alone or in combination of two or more.
  • aliphatic polyisocyanates in order to improve the scratch resistance of the coating film, it is preferable to use one or more selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate, and more preferably isophorone diisocyanate.
  • the (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acryloyl group.
  • Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
  • Divalent compounds such as acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate Mono (meth) acrylate of alcohol; trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di (meta) Mono- or di (meth) acrylate of trivalent alcohol such as acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups Mono- and di (meth) acrylates having hydroxyl groups modified with
  • the urethane (meth) acrylate (A2) since it can improve the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention, it has four or more (meth) acryloyl groups in one molecule. Those are preferred. Since the urethane (meth) acrylate (A2) has four or more (meth) acryloyl groups in one molecule, the (meth) acrylate (a2-2) has 2 (meth) acryloyl groups. Those having at least two are preferred.
  • Examples of such (meth) acrylate (a2-2) include trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, Glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipenta Examples include erythritol penta (meth) acrylate.
  • (meth) acrylates (a2-2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates.
  • these (meth) acrylates (a2-2) since scratch resistance can be further improved, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) Acrylates are preferred, and pentaerythritol tetra (meth) acrylate is more preferred.
  • the reaction of the polyisocyanate (a2-1) and the (meth) acrylate (a2-2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate
  • urethanization catalyst examples include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.
  • the high-refractive index polymerizable monomer (A3) having a refractive index of 1.55 or more is sufficient if it has a high refractive index of 1.55 or more before curing.
  • Preferable examples include 6 to 6 aromatic polymerizable monomers and fluorene polymerizable monomers.
  • polymerizable monomer (A) examples include compounds represented by the following general formula (1): phenylbenzyl such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate (Meth) acrylate compound having a group; (meth) acrylate compound having a phenylphenol group such as phenylphenol EO acrylate; propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, oxyethylene group Examples thereof include bisphenol compounds having 2 to 4 (meth) acryloyl groups such as bisphenol A di (meth) acrylate having an oxyethylene group and bisphenol A tri (meth) acrylate having an oxyethylene group.
  • phenylbenzyl such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate (Meth) acrylate compound having
  • These polymerizable monomers (A) can be used alone or in combination of two or more.
  • a compound represented by the following general formula (1) which has a phenylbenzyl group, can be obtained because a high refractive index can be easily controlled even when a specific organic solvent described later is used ( It is preferable to use one or more monomers selected from the group consisting of a meth) acrylate compound and a bisphenol compound having 2 to 4 (meth) acryloyl groups.
  • polymerizable monomer (A3) Commercially available products that can be used as the polymerizable monomer (A3) include “OGSOL EA-0200”, “OGSOL EA-0300”, “OGSOL GA-5060P” manufactured by Osaka Gas Chemical Co., Ltd .; DIC Corporation “UNIDIC EKZ-948”, “UNIDIC EQS-1179” manufactured by Shin-Nakamura Chemical Co., Ltd., “MIRAMER HR6042” manufactured by MIWON, etc. These polymerizable monomers (A) can be used alone or in combination of two or more.
  • R 1 and R 2 each represent a hydrogen group or a methyl group, and m and n each represent an integer of 0 to 5.
  • the resin (B) has an alicyclic structure and a quaternary ammonium salt.
  • Examples of the method for producing the resin (B) include the polymerizable monomer (b1) having an alicyclic structure and the polymerizable monomer (b2) having a quaternary ammonium salt as essential components. Examples thereof include a method of copolymerizing the monomer (b1) and the polymerizable monomer (b2) with a copolymerizable polymerizable monomer (b3).
  • the polymerizable monomer (b1) is a polymerizable monomer having an alicyclic structure.
  • the alicyclic structure include a monocyclic alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring; a bicycloundecane ring, a decahydro ring Naphthalene (decalin) ring, tricyclo [5.2.1.0 2,6 ] decane ring, bicyclo [4.3.0] nonane ring, tricyclo [5.3.1.1] dodecane ring, tricyclo [5.
  • polymerizable monomer (c1) examples include cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Examples include dicyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate.
  • polymerizable monomers (b1) can be used alone or in combination of two or more.
