WO2018105442A1 - Composition de résine de type durcissable par rayonnement d'énergie active, et film stratifié - Google Patents

Composition de résine de type durcissable par rayonnement d'énergie active, et film stratifié Download PDF

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Publication number
WO2018105442A1
WO2018105442A1 PCT/JP2017/042553 JP2017042553W WO2018105442A1 WO 2018105442 A1 WO2018105442 A1 WO 2018105442A1 JP 2017042553 W JP2017042553 W JP 2017042553W WO 2018105442 A1 WO2018105442 A1 WO 2018105442A1
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meth
acrylate
resin
film
lactone
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PCT/JP2017/042553
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English (en)
Japanese (ja)
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伊藤　正広
東美 申
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Dic株式会社
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Priority to JP2018554934A priority Critical patent/JP7024729B2/ja
Publication of WO2018105442A1 publication Critical patent/WO2018105442A1/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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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 provides an active energy ray-curable resin composition having high adhesion to an inorganic material and having excellent scratch resistance and anti-cracking properties in a cured coating film, a paint containing the same, and a coating comprising the paint.
  • the present invention relates to a film and a laminated film.
  • Inorganic fine particle dispersed resin material obtained by dispersing inorganic fine particles in the resin component has higher hardness of cured coating, improved scratch resistance, and blocking resistance compared to resin materials consisting of organic materials only. In recent years, it has attracted attention as a new material that can provide high performance and new functions.
  • the inorganic fine particle dispersed resin material has various uses. For example, it is widely used as a hard coat agent for protecting molded articles, display surfaces, and various film materials from scratches.
  • an active energy ray-curable resin composition containing silica fine particles, an acryloyl group-containing acrylic resin, and a polyacrylate compound of a lactone-modified polyvalent aliphatic alcohol is known ( Patent Document 1).
  • the reactive dispersion described in Patent Document 1 is characterized by high scratch resistance in a cured product as compared with a hard coating agent composed only of an organic system, but has low crack prevention properties, and thus is brittle such as a cycloolefin film. When the film was used as a base material, cracks and breaks were easily generated.
  • the problem to be solved by the present invention is an active energy ray-curable resin composition having high adhesion to an inorganic material and having excellent scratch resistance and crack prevention in a cured coating film, and a paint containing the same
  • An object of the present invention is to provide a coating film and a laminated film using the paint.
  • the present inventor has used a lactone-modified urethane (meth) acrylate resin as a matrix resin in a resin material containing inorganic fine particles, so that metals such as copper and silver or SiO x , Al 2 O 3 , TiO 2 , ITO, and other inorganic material thin films made of inorganic compounds, as well as high adhesion to various inorganic materials such as glass and silicon wafers, with excellent scratch resistance and crack prevention It discovered that a coating film was obtained and came to complete this invention.
  • the present invention contains inorganic fine particles (A) and a matrix resin (B) having a (meth) acryloyl group, and the matrix resin (B) is an essential component of the lactone-modified urethane (meth) acrylate resin (B1). It relates to an active energy ray-curable resin composition.
  • the present invention further relates to a paint containing the active energy ray-curable resin composition.
  • the present invention further relates to a coating film comprising the paint.
  • the present invention further relates to a laminated film having a layer composed of the coating film.
  • an active energy ray-curable resin composition having high adhesion to an inorganic material and having excellent scratch resistance and crack prevention in a cured coating film, a paint containing the same, and the paint
  • the coating film and laminated film which become can be provided.
  • the active energy ray-curable resin composition of the present invention contains inorganic fine particles (A) and a matrix resin (B) having a (meth) acryloyl group, and the matrix resin (B) is a lactone-modified urethane (meth) acrylate.
  • the resin (B1) is an essential component.
  • the (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group.
  • (Meth) acrylate is a general term for acrylate and methacrylate.
  • the inorganic fine particles (A) can be obtained by dispersing the inorganic particles (a) as a raw material in the matrix resin (B) or a mixture of the matrix resin (B) and an organic solvent.
  • the inorganic particles (a) include fine particles such as silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These may be used alone or in combination of two or more.
  • silica particles are preferred because they are readily available and easy to handle.
  • examples of the silica particles include various silica particles such as fumed silica, wet silica called precipitation method silica, gel silica, sol-gel silica, and the like, and any of them may be used.
  • the inorganic particles (a) may be those obtained by introducing functional groups on the surface of fine particles with various silane coupling agents. By introducing a functional group on the surface of the inorganic particles (a), the miscibility with the organic component such as the matrix resin (B) is increased, and the storage stability is improved.
  • silane coupling agent examples include [(meth) acryloyloxyalkyl] trialkylsilane, [(meth) acryloyloxyalkyl] dialkylalkoxysilane, [(meth) acryloyloxyalkyl] alkyldialkoxysilane, [(meth) [Acryloyloxyalkyl] trialkoxysilane, (meth) acryloyloxy silane coupling agent; trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane , Vinyl silane coupling agents such as trialkoxyallylsilane; styryltrialkyl, styryldialkylalkoxy Styrene silane coupling agents such as silane, st
  • (meth) acryloyloxy-based silane coupling agents are preferred because they are inorganic fine particles (A) excellent in miscibility with organic components such as the matrix resin (B).
  • [(Meth) acryloyloxyalkyl] trialkoxysilanes such as (meth) acryloyloxypropyltrimethoxysilane are particularly preferred.
  • the average particle size of the inorganic fine particles (A) is not particularly limited, and may be appropriately adjusted according to the desired cured product performance.
