WO2018230427A1 - 硬化性組成物及び積層フィルム - Google Patents
硬化性組成物及び積層フィルム Download PDFInfo
- Publication number
- WO2018230427A1 WO2018230427A1 PCT/JP2018/021823 JP2018021823W WO2018230427A1 WO 2018230427 A1 WO2018230427 A1 WO 2018230427A1 JP 2018021823 W JP2018021823 W JP 2018021823W WO 2018230427 A1 WO2018230427 A1 WO 2018230427A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- mass
- curable composition
- film
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
Definitions
- the present invention relates to a curable composition excellent in various performances such as substrate adhesion, surface hardness, low shrinkage, and flexibility in a cured product, and a coating film and a laminated film using the curable composition.
- a resin material having a (meth) acryloyl group can be easily and instantaneously cured by ultraviolet irradiation or the like, and is excellent in transparency and hardness of a cured product, so that it is widely used in the fields of paints and coating agents. It has been.
- the coating objects range from optical films, plastic molded products, woodwork, etc., and the required performance varies depending on the type and application of the coating object, so it was designed according to the purpose. Many resins have been proposed.
- An active energy ray-curable resin composition containing a (meth) acryloyl group-containing acrylic resin, pentaerythritol tetraacrylate, and pentaerythritol triacrylate is known as a resin material having a (meth) acryloyl group.
- Patent Document 1 Since the active energy ray-curable resin composition described in Patent Document 1 has an excellent balance between surface hardness and low curing shrinkage in a cured product, it is useful as a coating agent for coating relatively thin plastic films. is there. However, the adhesion to the film substrate, in particular the adhesion after long-term storage under high temperature and humidity conditions, is low, and there is a problem that peeling easily occurs.
- the problem to be solved by the present invention is that a curable composition excellent in various performances such as substrate adhesion, surface hardness, low shrinkage and flexibility in a cured product, and a coating comprising the curable composition are used. It is to provide a film and a laminated film.
- the present inventor contains a (meth) acryloyl group-containing acrylic resin and a (meth) acrylic ester of dipentaerythritol. ) It has been found that a curable composition having a hydroxyl value of acrylic esterified product in the range of 40 to 140 mgKOH / g is excellent in various properties such as substrate adhesion, surface hardness, low shrinkage and flexibility in the cured product. The present invention has been completed.
- the present invention is a curable composition containing a (meth) acryloyl group-containing acrylic resin (A) and a (meth) acrylic ester of dipentaerythritol (B), wherein the dipentaerythritol ((
- the present invention relates to a curable composition characterized in that the hydroxyl value of the (meth) acrylate ester (B) is in the range of 40 to 140 mgKOH / g.
- the present invention further relates to a coating film comprising the curable composition.
- the present invention further relates to a laminated film having a layer composed of the coating film.
- a curable composition excellent in various properties such as substrate adhesion, surface hardness, low shrinkage, and flexibility in a cured product, and a coating film and a laminate film using the curable composition. can do.
- the curable composition of the present invention contains a (meth) acryloyl group-containing acrylic resin (A) and a (meth) acrylic ester of dipentaerythritol (B), and the (meth) acrylic of the dipentaerythritol.
- the hydroxyl value of the acid esterified product (B) is in the range of 40 to 140 mgKOH / g.
- 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 (meth) acryloyl group acrylic resin (A) is obtained, for example, by polymerizing, as an essential component, a (meth) acrylate monomer ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxy group, an isocyanate group, or a glycidyl group. And an acrylic resin intermediate obtained by introducing a (meth) acryloyl group by further reacting a (meth) acrylate monomer ( ⁇ ) having a reactive functional group capable of reacting with these functional groups. .
- 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 copolymerized with the (meth) acrylate monomer ( ⁇ ) or other (meth) acrylate monomer or styrene derivative as required.
- 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 the curable composition has an excellent balance of curl resistance, flexibility, scratch resistance, etc. in the cured coating film. It is preferable to use it. Moreover, it is preferable that 80 mass% or more of the reaction raw material of (meth) acryloyl group acrylic resin (A) is a (meth) acrylate monomer which does not contain an aromatic ring.
- the reaction ratio of both is excellent in curability. Since it becomes a (meth) acryloyl group containing acrylic resin (A), it is preferable that the ratio of the said (meth) acrylate monomer ((alpha)) with respect to the sum total of both is 30 mass% or more.
- the total amount of the (meth) acrylate monomer ( ⁇ ) and the other polymerizable unsaturated group-containing compound ( The proportion of the (meth) acrylate monomer ( ⁇ ) is preferably in the range of 30 to 50% by mass.