  • Examples of the polymerizable monomer (b2) include those in which the counter anion such as 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride and 3-[(meth) acryloyloxy] propyltrimethylammonium chloride is chloride; Counter anions such as 2-[(meth) acryloyloxy] ethyltrimethylammonium bromide, 3-[(meth) acryloyloxy] propyltrimethylammonium bromide and the like, wherein 2-[(meth) acryloyloxy] ethyltrimethylammonium methylphenyl Sulfonate, 2-[(meth) acryloyloxy] ethyltrimethylammonium methylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylammonium methyl Phenylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylam
  • Examples of the polymerizable monomer (b3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n- Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Alkyl (meth) acrylates such as dodecyl (meth) acrylate; methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethyleneglycol / polypropyleneglycol mono (meth) acrylate, lauroxypoly
  • the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, mono (meth) acrylate of polyalkylene glycol is preferable, and methoxypolyethylene Glycol mono (meth) acrylate is more preferred.
  • the (meth) acrylate which has a fluorinated alkyl group is also preferable from the effect that the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
  • the number average molecular weight of the polyalkylene glycol is preferably in the range of 200 to 8,000, more preferably in the range of 300 to 6,000, still more preferably in the range of 400 to 4,000, and 400 to 2 Those in the range of 1,000 are particularly preferred.
  • the ratio of the polymerizable monomer (b1) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
  • the range of mass% is preferable, the range of 10 to 50 mass% is more preferable, and the range of 12 to 45 mass% is more preferable.
  • the ratio of the polymerizable monomer (b2) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
  • the range of ⁇ 90% by mass is preferred, the range of 40 ⁇ 80% by mass is more preferred, and the range of 45 ⁇ 70% by mass is more preferred.
  • the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
  • the ratio of the poly (alkylene glycol) mono (meth) acrylate in the total amount of the raw material of the resin (B) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and 20 to 40% by mass. The range of is more preferable.
  • the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
  • the ratio of the (meth) acrylate having a fluorinated alkyl group in the total amount of the raw material of the resin (B) is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass. The range of 1 to 5% by mass is more preferable.
  • the weight average molecular weight of the resin (B) is preferably in the range of 1,000 to 100,000 because the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
  • the range of ⁇ 50,000 is more preferred, and the range of 3,000 ⁇ 30,000 is more preferred.
  • the weight average molecular weight in this invention is the value in polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the compounding amount of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, it is based on 100 parts by mass of the active energy ray-curable compound (A).
  • the range of 0.1 to 30 parts by mass is preferable, the range of 0.3 to 20 parts by mass is more preferable, the range of 0.5 to 10 parts by mass is more preferable, and the range of 0.7 to 7 parts by mass is particularly preferable. preferable.
  • the organic solvent (C) must contain dimethylacetamide in order to obtain excellent water resistance.
  • Dimethylacetamide has good compatibility with the resin (B) and has a relatively high boiling point. Therefore, even if water is mixed in, dimethylacetamide is completely mixed and has high polymer solubility, so both hydrophilic and hydrophobic components are mixed. Even in the case of evaporation, since it evaporates in the drying step, problems such as whitening can be suppressed, and excellent water resistance can be obtained.
  • the content of the dimethylacetamide is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A) from the standpoint that even better water resistance is obtained.
  • the range of 7 to 150 parts by mass is more preferable.
  • the content of the dimethylacetamide is preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably 7% by mass in the organic solvent (C) from the viewpoint of obtaining further excellent water resistance. More preferred is 99% by mass or less.
  • organic solvent (C) in addition to the dimethylacetamide, for example, a hydrophobic solvent and a hydrophilic solvent other than the dimethylacetamide can be used.
  • hydrophobic solvent examples include diethyl ether, benzene, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, xylene, n-butanol, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, chloroform, propylene glycol.
  • examples thereof include monomethyl ether acetate.
  • solvents may be used alone or in combination of two or more.
  • the hydrophobic solvent the coating stability of the active energy ray-curable composition is further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained.
  • hydrophilic solvent examples include acetone, methanol, ethanol, n-propanol, isopropyl alcohol, diacetone alcohol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dioxolane, tetrahydrofuran, tetrahydropyran, dimethylformamide, and the like. . These solvents may be used alone or in combination of two or more. As the hydrophilic solvent, the coating stability of the active energy ray-curable composition is further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained.
  • the hydrophilic solvent refers to a solvent having a solubility in water of 10 g / 100 ml or more, and a solvent other than the dimethylacetamide is a hydrophobic solvent.
  • the solubility of the organic solvent in water accounts for the solubility in 100 ml of water (25 ° C.).
  • the coating stability of the active energy ray-curable composition can be further improved, cracks can be prevented from entering the cured coating film, and a more excellent coating appearance can be obtained.