  • the average particle diameter of the inorganic fine particles (A) is in the range of 80 to 250 nm. Is more preferable, and the range of 90 to 180 nm is more preferable, and the range of 100 to 150 nm is particularly preferable.
  • the average particle size of the inorganic fine particles (A) is a value obtained by measuring the particle size in the active energy ray-curable resin composition under the following conditions.
  • Particle size measuring device “ELSZ-2” manufactured by Otsuka Electronics Co., Ltd.
  • Particle size measurement sample A composition in which an active energy ray-curable resin composition is a methyl isobutyl ketone solution having a nonvolatile content of 1% by mass.
  • the content of the inorganic fine particles (A) is not particularly limited, and may be appropriately adjusted according to desired cured product performance and the like.
  • the mass ratio of the inorganic fine particles (A) to the matrix resin (B) [(A) / ( B)] is preferably in the range of 10/90 to 60/40, and more preferably in the range of 30/70 to 60/40 because a cured coating film having excellent blocking resistance can be obtained.
  • the lactone-modified urethane (meth) acrylate resin (B1) is not particularly limited as long as it is a (meth) acrylate compound having a ring opening structure of a lactone compound and a urethane bond site in the molecular structure, and a wide variety of compounds are used. Can do.
  • a reaction product using a polyisocyanate compound (x1) and a lactone-modified hydroxy (meth) acrylate compound (x2) as raw materials can be mentioned.
  • polyisocyanate compound (x1) examples include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone Alicyclic diisocyanate compounds such as diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate; Polymethylene polyphenylene having a repeating structure represented by the following structural formula (1) Sulfonyl polyisocyanates; these isocyanurate modified product, a biuret modified product
  • R 1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 2 is each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point that is linked to the structural moiety represented by the structural formula (1) via a methylene group marked with *.
  • l is 0 or an integer of 1 to 3
  • m is an integer of 1 or more.
  • polyisocyanate compounds (x1) an active energy ray-curable resin composition having an excellent balance between scratch resistance and crack prevention properties in a cured coating film can be obtained. Therefore, the aliphatic diisocyanate compound and the alicyclic compound are obtained. Diisocyanate compounds or these isocyanurate-modified products are preferred.
  • lactone-modified hydroxy (meth) acrylate compound (x2) examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylolpropane.
  • lactone-modified hydroxy (meth) acrylate compound (x2) examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylolpropane.
  • examples thereof include aliphatic hydroxy (meth) acrylate compounds such as tri (meth) acrylate and dipentaerythritol penta (meth) acrylate or those obtained by adding a lactone compound to these (poly) oxyalkylene
  • lactone compound examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -methylcaprolactone, ⁇ -ethylcaprolactone, ⁇ -propylcaprolactone, 3-pentene-4-olide, 12- Examples include dodecanolide and ⁇ -dodecanolactone. These may be used alone or in combination of two or more.
  • lactone-modified hydroxy (meth) acrylate compounds (x2) an active energy ray-curable resin composition having an excellent balance between scratch resistance and crack resistance in a cured coating film can be obtained.
  • the (meth) acrylate compound mono (meth) acrylate compounds such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate are preferably used.
  • the lactone compound is particularly preferably ⁇ -caprolactone.
  • the average number of moles added of the lactone compound is preferably in the range of 1 to 10, more preferably in the range of 1 to 5.
  • the average number of moles added of the lactone compound is a value calculated from the reaction ratio of the aliphatic hydroxy (meth) acrylate compound or these (poly) oxyalkylene modified products with the lactone compound.
  • the lactone-modified urethane (meth) acrylate resin (B1) is a part of a reaction raw material such as a polyol compound. May be included.
  • the reaction raw material contains other compounds
  • an active energy ray-curable resin composition having an excellent balance between scratch resistance and crack prevention in a cured coating film can be obtained, so that the lactone-modified urethane (meth) acrylate resin
  • the total mass of the polyisocyanate compound (x1) and the lactone-modified hydroxy (meth) acrylate compound (x2) is preferably 70% by mass or more and 90% by mass or more with respect to the total of the reaction raw materials of B1). More preferably.
  • the production of the lactone-modified urethane (meth) acrylate resin (B1) can be carried out under the same reaction conditions as in a general urethanization reaction.
  • reaction conditions raw materials are charged at a ratio such that the molar ratio of isocyanate group to hydroxyl group [(NCO) / (OH)] is in the range of 1 / 0.95 to 1 / 1.05.
  • Examples include a method of reacting with a known and usual urethanization catalyst under a temperature condition of about 0 ° C., if necessary.
  • the lactone-modified urethane (meth) acrylate resin (B1) preferably has a weight average molecular weight (Mw) in the range of 600 to 5,000.
  • Mw weight average molecular weight
  • the theoretical value of the (meth) acryloyl group equivalent calculated from the raw material charge ratio is preferably in the range of 300 to 2,500 g / equivalent, and more preferably in the range of 300 to 800 g / equivalent.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mn / Mw) are values measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device HLC-8220 manufactured by Tosoh Corporation Column: Tosoh Corporation guard column H XL -H + Tosoh Corporation TSKgel G5000H XL + Tosoh Corporation TSKgel G4000H XL + Tosoh Corporation TSKgel G3000H XL + Tosoh Corporation TSKgel G2000H XL Detector: RI (differential refractometer) Data processing: Tosoh Corporation SC-8010 Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; Polystyrene sample; 0.4% by mass tetrahydrofuran solution in terms of resin solids filtered through microfilter (100 ⁇ l)
  • the matrix resin (B) having the (meth) acryloyl group may contain other components other than the lactone-modified urethane (meth) acrylate compound (B1).