- the (meth) acrylate monomer ( ⁇ ) with respect to the total of the (meth) acrylate monomer ( ⁇ ) and the other polymerizable unsaturated group-containing compound. ) Is preferably 55% by mass or more.
- 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 reaction ratio between the two is preferably such that the (meth) acrylate monomer ( ⁇ ) is used in the range of 0.95 to 1.05 mol with respect to 1 mol of the functional group in the acrylic resin intermediate.
- the (meth) acryloyl group-containing acrylic resin (A) preferably has a mass average molecular weight (Mw) in the range of 3,000 to 80,000, more preferably in the range of 5,000 to 30,000. preferable.
- the (meth) acryloyl group equivalent is preferably in the range of 200 to 500 g / equivalent.
- mass 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 (meth) acrylic ester (B) of dipentaerythritol is obtained by converting part or all of the hydroxyl groups of dipentaerythritol into (meth) acrylic ester, and dipentaerythritol mono (meth) acrylate, di- Selected from the group consisting of pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Contains one or more.
- (pentaerythritol) (meth) acrylic ester (B) is produced by a method of esterifying dipentaerythritol and acrylic acid, a (meth) acrylic ester of dipentaerythritol ( As a by-product other than B), a high molecular weight component (b ′) such as an addition reaction product of dipentaerythritol (meth) acrylate may be generated.
- the high molecular weight component (b ′) may be purified and removed, or a dimethaerythritol (meth) acrylic ester (B) crude product containing this may be used as it is.
- the content of the high molecular weight component (b ') in the (meth) acrylic acid ester (B) crude product of dipentaerythritol is preferably in the range of 1 to 20% by mass.
- dipentaerythritol is a curable composition that is particularly excellent in substrate adhesion and surface hardness in a cured product
- dipentaerythritol penta (meth) acrylate and dipenta It is preferable to contain erythritol hexa (meth) acrylate.
- the mass ratio of the two is preferably in the range of 20/80 to 90/10, and more preferably in the range of 40/60 to 85/15.
- dipentaerythritol tetra (meth) acrylate in terms of becoming a curable composition having further excellent substrate adhesion.
- the content of dipentaerythritol tetra (meth) acrylate, dipentaerythritol It is preferably in the range of 1 to 30% by mass, more preferably in the range of 5 to 20% by mass with respect to the total of pentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
- the content of each component in the (meth) acrylic ester of dipentaerythritol (B) or a crude product containing the same, and the ratio of the content of each component were measured under the following conditions. It is a value calculated from the area ratio of the liquid chromatography chart.
- the hydroxyl value of the (meth) acrylic ester (B) of dipentaerythritol is in the range of 40 to 140 mgKOH / g. Furthermore, since it is a curable composition having excellent substrate adhesion in a cured product and further excellent balance of surface hardness, scratch resistance, curl resistance, flexibility, etc., in the range of 40 to 120 mgKOH / g. More preferably, it is in the range of 70 to 120 mgKOH / g.
- the (meth) acrylic ester (B) of dipentaerythritol is produced by a method of esterifying dipentaerythritol and acrylic acid, the high molecular weight component (b ′) and the like are added.
- the hydroxyl value of the crude product to be contained is preferably in the range of 40 to 140 mgKOH / g, and more preferably in the range of 80 to 140 mgKOH / g.
- the hydroxyl value of the (meth) acrylic ester of dipentaerythritol (B) crude product is an actual value measured according to JIS K 0070, and (meth) acrylic ester of dipentaerythritol.
- the hydroxyl value of the compound (B) is a calculated value calculated from the composition ratio of each component calculated from the area ratio of the liquid chromatography chart.
- the mass ratio [(A) / (B) of the (meth) acryloyl group-containing acrylic resin (A) and the (meth) acrylic ester of the dipentaerythritol (B). ] is a curable composition having excellent adhesion to a substrate in a cured product, and further excellent balance of surface hardness, scratch resistance, curl resistance, flexibility, and the like. It is preferable that it is the range of these.
- [(A) / (B)] is preferably in the range of 60/40 to 99/1 from the viewpoint of excellent substrate adhesion, curl resistance, flexibility and the like in the cured coating film.
- (A) / (B)] is preferably in the range of 30/70 to 55/45 from the viewpoint of excellent scratch resistance and surface hardness in the cured coating film.
- the curable composition of the present invention comprises a (meth) acrylate compound (C) other than the (meth) acryloyl group-containing acrylic resin (A) or the (meth) acrylic ester of dipentaerythritol (B). You may contain.
