WO2015198959A1 - Composition durcissable par un rayonnement d'énergie active et film l'utilisant - Google Patents

Composition durcissable par un rayonnement d'énergie active et film l'utilisant Download PDF

Info

Publication number
WO2015198959A1
WO2015198959A1 PCT/JP2015/067601 JP2015067601W WO2015198959A1 WO 2015198959 A1 WO2015198959 A1 WO 2015198959A1 JP 2015067601 W JP2015067601 W JP 2015067601W WO 2015198959 A1 WO2015198959 A1 WO 2015198959A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
active energy
energy ray
film
Prior art date
Application number
PCT/JP2015/067601
Other languages
English (en)
Japanese (ja)
Inventor
卓司 塚本
麸山　解
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to CN201580030392.9A priority Critical patent/CN106459240B/zh
Priority to KR1020167034439A priority patent/KR101784239B1/ko
Priority to JP2016529510A priority patent/JP6025010B2/ja
Publication of WO2015198959A1 publication Critical patent/WO2015198959A1/fr

Links

Classifications

    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/38—Esters containing sulfur
    • 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
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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'
    • C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen

Definitions

  • the present invention relates to an active energy ray-curable composition capable of forming a hard coat layer having high antistatic properties on a film surface by coating and curing the film surface, and a film using the same.
  • Various resin films include scratch prevention films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), decorative films (sheets) for interior and exterior of automobiles, It is used for various applications such as low reflection film for windows and heat ray cut film.
  • FPD flat panel displays
  • LCD liquid crystal displays
  • OLED organic EL displays
  • PDP plasma displays
  • decorative films sheets for interior and exterior of automobiles
  • a hard coat layer comprising a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this.
  • a hard coat layer comprising a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this.
  • the outline of the process of providing a hard coat layer is sent out from a film roll wound in a roll shape to a coating machine, a hard coat agent is applied, cured by ultraviolet irradiation to form a hard coat layer, and again It is wound up into a roll.
  • a method of adding an antistatic agent to the hard coat agent is generally performed.
  • a method of blending a quaternary ammonium base-containing polymer in a hard coat agent as an antistatic agent has been proposed (see, for example, Patent Document 1).
  • the counter anion of the quaternary ammonium salt used in the quaternary ammonium base-containing polymer used here is chloride, which is not preferable in consideration of the environment.
  • the problem to be solved by the present invention is that an active energy ray-curable composition capable of forming a cured coating film without using halogen such as chloride, that is, halogen-free and having an antistatic ability equal to or higher than that of the conventional one, and It is to provide a film using the same.
  • halogens such as chlorides can be obtained by blending a specific resin having a quaternary ammonium salt that does not contain halogens into the active energy ray-curable composition.
  • a cured coating film having an antistatic property equal to or higher than that of a conventional one can be formed without using a halogen, that is, halogen-free.
  • the present invention contains an active energy ray-curable compound (A) and an active energy ray-curable resin containing a resin (B) having a quaternary ammonium salt represented by the following general formula (1).
  • the present invention relates to an adhesive composition and a film using the same.
  • R 1 to R 3 each independently represents an alkyl group or a phenyl group
  • R 4 represents an alkyl group, an alkoxy group, a phenyl group or an oxyphenyl group.
  • the active energy ray-curable composition of the present invention is halogen-free and can be applied and cured on the surface of the resin film so that a hard coat layer having high antistatic properties can be formed on the surface of the resin film. It is a gentle material. Therefore, since the cured coating film of the active energy ray-curable composition of the present invention can suppress the generation of static electricity on the film surface, it can prevent sticking of various resin films and the adhesion of dust and the like due to static electricity. Therefore, the film having a cured coating film of the active energy ray-curable composition of the present invention is environmentally friendly, and troubles such as sticking and adhesion of dust, etc. when winding up into a roll or unwinding from a roll. Therefore, a film excellent in subsequent handling can be provided.
  • 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 used for various applications such as a film for preventing scratches on the surface of FPD, a protective film for touch panels, a decorative film (sheet) for interior and exterior of automobiles, a low reflection film for windows and a heat ray cut film. Furthermore, since it has excellent antistatic properties when used in these applications, adhesion of dust and the like can be suppressed.
  • LCD liquid crystal display
  • OLED organic electroluminescent display
  • PDP plasma display
  • the active energy ray-curable composition of the present invention contains an active energy ray-curable compound (A) and a resin (B) having a quaternary ammonium salt represented by the following general formula (1). .
  • R 1 to R 3 each independently represents an alkyl group or a phenyl group
  • R 4 represents an alkyl group, an alkoxy group, a phenyl group or an oxyphenyl group.
  • Examples of the active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2). These can be used alone or in combination of two or more.
  • (meth) acrylate refers to one or both of acrylate and methacrylate
  • (meth) acryloyl group refers to one or both of acryloyl group and methacryloyl group.