  • the other components include, for example, dendrimer type (meth) acrylate resin (B2), (meth) acryloyl group-containing acrylic resin (B3), urethane (meth) acrylate resin (B4) other than (B1), epoxy (meta) ) Acrylate resin (B5), mono (meth) acrylate compound and modified product (B6), aliphatic hydrocarbon type poly (meth) acrylate compound and modified product (B7), alicyclic poly (meth) acrylate compound and The modified body (B8), an aromatic poly (meth) acrylate compound, the modified body (B9), etc. are mentioned. These may be used alone or in combination of two or more.
  • the dendrimer type (meth) acrylate resin (B2) refers to a resin having a regular multi-branched structure and having a (meth) acryloyl group at the end of each branched chain. It is called a branch type or a star polymer. Examples of such compounds include, but are not limited to, those represented by the following structural formulas (2-1) to (2-8), and a regular multi-branched structure is not limited thereto. Any resin can be used as long as it has a (meth) acryloyl group at the end of each branched chain.
  • R 3 is a hydrogen atom or a methyl group
  • R 4 is a hydrocarbon group having 1 to 4 carbon atoms.
  • dendrimer type (meth) acrylate resin (B2) “Viscoat # 1000” manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500 to 2,000, average (meth) acryloyl per molecule Radix 14], “Biscoat 1020” [weight average molecular weight (Mw) 1,000 to 3,000], “SIRIUS501” [weight average molecular weight (Mw) 15,000 to 23,000], “SP-1106 manufactured by MIWON [Weight average molecular weight (Mw) 1,630, average number of (meth) acryloyl groups 18 per molecule], “CN2301”, “CN2302” [average number of (meth) acryloyl groups 16 per molecule] manufactured by SARTOMER, “ CN2303 ”[average number of 6 (meth) acryloyl groups per molecule],“ CN2304 ”[ Average number of (meth) acryloyl groups per molecule 18], “Esdrimer
  • the dendrimer type (meth) acrylate resin (B2) preferably has a weight average molecular weight (Mw) in the range of 1,000 to 30,000. Further, those having an average (meth) acryloyl group number per molecule of 5 to 30 are preferable.
  • the (meth) acryloyl group-containing acrylic resin (B3) is obtained by polymerizing, for example, a (meth) acrylate monomer ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxy group, an isocyanate group, or a glycidyl group as an essential component. What can be obtained by introducing a (meth) acryloyl group by further reacting the resulting acrylic resin intermediate with a (meth) acrylate monomer ( ⁇ ) having a reactive functional group capable of reacting with these functional groups. It is done.
  • the (meth) acrylate monomer ( ⁇ ) having a reactive functional group is, for example, a hydroxyl group-containing (meth) acrylate monomer such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; a carboxy such as (meth) acrylic acid Group-containing (meth) acrylate monomer; isocyanate group-containing (meth) acrylate monomer such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl (meth) acrylate And glycidyl group-containing (meth) acrylate monomers such as 4-hydroxybutyl acrylate glycidyl ether. These may be used alone or in combination of two or more.
  • the acrylic resin intermediate may be a copolymer obtained by copolymerizing other polymerizable unsaturated group-containing compound as required in addition to the (meth) acrylate monomer ( ⁇ ).
  • the other polymerizable unsaturated group-containing compound include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
  • Acrylic acid alkyl ester Cyclo ring-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl acrylate Aromatic ring-containing (meth) acrylates; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, ⁇ -methylstyrene, chlorostyrene, etc. .
  • the (meth) acrylic acid alkyl ester is used because it becomes an active energy ray-curable resin composition excellent in scratch resistance and crack prevention in a cured coating film. It is preferable.
  • the reaction ratio of both is excellent in curability. Since it becomes the (meth) acryloyl group-containing acrylic resin (B3), the ratio of the (meth) acrylate monomer ( ⁇ ) to the total of both is preferably in the range of 20 to 70 parts by mass, and 30 to 60% by mass. More preferably, it is in the range of part%.
  • the acrylic resin intermediate can be produced by the same method as a general acrylic resin.
  • it can be produced, for example, by polymerizing various monomers in the temperature range of 60 ° C. to 150 ° C. in the presence of a polymerization initiator.
  • the polymerization method include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
  • the polymerization mode include random copolymers, block copolymers, and graft copolymers.
  • a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone
  • a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether is preferably used.
  • a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone
  • a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether is preferably used.
  • the (meth) acrylate monomer ( ⁇ ) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate monomer ( ⁇ ), but is the following combination from the viewpoint of reactivity. Is preferred. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ ), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer ( ⁇ ).
  • the carboxy group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ )
  • the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ )
  • the hydroxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer ( ⁇ ).
  • the carboxy group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer ( ⁇ ).
  • the reaction between the acrylic resin intermediate and the (meth) acrylate monomer ( ⁇ ) is, for example, an esterification catalyst such as triphenylphosphine in a temperature range of 60 to 150 ° C. when the reaction is an esterification reaction. Can be used as appropriate. Further, when the reaction is a urethanization reaction, a method of reacting the acrylic resin intermediate while dropping the compound ( ⁇ ) in a temperature range of 50 to 120 ° C. can be used.
  • the weight-average molecular weight (Mw) of the (meth) acryloyl group-containing acrylic resin (B3) is preferably in the range of 5,000 to 80,000.
  • the (meth) acryloyl group equivalent is preferably in the range of 200 to 500 g / equivalent.
  • the urethane (meth) acrylate resin (B4) other than (B1) is obtained by reacting, for example, various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as required. Can be mentioned.
  • the polyisocyanate compound include various polyisocyanate compounds exemplified as the polyisocyanate compound (x1).