- (meth) acrylate compounds (C) include, for example, dendrimer type (meth) acrylate resin (C1), urethane (meth) acrylate resin (C2), epoxy (meth) acrylate resin (C3), and mono (meth) acrylate Compound and its modified body (C4), aliphatic hydrocarbon type poly (meth) acrylate compound and its modified body (C5), alicyclic poly (meth) acrylate compound and its modified body (C6), aromatic poly (meta) ) Acrylate compound and its modified body (C7). These may be used alone or in combination of two or more.
- the dendrimer type (meth) acrylate resin (C1) 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 (1-1) to (1-8), 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 1 is a hydrogen atom or a methyl group
- R 2 is a hydrocarbon group having 1 to 4 carbon atoms.
- the dendrimer type (meth) acrylate resin (C1) preferably has a mass 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.
- Examples of the urethane (meth) acrylate resin (C2) include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as necessary.
- Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, water Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; Aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-n
- R 3 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
- R 4 is each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point that is linked to a structural moiety represented by the structural formula (2) via a methylene group marked with *.
- l is 0 or an integer of 1 to 3
- m is an integer of 1 or more.
- 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, ( (Poly) oxyalkylene chain-modified (poly) oxyalkylene chain such as poly) oxytetramethylene chain; (poly) lactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds Lactone-modified products thereof were.
- 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.
- Modified body lactone modified body in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds.
- Examples of the epoxy (meth) acrylate resin (C3) 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 (C4) 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 5 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 (C5) thereof 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; 4 or more functional groups such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate Aliphatic poly (meth) acrylate compound; (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc.
- Examples of alicyclic poly (meth) acrylate compounds and modified products (C6) 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 compound and the modified product (C7) are, for example, biphenol di (meth) acrylate, bisphenol di (meth) acrylate, the following structural formula (4)
- each R 6 is independently a (meth) acryloyl group, a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- R 7 is independently a (meth) acryloyl group, a (meth) acryloyloxy group or 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 effects exhibited by the present invention are sufficiently exerted, so the total of (meth) acryloyl group-containing compound components contained in the curable composition is included.
- the total of the (meth) acryloyl group-containing acrylic resin (A) and the (meth) acrylic ester (B) of dipentaerythritol is preferably 70% by mass or more, and 90% by mass or more. More preferred.
- the (meth) acryloyl group content in the total of (meth) acryloyl group-containing compound components is preferably in the range of 3.8 to 8.5 mmol / g.
- the curable composition of the present invention can be cured, for example, by irradiation with active energy rays.
- a 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
- the polymerization initiator is preferably used in an amount of 0.05 to 20 parts by weight, based on 100 parts by weight of the component excluding the organic solvent in the curable composition, and 0.1 to 10 parts by weight. It is more preferable to use within a range.
- the curable composition of the present invention may further contain other components.
- the other components include, for example, inorganic fine particles, silane coupling agents, phosphate ester compounds, solvents, ultraviolet absorbers, antioxidants, silicon additives, fluorine additives, antistatic agents, organic beads, quantum dots (QD), rheology control agent, defoaming agent, antifogging agent, colorant and the like.
- the inorganic fine particles are added for the purpose of adjusting the hardness, refractive index and the like in the cured coating film of the curable composition, and various publicly known inorganic fine particles can be used.
- 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 having particularly high versatility include various types 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 surface of the inorganic fine particles may be modified with a silane coupling agent or the like.
- the particle size of the inorganic fine particles is appropriately adjusted according to the desired coating film performance and the like, but the measured value by the dynamic light scattering method is preferably in the range of 10 to 250 nm.
- the addition amount is preferably in the range of 0.1 to 60% by mass with respect to the total of components other than the solvent of the curable composition.
- silane coupling agent examples include [(meth) acryloyloxyalkyl] trialkylsilane, [(meth) acryloyloxyalkyl] dialkylalkoxysilane, [(meth) acryloyloxyalkyl] alkyldialkoxysilane, and [(meth) acryloyl.
- (Meth) acryloyloxy silane coupling agents such as oxyalkyl] trialkoxysilane; trialkylvinylsilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, tri Vinyl-based silane coupling agents such as alkoxyallylsilane; styryltrialkyl, styryldialkylalkoxysilane Styrene-based silane coupling agents such as styrene, styrylalkyldialkoxysilane, styryltrialkoxysilane; (glycidyloxyalkyl) trialkylsilane, (glycidyloxyalkyl) dialkylalkoxysilane, (glycidyloxyalkyl) alkyl
- Poxy-based silane coupling agents (isocyanate alkyl) trialkylsilane, (isocyanatealkyl) dialkylalkoxysilane, (isocyanatealkyl) alkyldialkoxysilane, (isocyanatealkyl) trialkoxysilane and other isocyanate-based silane coupling agents It is done. These may be used alone or in combination of two or more.