  • 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 Pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferred.
  • the urethane (meth) acrylate (A2) is obtained by reacting polyisocyanate (a2-1) with (meth) acrylate (a2-2) having a hydroxyl group.
  • 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, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a linear aliphatic hydrocarbon diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, isophorone Diisocyanate is preferred.
  • 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, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Can be mentioned.
  • (meth) acrylates (a2-2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates.
  • pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.
  • 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.
  • active energy ray-curable compound (A) other than said polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2) epoxy (meth) acrylate, polyester (meth) An acrylate, a polyether (meth) acrylate, etc. can be used.
  • the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid with bisphenol-type epoxy resin, novolac-type epoxy resin, polyglycidyl methacrylate and the like and esterifying it.
  • polyester (meth) acrylate (meth) acrylic acid is made to react and esterify with the polyester which the both terminal obtained by polycondensation of polyhydric carboxylic acid and polyhydric alcohol is a hydroxyl group, for example. Or a product obtained by reacting (meth) acrylic acid with ester obtained by adding an alkylene oxide to a polyvalent carboxylic acid.
  • polyether (meth) acrylate what was obtained by reacting (meth) acrylic acid with polyether polyol and esterifying is mentioned, for example.
  • the resin (B) has a quaternary ammonium salt represented by the following general formula (1).
  • R 1 to R 3 each independently represents an alkyl group or a phenyl group
  • R 4 represents an alkyl group, an alkoxy group, a phenyl group or an oxyphenyl group.
  • R 1 to R 3 in the general formula (1) are each independently an alkyl group or a phenyl group, and in the case of an alkyl group, those having 1 to 6 carbon atoms are preferred, and those having 1 to 3 are preferred. More preferred is a methyl group.
  • a phenyl group it may have a substituent on the benzene ring, and may be, for example, an alkyl-substituted phenyl group such as a methylphenyl group or an ethylphenyl group.
  • R 4 is an alkyl group, an alkoxy group, a phenyl group or an oxyphenyl group.
  • the number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3. preferable.
  • the benzene ring may have a substituent.
  • the phenyl group include alkyl-substituted phenyl groups such as a methylphenyl group and an ethylphenyl group.
  • the group include oxyalkyl-substituted phenyl groups such as oxymethylphenyl group and oxyethylphenyl group.
  • R 1 to R 3 in the general formula (1) are preferably alkyl groups, and more preferably all methyl groups.
  • R 4 in the general formula (1) is preferably a phenyl group or an alkyl-substituted phenyl group.
  • Examples of the method for producing the resin (B) include, as an essential component, a polymerizable monomer (b1) having a quaternary ammonium salt represented by the following general formula (1). And a polymerizable monomer (b2) copolymerizable with (A).
  • polymerizable monomer (b1) examples include 2- (methacryloyloxy) ethyltrimethylammonium methylphenylsulfonate, 2- (methacryloyloxy) ethyltrimethylammonium methylsulfonate, 3- (methacryloyloxy) propyltrimethylammonium methyl.
  • examples thereof include phenylsulfonate, 3- (methacryloyloxy) propyltrimethylammonium methylsulfonate, 2- (methacryloyloxy) ethyltrimethylammonium methyl sulfate, 3- (methacrylamide) propyltrimethylammonium methyl sulfate, and the like.
  • Examples of the polymerizable monomer (b2) 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; (meth) acrylates having an alicyclic structure such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; methoxypolyethylene glyco
  • polymerizable monomers (b2) since 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 number average molecular weight of the polyalkylene glycol is preferably in the range of 500 to 8,000, more preferably in the range of 1,000 to 6,000, and still more preferably in the range of 2,000 to 5,000. .
  • the ratio of the polymerizable monomer (b1) in the raw material of the resin (B) is preferably in the range of 40 to 90% by mass, more preferably in the range of 50 to 80% by mass, and in the range of 60 to 70% by mass. Is more preferable.
  • the ratio of the mono (meth) acrylate of the polyalkylene glycol in the raw material of the resin (B) is 10
  • the range of ⁇ 60 mass% is preferred, the range of 20 ⁇ 50 mass% is more preferred, and the range of 30 ⁇ 40 mass% is more preferred.
  • the blending amount of the resin (B) is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A) because the antistatic property can be further improved.
  • the range of parts is more preferable, and the range of 3 to 15 parts by mass is more preferable.
  • the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate.
  • the active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • a photopolymerization initiator (C) to the active energy ray-curable composition of the present invention.
  • a photosensitizer (D) can be further added to improve curability.
  • ionizing radiation such as electron beam, ⁇ -ray, ⁇ -ray, ⁇ -ray, etc.
  • it cures quickly without using a photopolymerization initiator (C) or photosensitizer (D). It is not necessary to add a photopolymerization initiator (C) or a photosensitizer (D).
  • Examples of the photopolymerization initiator (C) 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 (D) 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 photopolymerization initiator (C) and the photosensitizer (D) are used in the active energy ray-curable compound (A) and the compound (B) in the active energy ray-curable composition of the present invention. Is preferably 0.05 to 20 parts by mass, and more preferably 0.5 to 10% by mass with respect to 100 parts by mass in total.