  • hydroxyl group-containing (meth) acrylate compound examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylolpropane tri (meth).
  • Hydroxyl group-containing (meth) acrylate compounds such as acrylate and dipentaerythritol penta (meth) acrylate; in the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds, (poly) oxyethylene chain, (poly) oxypropylene chain, ( And a (poly) oxyalkylene-modified product in which a (poly) oxyalkylene chain such as a poly) oxytetramethylene chain is introduced.
  • polyol compound examples include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatics such as biphenol and bisphenol.
  • poly) oxyalkylene in which (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, or other (poly) oxyalkylene chain is introduced into the molecular structure of the various polyol compounds. Examples include modified products.
  • Examples of the epoxy (meth) acrylate resin (B5) include those obtained by reacting an epoxy resin with (meth) acrylic acid or its anhydride.
  • Examples of the epoxy resin include diglycidyl ethers of dihydric phenols such as hydroquinone and catechol; diglycidyl ethers of biphenol compounds such as 3,3′-biphenyldiol and 4,4′-biphenyldiol; bisphenol A type epoxy resins; Bisphenol type epoxy resins such as bisphenol B type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalene Polyglycidyl ethers of naphthol compounds such as diols, 2,7-naphthalenediol, binaphthol, bis (2,7-dihydroxynaphthyl) methane; triglycid
  • Examples of the mono (meth) acrylate compound and the modified product (B6) include methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, propyl (meth) acrylate, hydroxypropyl (meth) acrylate, Aliphatic mono (meth) acrylate compounds such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; cycloaliphatic mono (meta) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate ) Acrylate compounds; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, pheno
  • R 3 is a hydrogen atom or a methyl group.
  • Mono (meth) acrylate compounds such as compounds represented by: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. in the molecular structure of the various mono (meth) acrylate compounds (Poly) oxyalkylene-modified products in which a (poly) oxyalkylene chain is introduced; lactone-modified products in which a (poly) lactone structure is introduced into the molecular structure of the various mono (meth) acrylate compounds.
  • Examples of the aliphatic hydrocarbon type poly (meth) acrylate compound and the modified product (B7) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol diene.
  • Aliphatic di (meth) acrylate compounds such as (meth) acrylate and neopentyl glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol Aliphatic tri (meth) acrylate compounds such as propane tri (meth) acrylate and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate and ditrimethylol
  • Four or more functional aliphatic poly (meth) acrylate compounds such as lopantetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acryl
  • Examples of alicyclic poly (meth) acrylate compounds and modified products (B8) thereof include 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, Cycloaliphatic di (meth) acrylate compounds such as cyclopentanyl di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate; in the molecular structure of the various alicyclic poly (meth) acrylate compounds (poly ) (Poly) oxyalkylene modified products in which a (poly) oxyalkylene chain such as an oxyethylene chain, (poly) oxypropylene chain, or (poly) oxytetramethylene chain is introduced; various alicyclic poly (meth) acrylate compounds described above Modified lactone with (poly) lactone structure in the molecular structure And the like.
  • Aromatic poly (meth) acrylate compounds and modified products (B9) thereof include, for example, biphenol di (meth) acrylate, bisphenol di (meth) acrylate, the following structural formula (4)
  • each R 5 independently represents any of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group.
  • each R 5 independently represents any of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group.
  • An aromatic di (meth) acrylate compound such as a fluorene compound represented by: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) in the molecular structure of the various aromatic poly (meth) acrylate compounds (Poly) oxyalkylene modified products in which (poly) oxyalkylene chains such as oxytetramethylene chains are introduced; lactone modified products in which (poly) lactone structures are introduced into the molecular structures of the various aromatic poly (meth) acrylate compounds Etc.
  • the matrix resin (B) having the (meth) acryloyl group contains other components other than the lactone-modified urethane (meth) acrylate resin (B1), scratch resistance and crack prevention in the cured coating film produced by the present invention
  • the content of the lactone-modified urethane (meth) acrylate resin (B1) with respect to the total mass of the matrix resin (B) is in the range of 10 to 80% by mass. A range of 20 to 70% by mass is more preferable.
  • a dendrimer type poly (meth) acrylate resin (B2) or a (meth) acryloyl group-containing acrylic resin (B3) as the other component.
  • these components (B2) or (B3) are preferably used in the range of 5 to 70% by mass, more preferably in the range of 20 to 50% by mass with respect to the total mass of the matrix resin (B). preferable.
  • the mono (meth) acrylate compound and its modified product (B6), the aliphatic hydrocarbon poly (meth) acrylate compound and its modified product It is preferable to appropriately use each component of B7), the alicyclic poly (meth) acrylate compound and its modified product (B8), and the aromatic poly (meth) acrylate compound and its modified product (B9).
  • these components (B6) to (B9) are preferably used in the range of 3 to 50% by weight, more preferably in the range of 5 to 40% by weight, based on the total weight of the matrix resin (B). preferable.
  • the matrix resin (B) contains a structural portion derived from a lactone compound contained in the lactone-modified urethane (meth) acrylate resin (B1) in the range of 10 to 25% by mass.
  • the lactone structure ratio (mass%) in the matrix resin (B) is [total mass of structural sites derived from the lactone compound possessed by the lactone-modified urethane (meth) acrylate resin (B1)] / [matrix resin (B) component
  • the total mass] ⁇ 100 (% by mass) is a value calculated from the above [the total mass of the structural portion derived from the lactone compound possessed by the lactone-modified urethane (meth) acrylate resin (B1), etc.]. It is a value calculated from the raw material charge ratio or a value calculated from the published structural formula of the manufacturer.