  • dimethylacetamide in combination with other hydrophilic solvents, or in combination with dimethylacetamide, other hydrophilic solvents and hydrophobic solvents.
  • the amount of the hydrophilic solvent used in combination with dimethylacetamide and the other hydrophilic solvent is 100 parts by mass of the active energy ray-curable compound (A).
  • the range is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass.
  • the amount of the hydrophilic solvent used is the active energy ray-curable compound (A).
  • the range of 0.1 to 40 parts by mass with respect to 100 parts by mass is preferable, and the range of 3 to 25 parts by mass is more preferable.
  • the amount of the hydrophobic solvent used is the active energy ray-curable compound (A).
  • the range of 10 to 95 parts by mass is preferable with respect to 100 parts by mass, and the range of 30 to 93 parts by mass is more preferable.
  • the blending amount of the organic solvent (C) in the active energy ray-curable composition of the present invention is preferably an amount that provides a viscosity suitable for a coating method described later.
  • the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after coating on a substrate.
  • the active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • a photopolymerization initiator (D) to the active energy ray curable composition of the present invention to improve curability.
  • a photosensitizer (E) can be further added to improve curability.
  • Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo ⁇ 2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone ⁇ , benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, benzo Benzoin compounds such as isopropyl ether; acylphosphine oxide compounds such as 2,4,6-
  • Examples of the photosensitizer (E) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuro And sulfur compounds such as nitro-p-toluenesulfonate.
  • tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine
  • urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuro
  • sulfur compounds such as nitro-p-toluenesulfonate.
  • the usage-amount of said photoinitiator (D) and photosensitizer (E) is 100 mass parts of said active energy ray-curable compounds (A) in the active energy ray-curable composition of the present invention.
  • Each is preferably 0.05 to 20 parts by mass, more preferably 0.5 to 10% by mass.
  • a polymerization inhibitor as a compound other than the above components (A) to (E), a polymerization inhibitor, a surface conditioner, and an antistatic agent can be used depending on applications and required properties. Addition of antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, UV absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, silica beads, organic beads, etc. Agents: Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.
  • the film of the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one surface of a film substrate, and then irradiating the active energy ray to form a cured coating film. is there.
  • the material of the film base used in the film of the present invention is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polypropylene, polyethylene, polymethylpentene-1 Polyolefin resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate and other cellulose resins; poly Acrylic resins such as methyl methacrylate; polyvinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-acetic acid Nyl copolymer; polystyrene; polyamide; polycarbonate; polysulfone; polyethersulfone; polyetheretherketone; polyimide resin
  • the film substrate may be in the form of a film or a sheet, and the thickness is preferably in the range of 20 to 500 ⁇ m.
  • the thickness is preferably in the range of 20 to 200 ⁇ m, more preferably in the range of 30 to 150 ⁇ m, and still more preferably in the range of 40 to 130 ⁇ m.
  • Examples of the method for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and dip coating. , Spinner coating, brush coating, solid coating by silk screen, wire bar coating, flow coating and the like.
  • the drying conditions are not particularly limited as long as the organic solvent (C) is volatilized. Usually, the drying is performed at a temperature of 50 to 100 ° C. and for a time of 0.5 to 10 minutes. It is preferable to do.
  • the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • ultraviolet rays examples of devices that emit ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Examples thereof include a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium / cadmium laser, an argon laser, sunlight, and an LED lamp.
  • the film thickness of the cured coating film when forming the cured coating film of the active energy ray-curable composition of the present invention on the film substrate is sufficient for the hardness of the cured coating film and curing of the coating film. Since the curling of the film due to shrinkage can be suppressed, the range of 1 to 30 ⁇ m is preferable, the range of 3 to 15 ⁇ m is more preferable, and the range of 4 to 10 ⁇ m is more preferable.
  • the weight average molecular weight of the resin (B-1) obtained above was measured by the gel permeation chromatography (GPC) method under the following conditions.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • Example 1 50 parts by mass of dipentaerythritol hexaacrylate (hereinafter abbreviated as “DPHA”), urethane acrylate (reaction product of pentaerythritol tetraacrylate and isophorone diisocyanate, solid content 100 mass%, hereinafter abbreviated as “UA1”) 50 Parts by weight, 2.2 parts by weight of a 45% by weight solution of the resin (C-1) obtained in Production Example 1 (1 part by weight as the resin (C-1)), photopolymerization initiator (BASF Japan Ltd.