- Examples of commercially available phosphoric acid ester compounds include, for example, “Kayamar PM-2” and “Kayamar PM-21” manufactured by Nippon Kayaku Co., Ltd., which are phosphoric acid ester compounds having a (meth) acryloyl group in the molecular structure.
- the solvent is added for the purpose of adjusting the coating viscosity of the curable composition, and the type and amount of the solvent are appropriately adjusted according to the desired performance.
- the curable composition is used so that the nonvolatile content is in the range of 10 to 90% by mass.
- the solvent include, for example, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate and butyl acetate; aromatics such as toluene and xylene.
- Solvents include cycloaliphatic, methylcyclohexane and other alicyclic solvents; carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether and other alcohol solvents; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Examples include glycol ether solvents such as glycol monopropyl ether. These may be used alone or in combination of two or more.
- 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.
- 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.
- the quantum dot is a group II-V semiconductor compound, a group II-VI semiconductor compound, a group III-IV semiconductor compound, a group III-V semiconductor compound, a group III-VI semiconductor compound, a group IV-VI semiconductor compound, Examples include I-III-VI group semiconductor compounds, II-IV-VI group semiconductor compounds, II-IV-V group semiconductor compounds, I-II-IV-VI group semiconductor compounds, group IV elements or compounds containing these. .
- Examples of the II-VI group semiconductor compound include binary compounds such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe; ZnSeS, ZnSeTe, ZnSTe, CdZnSe, CdZnSe, CdZnTe, CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, ternary compounds such as HgZnTe; CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgZnTe, HgZnSeS, HgZnSeTe, such HgZn
- the group III-IV semiconductor compound examples include B 4 C 3 , Al 4 C 3 , and Ga 4 C 3 .
- the III-V group semiconductor compound is, for example, a binary compound such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb; GANP, GANAS, GaNSb, Ternary compounds such as GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP; GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInPAsInGas And quaternary compounds such as InAlNAs, InAlNSb, InAlPAs, and InAlPSb.
- III-VI semiconductor compound examples include Al 2 S 3 , Al 2 Se 3 , Al 2 Te 3 , Ga 2 S 3 , Ga 2 Se 3 , Ga 2 Te 3 , GaTe, In 2 S 3 , In 2.
- examples include Se 3 , In 2 Te 3 , InTe, and the like.
- IV-VI group semiconductor compound examples include binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, PbTe; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbSe, SnPbSe, SnPbSe, SnPbSe Quaternary compounds such as SnPbSSe, SnPbSeTe, and SnPbSTe;
- I-III-VI group semiconductor compound examples include CuInS 2 , CuInSe 2 , CuInTe 2 , CuGaS 2 , CuGaSe 2 , CuGaSe 2 , AgInS 2 , AgInSe 2 , AgInTe 2 , AgGaSe 2 , AgGaTe 2 , AgGaTe 2, etc.
- Examples of the group IV element or the compound containing the element include C, Si, Ge, SiC, and SiGe.
- the quantum dot may be composed of a single semiconductor compound or may have a core-shell structure composed of a plurality of semiconductor compounds. Moreover, the surface may be modified with an organic compound.
- additives can be added in an arbitrary amount depending on the desired performance and the like, but usually 0.01 to 40 mass in 100 mass parts of the components excluding the solvent in the curable composition. It is preferable to use within the range of parts.
- the curable composition of the present invention is produced by mixing the above-described blending components.
- the mixing method is not particularly limited, and a paint shaker, a disper, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, or the like may be used.
- the curable composition of the present invention has a low curing shrinkage and has excellent characteristics such as moisture and heat resistance, curl resistance, surface hardness, scratch resistance, and flexibility in a cured coating film. It can be suitably used for paint applications for protecting articles, display members, and various film materials from scratches.
- the curable composition of the present invention can form a coating film that protects the surface of the substrate by applying it on various substrates and irradiating and curing with an active energy ray.
- the curable composition of the present invention may be directly applied to a surface-protecting member, or may be applied on a plastic film as a protective film. Or you may use what applied the curable composition 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, you may pile up the layer which consists of other coating materials other than the curable composition of this invention, etc.
- 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 curable composition of the present invention has high scratch resistance and transparency even when a triacetyl cellulose film is used as a base material, and further has an effect of excellent curling resistance and toughness. I can do it.
- the coating amount when applying the curable composition 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 to apply to.