  • the active energy ray-curable resin composition of the present invention may contain various additive components according to desired performance in addition to the inorganic fine particles (A) and the matrix resin (B).
  • Additive components include, for example, photopolymerization initiators, photosensitizers, organic solvents, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, antistatic agents, silane coupling agents, and adhesion assistants. , Organic beads, rheology control agents, defoaming agents, antifogging agents, coloring agents and the like.
  • the photopolymerization initiator may be selected and used according to the type of active energy ray to be irradiated.
  • Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) Alkylphenone photopolymerization initiators such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples include acylphosphine oxide photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.
  • photopolymerization initiators include, for example, “IRGACURE127”, “IRGACURE184”, “IRGACURE250”, “IRGACURE270”, “IRGACURE290”, “IRGACURE369E”, “IRGACURE379EG”, “IRGACURE500”, “IRGACURE500”, manufactured by BASF. , “IRGACURE 754”, “IRGACURE 819”, “IRGACURE 907”, “IRGACURE 1173”, “IRGACURE 2959”, “IRGACURE MBF”, “IRGACURE TPO”, “IRGACURE OXE 01”, “IRGACURE OX”, etc.
  • the photopolymerization initiator is preferably used in an amount of 0.05 to 20 parts by mass with respect to 100 parts by mass of the component excluding the organic solvent in the active energy ray-curable resin composition. More preferably, it is used in the range of 1 to 10 parts by mass.
  • photosensitizer examples include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.
  • organic solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone (ketone solvents such as tetrahydrofuran; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono Examples include glycol ether solvents such as propyl ether, etc. These may be used alone or in combination of two or more. And it may be.
  • the organic solvent is used mainly for the purpose of adjusting the viscosity of the active energy ray-curable resin composition, but is usually preferably adjusted so that the nonvolatile content is in the range of 10 to 60% by mass.
  • Examples of the ultraviolet absorber include 2- [4- ⁇ (2-hydroxy-3-dodecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4- ⁇ (2-hydroxy-3-tridecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 Triazine derivatives such as 1,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- And xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These may be used alone or in combination of two or more.
  • antioxidants examples include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants. These may be used alone or in combination of two or more.
  • silicon-based additive examples include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl.
  • examples include polyorganosiloxanes having alkyl groups and phenyl groups, such as polysiloxane copolymers and amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes having polyether-modified acrylic groups, and polydimethylsiloxanes having polyester-modified acrylic groups. It is done. These may be used alone or in combination of two or more.
  • fluorine-based additive examples include DIC Corporation “Megaface” series. These may be used alone or in combination of two or more.
  • antistatic agent examples include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis (trifluoromethanesulfonyl) imide or bis (fluorosulfonyl) imide. These may be used alone or in combination of two or more.
  • silane coupling agent examples are the same as those used for the surface modification of the inorganic fine particles (A). These may be used alone or in combination of two or more.
  • adhesion assistant examples include phosphate compounds such as isopropyl acid phosphate, triisodecyl phosphite, ethylene oxide-modified phosphate dimethacrylate, and the like. These may be used alone or in combination of two or more.
  • examples of commercially available dispersion aids include “Kayamar PM-21” and “Kayamer PM-2” manufactured by Nippon Kayaku Co., Ltd., “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd., and the like.
  • organic beads examples include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads. These may be used alone or in combination of two or more. These organic beads preferably have an average particle size in the range of 1 to 10 ⁇ m.
  • additives can be added in any amount depending on the desired performance and the like, but usually used in the range of 0.01 to 40 parts by mass in 100 parts by mass of the active energy ray-curable resin composition. It is preferable.
  • the method for producing the active energy ray-curable resin composition is not particularly limited, and may be produced by any method.
  • a dispersion machine having a stirring blade such as a disper or a turbine blade, a dispersion machine such as a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, or a bead mill is used. It can be produced by a method of mixing and dispersing in a matrix component such as a matrix resin (B) having an (meth) acryloyl group and an organic solvent. Among these, it is preferable to use a ball mill or a bead mill because a uniform and stable dispersion can be obtained.
  • the method of mixing and dispersing the inorganic particles (a) in the matrix component may be, for example, a method of dispersing the inorganic particles (a) in the total amount of the matrix component and producing the active energy ray-curable resin composition in a lump, Alternatively, the inorganic particles (a) may be dispersed in a part of the matrix component to produce a pre-dispersion, and then the remaining matrix component may be blended. Various additives may be added in the dispersion step, or may be added after the inorganic particles (a) are dispersed in the matrix component.
  • the active energy ray-curable resin composition of the present invention has a high scratch resistance characteristic in a cured coating film, it is suitable for coating applications for protecting molded products, display members, and various film materials from scratches. Can be used. Furthermore, taking advantage of the high crack-preventing property of the cured product, it can be suitably used particularly as a paint for plastic films.
  • the paint containing the active energy ray-curable resin composition can be applied on various substrates and irradiated with active energy rays to be cured, thereby forming a coating film for protecting the substrate surface.
  • the coating material of the present invention may be used by directly applying to the surface protection member, or a coating applied on a plastic film may be used as the protective film. Or you may use what applied the coating material of this invention on the plastic film, and formed the coating film as optical films, such as an antireflection film, a diffusion film, and a prism sheet. Furthermore, a layer made of other paints other than the paint of the present invention may be stacked.
  • plastic film examples include triacetyl cellulose film, polyester film, acrylic film, cycloolefin polymer film, polyamide film, polyimide film, polystyrene film, polycarbonate film, and polypropylene film.