  • DPHA dipentaerythritol hexaacrylate
  • UUA1 urethane acrylate
  • U1 solid content 100 mass%
  • Irgacure 184 ; 1-hydroxycyclohexyl phenyl ketone, hereinafter abbreviated as” Irg184
  • DMAC dimethylacetamide
  • PGME 8.5 parts by mass of ethanol
  • An energy ray curable composition (1) was obtained.
  • Example 2 50 parts by mass of DPHA, 50 parts by mass of UA1, 6.6 parts by mass of a 45% by mass resin (C-1) solution obtained in Production Example 1 (3 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part by mass, 36 parts by mass of DMAC, 54 parts by mass of dimethyl carbonate (hereinafter abbreviated as “DMC”), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol are mixed to obtain an activity.
  • An energy ray-curable composition (2) was obtained.
  • Example 3 50 parts by mass of DPHA, 50 parts by mass of UA1, 11.1 parts by mass of a 45% by mass resin (C-1) obtained in Production Example 1 (5 parts by mass as resin (C-1)), and 5 parts by mass of Irg184 Part, DMAC 10 parts by mass, methyl ethyl ketone (hereinafter abbreviated as “MEK”) 30 parts by mass and DMC 60 parts by mass were uniformly mixed to obtain an active energy ray-curable composition (3).
  • MEK methyl ethyl ketone
  • Example 4 70 parts by mass of DPHA, 30 parts by mass of “MIRAMER HR6042” (refractive index: 1.618, hereinafter abbreviated as “HR6042”) manufactured by MIWON, 45% by mass solution of the resin (C-1) obtained in Production Example 1 6.6 parts by mass (3 parts by mass as resin (C-1)), 5 parts by mass of Irg184, and 100 parts by mass of DMAC were uniformly mixed to obtain an active energy ray-curable composition (4).
  • MIRAMER HR6042 reffractive index: 1.618, hereinafter abbreviated as “HR6042”
  • Comparative Example 2 An active energy ray-curable composition (R2) was obtained in the same manner as in Comparative Example 1 except that MEK was changed to DMC.
  • Comparative Example 3 Comparative Example, except that 100 parts by mass of MEK was changed to 90 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol.
  • MIBK methyl isobutyl ketone
  • R3 active energy ray-curable composition
  • the active energy ray-curable composition was applied to a 60 ⁇ m-thick triacetylcellulose (TAC) film (manufactured by Fuji Film Co., Ltd.) with a bar coater so as to have a film thickness of 5 ⁇ m, and then at 60 ° C. for 1.5 minutes. After drying, irradiation was performed with an integrated light quantity of 3 kJ / m 2 using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) in an air atmosphere, and a TAC film having a cured coating film was obtained as an evaluation sample. .
  • TAC triacetylcellulose
  • Comparative Examples 1 to 3 were embodiments in which dimethylacetamide was used as the organic solvent (C), but all had poor water resistance. Further, in Comparative Example 3, the surface resistance value exceeded 10 13 and it was confirmed that the antistatic property was inferior.

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Abstract

La présente invention concerne une composition durcissable par rayonnement d'énergie active caractérisée en ce qu'elle comprend un composé durcissable par rayonnement d'énergie active (A), une résine (B) ayant une structure alicyclique et un sel d'ammonium quaternaire, et un solvant organique (C) contenant du diméthylacétamide. L'invention concerne également un produit durci de la composition durcissable par rayonnement d'énergie active et un film ayant un revêtement durci. La teneur en diméthylacétamide est de préférence dans une plage de 5 à 200 parties en masse par rapport à 100 parties en masse du composé durcissable par rayonnement d'énergie active (A). La présente invention aborde le problème de la fourniture d'une composition durcissable par rayonnement d'énergie active qui n'est pas sujette au blanchiment, à la gélification, et à la sédimentation et est donc très appropriée pour une production continue en raison de la bonne résistance à l'eau du liquide de revêtement vis-à-vis de l'humidité dans l'air et de la condensation et qui est capable de former une couche de revêtement dur ayant d'excellentes propriétés antistatiques.
PCT/JP2018/006389 2017-03-06 2018-02-22 Composition durcissable par rayonnement d'énergie active, produit durci et film Ceased WO2018163837A1 (fr)

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JP2018526604A JP6388189B1 (ja) 2017-03-06 2018-02-22 活性エネルギー線硬化性組成物、硬化物、及び、フィルム
KR1020197024169A KR102405075B1 (ko) 2017-03-06 2018-02-22 활성 에너지선 경화성 조성물, 경화물, 및, 필름

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