  • the active energy ray-curable composition of the present invention includes an organic solvent and a polymerization depending on applications and required characteristics.
  • the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and it is particularly easy to adjust the film thickness for thin film coating.
  • the organic solvent that can be used here include alcohols such as methanol, ethanol, isopropanol, and t-butanol; ester compounds such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • the base film used in the film of the present invention 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 material of the base film is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate; a polyolefin resin such as polypropylene, polyethylene, or polymethylpentene-1.
  • Cellulose acetates such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, etc .; polymethyl methacrylate, etc.
  • Acrylic resin Vinyl chloride resin such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymer; Poly Polyethylene; Polysulfone; Polyethersulfone; Polyetheretherketone; Polyimide resin such as polyimide and polyetherimide; Norbornene resin (for example, “ZEONOR” manufactured by Nippon Zeon Co., Ltd.), modified norbornene resin (for example, , “Arton” manufactured by JSR Corporation), cyclic olefin copolymers (for example, “Apel” manufactured by Mitsui Chemicals, Inc.), and the like. Furthermore, you may use what bonded together 2 or more types of base materials which consist of these resin.
  • the thickness of the resin film 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.
  • 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 the film and then irradiating the active energy ray to form a cured coating film.
  • the method for applying the active energy ray-curable composition of the present invention to a film include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, and dip coating. Examples thereof include a coat, a spinner coat, a wheeler coat, a brush coat, a solid coat by silk screen, a wire bar coat, and a flow coat.
  • the active energy ray-curable composition of the present invention contains an organic solvent
  • the organic solvent In order to volatilize and to segregate the resin (B) on the coating film surface, it is preferable to heat or dry at room temperature.
  • the conditions for heat drying are not particularly limited as long as the organic solvent volatilizes. Usually, the heat drying is performed at a temperature in the range of 50 to 100 ° C. and for a time in the range of 0.5 to 10 minutes. preferable.
  • a device for irradiating ultraviolet rays to cure the active energy ray-curable composition for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical Lamp, black light lamp, mercury-xenon lamp, short arc lamp, helium / cadmium laser, argon laser, sunlight, LED lamp, and the like.
  • the film having a cured coating film of the active energy ray-curable composition of the present invention is applicable to various applications because of its excellent anti-blocking property and excellent scratch resistance on its surface.
  • an optical film used for an image display unit of an image display device such as an organic EL display (OLED).
  • OLED organic EL display
  • it since it has excellent scratch resistance even if it is thin, for example, electronic notebooks, mobile phones, smartphones, portable audio players, mobile personal computers, tablet terminals, etc. It can use suitably as an optical film of the image display part of this image display apparatus.
  • it can use as a protective film used for the outermost surface of the image display part of an image display apparatus, and a base material of a touch panel.
  • the transparent panel when used as a protective film, for example, in an image display device having a configuration in which a transparent panel for protecting the image display module is provided on the upper part of an image display module such as an LCD module or an OLED module, the transparent panel By sticking to the front or back surface of the plate, it is effective for preventing damage and preventing scattering when the transparent panel is damaged.
  • Example 1 90% by mass of the base resin obtained in Preparation Example 1 (45.8 parts by mass as the resin content) and a 45% by mass solution of the resin (1) having the quaternary ammonium salt (sulfonate) obtained in Synthesis Example 1 4.1 parts by mass (1.8 parts by mass as a resin) was uniformly mixed to obtain an active energy ray-curable composition (1).
  • Example 2 90% by mass of the base resin obtained in Preparation Example 1 (45.8 parts by mass as the resin content) and a 45% by mass solution of the resin (1) having the quaternary ammonium salt (sulfonate) obtained in Synthesis Example 1 10.2 parts by mass (4.6 parts by mass as a resin) were uniformly mixed to obtain an active energy ray-curable composition (2).
  • Example 3 90% by mass of the base resin obtained in Preparation Example 1 (45.8 parts by mass as the resin content) and a 45% by mass solution of the resin (2) having the quaternary ammonium salt (sulfonate) obtained in Synthesis Example 2 10.2 parts by mass (4.6 parts by mass as a resin) were uniformly mixed to obtain an active energy ray-curable composition (3).
  • TAC triacetyl cellulose
  • Table 1 shows the results of evaluation or measurement as described above.
  • the active energy ray-curable compositions of the present invention of Examples 1 to 3 are environment-friendly materials that are halogen-free and have excellent coating material appearance. Further, it was found that the cured coating film of the active energy ray-curable composition of the present invention has an excellent coating film appearance, and its surface resistance value is on the order of 10 9 to the 10th power and has high antistatic ability.
  • Comparative Example 1 is an example using a material having a quaternary ammonium salt containing chloride, but the coating material appearance, coating film appearance and surface resistance value were satisfactory levels, but it was not halogen-free. was there.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