  • the triacetyl cellulose film is a film that is particularly suitably used for polarizing plate applications in liquid crystal displays.
  • the thickness is generally as thin as 40 to 100 ⁇ m, it is resistant even when a hard coat layer is provided. It is difficult to make the scratch resistance sufficiently high, and it is easy to curl large.
  • the coating film made of the resin composition of the present invention has high scratch resistance, excellent curl resistance, toughness, and transparency even when a triacetyl cellulose film is used as a base material. Can be used.
  • the coating amount when applying the coating material of the present invention is such that the film thickness after drying is in the range of 4 to 20 ⁇ m, preferably in the range of 6 to 15 ⁇ m. It is preferable.
  • the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
  • the polyester film is, for example, polyethylene terephthalate, and the thickness thereof is generally about 100 to 300 ⁇ m. Although it is a cheap and easy to process film, it is a film used for various applications such as a touch panel display. However, it is very soft and has a feature that it is difficult to sufficiently increase the scratch resistance even when a hard coat layer is provided.
  • the coating amount when applying the coating material of the present invention is in the range of 5 to 100 ⁇ m, preferably 7 to 80 ⁇ m after drying, depending on the application. It is preferable to apply as described above.
  • the paint of the present invention is excellent in curling resistance. Since it has characteristics, curling hardly occurs even when it is applied with a relatively high film thickness exceeding 30 ⁇ m, and it can be suitably used.
  • the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
  • polymethylmethacrylate film is generally relatively thick and durable with a thickness of about 100 to 2,000 ⁇ m, so it is suitable for applications that require particularly high scratch resistance, such as liquid crystal display front plate applications. It is the film used for.
  • the coating amount when applying the coating material of the present invention is in the range of 5 to 100 ⁇ m, preferably 7 to 80 ⁇ m after drying, depending on the application. It is preferable to apply so that it becomes.
  • a coating is applied on a relatively thick film such as a polymethyl methacrylate film to a film thickness exceeding 30 ⁇ m, it becomes a highly scratch-resistant laminated film, but the transparency tends to decrease.
  • the paint of the present invention has a very high transparency as compared with the conventional paint, a laminated film having high scratch resistance and transparency can be obtained.
  • the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
  • the cured coating film obtained from the resin composition of the present invention is excellent in the followability to the film itself and has flexibility even in such a fragile film, and thus effectively cracks the film when bent. Can be prevented.
  • the thickness of the cured coating film is preferably adjusted in the range of 0.1 to 10 ⁇ m. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
  • Examples of the active energy rays irradiated when the paint of the present invention is cured to form a coating film include ultraviolet rays and electron beams.
  • an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED lamp or the like as a light source is used, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary.
  • a high-pressure mercury lamp it is preferable to cure at a conveyance speed of 5 to 50 m / min with respect to one lamp having a light quantity that is usually in the range of 80 to 160 W / cm.
  • an electron beam accelerator having an accelerating voltage that is usually in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m / min.
  • the base material to which the paint of the present invention is applied can be suitably used not only as a plastic film but also as a surface coating agent for various plastic molded products, for example, cellular phones, electric appliances, automobile bumpers and the like.
  • examples of the method for forming the coating film include a coating method, a transfer method, and a sheet bonding method.
  • the coating method is a method in which the paint is spray-coated or coated as a top coat on a molded product using a printing device such as a curtain coater, roll coater, gravure coater, etc., and then cured by irradiation with active energy rays. is there.
  • a transfer material obtained by applying the above-described coating material of the present invention on a substrate sheet having releasability is adhered to the surface of the molded product, and then the substrate sheet is peeled off to top coat the surface of the molded product.
  • curing by irradiation with active energy rays, or by bonding the transfer material to the surface of the molded article, curing by irradiation with active energy rays, and then peeling the substrate sheet A method of transferring the top coat to the surface is mentioned.
  • a protective sheet having a coating film made of the paint of the present invention on a base sheet, or a protective sheet having a coating film made of the paint and a decorative layer on a base sheet is plastic molded.
  • a protective layer is formed on the surface of the molded product by bonding to the product.
  • the coating material of the present invention can be preferably used for the transfer method and the sheet adhesion method.
  • a transfer material is first prepared.
  • the transfer material can be produced, for example, by applying the paint alone or mixed with a polyisocyanate compound onto a base sheet and heating to semi-cure (B-stage) the coating film. .
  • the matrix resin (B) having the (meth) acryloyl group contained in the active energy ray-curable compound of the present invention is a compound having a hydroxyl group in the molecular structure, the B-staging step is more efficient.
  • it may be used in combination with a polyisocyanate compound.
  • the above-described paint of the present invention is applied onto a base sheet.
  • the method for applying the paint include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a coating method such as a comma coating method, and a printing method such as a gravure printing method and a screen printing method.
  • the coating thickness is preferably such that the thickness of the cured coating film is 0.1 to 30 ⁇ m because the wear resistance and chemical resistance are good, and it is preferably 1 to 6 ⁇ m. It is more preferable to paint so that
  • the coating film is semi-cured (B-stage) by heating and drying.
  • the heating is usually 55 to 160 ° C, preferably 100 to 140 ° C.
  • the heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes.
  • the surface protective layer of the molded product using the transfer material may be formed by, for example, bonding the B-staged resin layer of the transfer material and the molded product, and then irradiating active energy rays to cure the resin layer.
  • the B-staged resin layer of the transfer material is adhered to the surface of the molded product, and then the base sheet of the transfer material is peeled to remove the B-staged resin layer of the transfer material.
  • energy rays are cured by irradiation with active energy rays to cure the resin layer by cross-linking (transfer method), or the transfer material is sandwiched in a mold and the resin is placed in the cavity.
  • a transfer material is adhered to the surface, the substrate sheet is peeled off and transferred onto the molded product, and then the energy beam is cured by irradiation with active energy rays to crosslink and cure the resin layer. And the like (molding simultaneous transfer method).
  • the sheet bonding method is specifically a resin layer formed by bonding a base sheet of a protective layer forming sheet prepared in advance and a molded product, and then thermally curing by heating to form a B-stage.
  • a method of performing cross-linking curing (post-adhesion method), and the protective layer forming sheet is sandwiched in a molding die, and a resin is injected and filled in the cavity to obtain a resin molded product, and at the same time, the surface and the protective layer are formed.
  • a method in which a resin sheet is bonded and then thermally cured by heating to crosslink and cure the resin layer (molding simultaneous bonding method).
  • the coating film of the present invention is a coating film formed by applying and curing the coating material of the present invention on a substrate such as the plastic film, or the coating material of the present invention as a surface protective agent for plastic molded products. It is a coating film formed by coating and curing.
  • the laminated film of the present invention is a film in which the coating film is formed on a base film such as the plastic film.
  • the laminated film of the present invention may have other layer configurations in addition to the coating film made of the paint of the present invention.
  • it may have a coating film made of the coating material of the present invention on the base film, and may further have an inorganic material on the surface of the coating film.
  • the formation method of these various layer structures is not particularly limited, and for example, the resin raw material may be directly applied, or a sheet-shaped material may be bonded together with an adhesive.
  • the inorganic material examples include an inorganic material thin film made of a metal such as copper or silver, or an inorganic compound such as SiO x , Al 2 O 3 , TiO 2 , or ITO, and glass or a silicon wafer.
  • a film obtained by applying the paint of the present invention on a plastic film and irradiating an active energy ray is used as a protective film for a polarizing plate used for a liquid crystal display, a touch panel display or the like. It is preferable to use as the coating film hardness.
  • the coating film hardness when the paint of the present invention is applied to a protective film of a polarizing plate used for a liquid crystal display, a touch panel display, etc., and the film is formed by irradiating and curing active energy rays, the cured coating film has a high hardness. It becomes a protective film having high transparency.
  • the adhesive layer may be formed in the surface on the opposite side of the coating layer which apply
  • the laminated film of the present invention makes use of the features of high scratch resistance and crack prevention, and is used for display members, automobile members, building materials, surface protection films for various electronic devices, home appliances, furniture, plating substitutes, paint substitutes It can use suitably for various uses.
  • Example of this invention it is the value measured on condition of the following using a weight average molecular weight (Mw) and a gel permeation chromatograph (GPC).
  • Mw weight average molecular weight
  • GPC gel permeation chromatograph
  • Measuring device HLC-8220 manufactured by Tosoh Corporation Column: Tosoh Corporation guard column H XL -H + Tosoh Corporation TSKgel G5000HXL + Tosoh Corporation TSKgel G4000HXL + Tosoh Corporation TSKgel G3000HXL + Tosoh Corporation TSKgel G2000HXL Detector: RI (differential refractometer) Data processing: Tosoh Corporation SC-8010 Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; Polystyrene sample; 0.4% by mass tetrahydrofuran solution in terms of resin solids filtered through microfilter (100 ⁇ l)
  • the average particle diameter of the inorganic fine particles (A) is a value obtained by measuring the particle diameter in the active energy ray-curable resin composition under the following conditions.
  • Particle size measuring device “ELSZ-2” manufactured by Otsuka Electronics Co., Ltd.
  • Particle size measurement sample A composition in which an active energy ray-curable resin composition is a methyl isobutyl ketone solution having a nonvolatile content of 1% by mass.
  • the lactone structure ratio (% by mass) in the matrix resin (B) is [total mass of structural sites derived from the lactone compound possessed by the lactone-modified urethane (meth) acrylate resin (B1)] / [matrix resin. (B) Total mass of component] ⁇ 100 (% by mass), and the [total mass of the structural portion derived from the lactone compound possessed by the lactone-modified urethane (meth) acrylate resin (B1)] is It is a value calculated from the raw material charge ratio at the time of manufacturing the resin, or a value calculated from a sales maker's published structural formula.
  • Production Example 1 Production of Lactone Modified Hydroxy (meth) acrylate Compound (x2-1)
  • a reaction apparatus equipped with a stirrer 400 parts by mass of ⁇ -caprolactone, 208 parts by mass of hydroxyethyl acrylate, 0.1 part by mass of dibutyltin dilaurate and 0.1 part by weight of methoquinone was added and reacted at 130 ° C. for 8 hours with stirring to obtain a lactone-modified hydroxy (meth) acrylate compound (x2-1).
  • Lactone-Modified Urethane (Meth) acrylate Resin (B1-1) A reaction apparatus equipped with a stirrer was charged with a polyisocyanate compound (“Bernock DN-901S” hexamethylene diisocyanate modified from DIC Corporation, (Isocyanate group content 23.5% by mass) 342 parts by mass, dibutyltin dilaurate 2 parts by mass and methoquinone 2 parts by mass were added, and the temperature was raised to 60 ° C. with stirring. Next, 658 parts by mass of the lactone-modified hydroxy (meth) acrylate compound (x2-1) was added in portions over about one hour. The mixture was heated to 80 ° C.
  • a polyisocyanate compound (“Bernock DN-901S” hexamethylene diisocyanate modified from DIC Corporation, (Isocyanate group content 23.5% by mass) 342 parts by mass, dibutyltin dilaurate 2 parts by mass and
  • the reaction was terminated, and the lactone-modified urethane (meth) acrylate resin (B1-2) was obtained. Obtained.