Cette invention concerne : une composition durcissable par un rayonnement d'énergie active comprenant un composé durcissable par un rayonnement d'énergie active (A) et une résine (B) contenant un sel d'ammonium quaternaire représentée par la formule générale (1) ; et un film utilisant ladite composition. Cette composition durcissable par un rayonnement d'énergie active est capable de former un film de revêtement durci ayant des propriétés antistatiques comparables ou supérieures aux propriétés antistatiques des compositions classiques sans qu'il soit nécessaire de recourir à des halogènes tels que des chlorures, c'est-à-dire, tout en étant exempte d'halogènes. (Dans la formule, R1 à R3 représentent chacun indépendamment un groupe alkyle ou un groupe phényle, et R4 représente un groupe alkyle, un groupe alcoxy, un groupe phényle, ou un groupe oxyphényle).
PCT/JP2015/067601 2014-06-27 2015-06-18 Composition durcissable par un rayonnement d'énergie active et film l'utilisant WO2015198959A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201580030392.9A CN106459240B (zh) 2014-06-27 2015-06-18 活性能量射线固化性组合物及使用其的膜
KR1020167034439A KR101784239B1 (ko) 2014-06-27 2015-06-18 활성 에너지선 경화성 조성물 및 그를 사용한 필름
JP2016529510A JP6025010B2 (ja) 2014-06-27 2015-06-18 活性エネルギー線硬化性組成物及びそれを用いたフィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014132094 2014-06-27
JP2014-132094 2014-06-27