  • the weight average molecular weight (Mw) of the lactone-modified urethane (meth) acrylate resin (B1-2) was 1,500, and the theoretical value of the (meth) acryloyl group equivalent calculated from the raw material charge ratio was 460 g / equivalent.
  • Production Example 4 Production of Lactone-Modified (Meth) acrylate Resin (B1-3) To a reaction apparatus equipped with a stirrer, 223 parts by mass of isophorone diisocyanate, 2 parts by mass of dibutyltin dilaurate and 2 parts by mass of methoquinone were added and stirred. The temperature was raised to ° C. Next, 757 parts by mass of the lactone-modified hydroxy (meth) acrylate compound (x2-1) was added in portions over about one hour. The mixture was heated to 80 ° C. and further reacted for 3 hours.
  • the (meth) acryloyl group-containing acrylic resin (B3-1) has a weight average molecular weight (Mw) of 20,000, a theoretical value of (meth) acryloyl group equivalent calculated from the raw material charge ratio is 309 g / equivalent, hydroxyl value Was 182 mg KOH / g.
  • Example 1 Production and Evaluation of Active Energy Ray Curable Resin Composition An active energy ray curable resin composition and a laminated film were produced in the following manner, and various evaluation tests were performed. The results are shown in Table 1.
  • active energy ray-curable resin composition 150 parts by mass of the lactone-modified urethane (meth) acrylate resin (B1-1) and 200 parts by mass of a methyl isobutyl ketone solution of the (meth) acryloyl group-containing acrylic resin (B3-1) (Resin solid content 100 parts by weight), aliphatic hydrocarbon type poly (meth) acrylate compound (B7-1) 25 parts by weight, inorganic fine particles (A-1) [“Aerosil R7200” manufactured by Nippon Aerosil Co., Ltd., primary average A wet ball mill having a particle diameter of 12 nm and fumed silica fine particles having a (meth) acryloyl group on the particle surface] 225 parts by mass and methyl isobutyl ketone 400 parts by mass to obtain a slurry having a nonvolatile content of 50% by mass (Ashizawa Co., Ltd. “Star Mill LMZ015”) is mixed and disper
  • Each condition of dispersion by the wet ball mill is as follows.
  • Media Zirconia beads having a median diameter of 100 ⁇ m
  • Filling ratio of resin composition with respect to the inner volume of the mill 70% by volume
  • Peripheral speed of the tip of the stirring blade 12 m / sec
  • Flow rate of resin composition 200 ml / min
  • Dispersion time 60 minutes
  • Non-volatile content 50% by mass 100 parts by mass of the obtained dispersion (non-volatile content 50% by mass) was added, and methyl isobutyl ketone and propylene glycol monomethyl ether were further added.
  • the active energy ray-curable resin composition was obtained by adjusting the nonvolatile content to 30% by mass.
  • the active energy ray-curable resin composition was applied onto a cycloolefin film (film thickness 100 ⁇ m) with a bar coater so that the film thickness after curing was 2 ⁇ m, and dried at 80 ° C. for 2 minutes.
  • a laminated film was obtained by passing and curing at a dose of 500 mJ / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere.
  • the film for a test was obtained by making it pass and harden
  • the laminated film and the test film were stacked so that their painted surfaces were in contact with each other, and rubbed together under a load.
  • the case of smooth sliding (with anti-blocking property) was designated as A
  • the case of non-sliding (blocking) was designated as B.
  • the laminated film prepared above was placed in a sputtering apparatus, and a conductive film having a copper thin film having a thickness of 400 nm was obtained by sputtering using a Cu target in an Ar gas 20 cc / min atmosphere. Next, an adhesive tape peeling test of 100 squares of 1 mm square was performed on the surface of the copper thin film formed on the conductive film in accordance with JIS K-5400. Adhesion was evaluated by measuring the number of grids that did not peel.
  • “Inorganic fine particles (A-2)” in Table 1 indicate hydrophobic fumed silica (“Aerosil R8200” manufactured by Nippon Aerosil Co., Ltd.).

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Abstract

L'invention fournit une composition de résine de type durcissable par rayonnement d'énergie active, un matériau de revêtement comprenant celle-ci, un film de revêtement constitué à l'aide dudit matériau de revêtement, et un film stratifié. Ladite composition de résine de type durcissable par rayonnement d'énergie active est caractéristique en ce qu'elle comprend des microparticules inorganiques (A), et une résine matrice (B) possédant un groupe (méth)acryloyle. Ladite résine matrice (B) a pour composant essentiel une résine (méth)acrylate uréthane modifié par lactone (B1). Cette composition de résine de type durcissable par rayonnement d'énergie active présente une adhérence élevée vis-à-vis d'un matériau inorganique, et permet de former un film de revêtement dur doté d'excellentes propriétés de résistance à l'abrasion et de prévention de fissure.
PCT/JP2017/042553 2016-12-08 2017-11-28 Composition de résine de type durcissable par rayonnement d'énergie active, et film stratifié WO2018105442A1 (fr)

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JPWO2020209264A1 (ja) * 2019-04-10 2021-10-07 Dic株式会社 活性エネルギー線硬化性樹脂組成物、硬化物、積層体及び物品
CN114656767A (zh) * 2020-12-22 2022-06-24 Dic株式会社 活性能量射线固化性树脂组合物、固化物及物品

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JP6780799B1 (ja) * 2020-04-07 2020-11-04 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化性ハードコート剤、積層体、透明導電フィルム、光学部材、および電子機器

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