Publications (1)

Publication Number Publication Date
WO2015198959A1 true WO2015198959A1 (fr) 2015-12-30

Family

ID=54938044

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/067601 WO2015198959A1 (fr) 2014-06-27 2015-06-18 Composition durcissable par un rayonnement d'énergie active et film l'utilisant

Country Status (5)

Country Link
JP (1) JP6025010B2 (fr)
KR (1) KR101784239B1 (fr)
CN (1) CN106459240B (fr)
TW (1) TWI663229B (fr)
WO (1) WO2015198959A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019073616A (ja) * 2017-10-16 2019-05-16 Dic株式会社 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP2019073617A (ja) * 2017-10-16 2019-05-16 Dic株式会社 活性エネルギー線硬化性組成物及びそれを用いたフィルム
TWI736341B (zh) * 2019-07-04 2021-08-11 日商信越化學工業股份有限公司 正型阻劑材料及圖案形成方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111566129B (zh) * 2017-12-18 2022-06-14 Dic株式会社 活性能量射线固化性组合物及使用其的薄膜
JP7192868B2 (ja) * 2018-09-10 2022-12-20 Dic株式会社 活性エネルギー線硬化性組成物、及び、それを用いたフィルム
JP7334683B2 (ja) * 2019-08-02 2023-08-29 信越化学工業株式会社 ポジ型レジスト材料及びパターン形成方法
CN112300358A (zh) * 2020-05-27 2021-02-02 南京山维新材料科技有限公司 一种无溶剂型紫外光固化季铵盐树脂及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001098188A (ja) * 1999-09-29 2001-04-10 Mitsubishi Chemicals Corp 活性エネルギー線硬化性被覆組成物
JP2002121208A (ja) * 2000-08-11 2002-04-23 Mitsubishi Chemicals Corp 活性エネルギー線硬化性材料および帯電防止性トップコート剤
JP2006213802A (ja) * 2005-02-02 2006-08-17 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線硬化型樹脂組成物
JP2008069270A (ja) * 2006-09-14 2008-03-27 Dainippon Printing Co Ltd 帯電防止性光硬化型樹脂組成物、及び、それを用いた帯電防止膜及び物品
JP2012031297A (ja) * 2010-07-30 2012-02-16 Arakawa Chem Ind Co Ltd 活性エネルギー線硬化型樹脂組成物用帯電防止剤、活性エネルギー線硬化型組成物、硬化皮膜および帯電防止処理光学フィルム
JP2013227485A (ja) * 2011-12-09 2013-11-07 Nippon Shokubai Co Ltd 硬化性樹脂組成物及びその用途

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4670745B2 (ja) 2006-06-12 2011-04-13 日本化成株式会社 帯電防止組成物、帯電防止層および帯電防止フィルム
JP2008038092A (ja) * 2006-08-09 2008-02-21 Nippon Kasei Chem Co Ltd 帯電防止性樹脂組成物、帯電防止層、及び積層材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001098188A (ja) * 1999-09-29 2001-04-10 Mitsubishi Chemicals Corp 活性エネルギー線硬化性被覆組成物
JP2002121208A (ja) * 2000-08-11 2002-04-23 Mitsubishi Chemicals Corp 活性エネルギー線硬化性材料および帯電防止性トップコート剤
JP2006213802A (ja) * 2005-02-02 2006-08-17 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線硬化型樹脂組成物
JP2008069270A (ja) * 2006-09-14 2008-03-27 Dainippon Printing Co Ltd 帯電防止性光硬化型樹脂組成物、及び、それを用いた帯電防止膜及び物品
JP2012031297A (ja) * 2010-07-30 2012-02-16 Arakawa Chem Ind Co Ltd 活性エネルギー線硬化型樹脂組成物用帯電防止剤、活性エネルギー線硬化型組成物、硬化皮膜および帯電防止処理光学フィルム
JP2013227485A (ja) * 2011-12-09 2013-11-07 Nippon Shokubai Co Ltd 硬化性樹脂組成物及びその用途

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019073616A (ja) * 2017-10-16 2019-05-16 Dic株式会社 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP2019073617A (ja) * 2017-10-16 2019-05-16 Dic株式会社 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP7024309B2 (ja) 2017-10-16 2022-02-24 Dic株式会社 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP7114874B2 (ja) 2017-10-16 2022-08-09 Dic株式会社 活性エネルギー線硬化性組成物及びそれを用いたフィルム
TWI736341B (zh) * 2019-07-04 2021-08-11 日商信越化學工業股份有限公司 正型阻劑材料及圖案形成方法

Also Published As

Publication number Publication date
CN106459240B (zh) 2018-04-20
JP6025010B2 (ja) 2016-11-16
CN106459240A (zh) 2017-02-22
TW201606006A (zh) 2016-02-16
KR101784239B1 (ko) 2017-10-11
TWI663229B (zh) 2019-06-21
JPWO2015198959A1 (ja) 2017-04-20
KR20170010314A (ko) 2017-01-26

Similar Documents

Publication Publication Date Title
JP6025010B2 (ja) 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP5954505B2 (ja) 活性エネルギー線硬化性組成物、その硬化物及びその硬化塗膜を有する物品
WO2015098495A1 (fr) Film de revêtement dur et dispositif d'affichage d'information
JP6372685B2 (ja) 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP2014189566A (ja) 環状オレフィン樹脂用活性エネルギー線硬化性組成物及びそれを用いた環状オレフィン樹脂フィルム
TWI791642B (zh) 活性能量線硬化性組合物及使用其的硬化物及膜
TWI749213B (zh) 活性能量線硬化性組成物、及硬塗膜
WO2014192654A1 (fr) Composition durcissable par rayonnements d'énergie active et film produit à l'aide de celle-ci
JP6725864B2 (ja) 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP6135234B2 (ja) 環状オレフィン樹脂用活性エネルギー線硬化性組成物及びそれを用いた環状オレフィン樹脂フィルム
JPWO2018100929A1 (ja) 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP6388189B1 (ja) 活性エネルギー線硬化性組成物、硬化物、及び、フィルム
JP6418474B2 (ja) 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JP6331115B2 (ja) 環状オレフィン樹脂フィルム
JP5773099B2 (ja) 環状オレフィン樹脂フィルム
JP6288538B1 (ja) 活性エネルギー線硬化性組成物及びそれを用いたフィルム
JPWO2019235206A1 (ja) 活性エネルギー線硬化性組成物及びそれを用いたフィルム
CN109666173B (zh) 层叠体
JPWO2020054502A1 (ja) 活性エネルギー線硬化性組成物、及び、それを用いたフィルム
JP2019073617A (ja) 活性エネルギー線硬化性組成物及びそれを用いたフィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15812209

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016529510

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20167034439

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15812209

Country of ref document: EP

Kind code of ref document: A1