- 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 curable composition of the present invention is such that the film thickness after drying is in the range of 5 to 100 ⁇ m, preferably 7 to 80 ⁇ m, in accordance with the application. It is preferable to apply in such a range.
- 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 curable composition of the present invention is in the range of 5 to 100 ⁇ m, preferably 7 to 7 after drying depending on the application. It is preferable to apply in a range of 80 ⁇ m.
- 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 curable composition of the present invention has very high transparency as compared with the conventional paint, a laminated film having both 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.
- cycloolefin polymer films are generally weak against lateral forces such as tearing, and are known to have poor folding resistance. It is spreading.
- the cured coating film obtained from the curable 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 curable composition 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 curable composition of the present invention is applied is suitably used not only as a plastic film but also as a surface coating agent for various plastic molded articles, for example, cellular phones, electric appliances, automobile bumpers and the like. be able to.
- 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 curable composition of the present invention onto a substrate sheet having releasability is adhered to the surface of the molded product, and then the substrate sheet is peeled off to peel off the surface of the molded product.
- a method of transferring the top coat to the substrate and then irradiating and curing the active energy ray, or adhering the transfer material to the surface of the molded article, irradiating and curing the active energy ray, and then peeling the substrate sheet. can be used to transfer the top coat onto the surface of the molded product.
- the sheet bonding method includes a protective sheet having a coating film made of the curable composition of the present invention on a base sheet, or a coating film and a decorative layer made of the curable composition of the present invention on a base sheet. Is bonded to a plastic molded product to form a protective layer on the surface of the molded 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 (meth) acryloyl group-containing resin contained in the curable composition of the present invention is a compound having a hydroxyl group in the molecular structure, it is used in combination with a polyisocyanate compound for the purpose of more efficiently performing the B-staging step. May be.
- the above-described curable composition of the present invention is coated on a substrate sheet.
- the coating method 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, 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 is 0.1 to 30 ⁇ m, since the scratch resistance and the like are good, and the coating is preferably 1 to 6 ⁇ m. It is more preferable.
- 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 curable composition of the present invention on a substrate such as the plastic film, or the surface protection agent of a plastic molded product. It is a coating film formed by coating and curing the curable composition.
- 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 curable composition of the present invention.
- the method for forming these various layer configurations is not particularly limited, and for example, the resin raw material may be directly applied, or a sheet-like material may be bonded together with an adhesive.
- a film obtained by applying the curable composition of the present invention on a plastic film and irradiating an active energy ray is used for a polarizing liquid crystal display or a touch panel display. It is preferable to use it as a protective film for a plate from the viewpoint of excellent coating film hardness.
- the curable composition of the present invention is applied on a protective film of a polarizing plate used for a liquid crystal display, a touch panel display, etc., and a film formed by irradiating and curing active energy rays, It is a protective film that combines high hardness and 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 can be suitably used for various applications such as surface protection films for various electronic devices, home appliances, furniture, plating replacement, painting replacement, in addition to display members, automobile members, and building materials.
- the mass average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).
- 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 (meth) acryloyl group-containing acrylic resin (A-1) has an acryloyl group equivalent of 213 g / equivalent, a number average molecular weight (Mn) of 12,000, a mass average molecular weight (Mw) of 22,000, and measured with an E-type viscometer. The viscosity was 1200 mPa ⁇ s.
- the (meth) acryloyl group-containing acrylic resin (A-2) has an acryloyl group equivalent of 250 g / equivalent, a number average molecular weight (Mn) of 11,000, a mass average molecular weight (Mw) of 20,500, and measured with an E-type viscometer.
- the viscosity was 1080 mPa ⁇ s.
- the (meth) acryloyl group-containing acrylic resin (A-3) has an acryloyl group equivalent of 313 g / equivalent, a number average molecular weight (Mn) of 4,200, a weight average molecular weight (Mw) of 8,400, and measured with an E-type viscometer. The viscosity was 360 mPa ⁇ s.
- the (meth) acryloyl group-containing acrylic resin (A-4) has an acryloyl group equivalent of 417 g / equivalent, a number average molecular weight (Mn) of 5,200, a weight average molecular weight (Mw) of 24,700, and measured with an E-type viscometer. The viscosity was 15,200 mPa ⁇ s.
- the (meth) acryloyl group-containing acrylic resin (A-5) has a methacryloyl group equivalent of 313 g / equivalent, a number average molecular weight (Mn) of 6,700, a mass average molecular weight (Mw) of 14,000, and measured with an E-type viscometer. The viscosity was 960 mPa ⁇ s.
- the hydroxyl value of the product measured according to JIS K 0070 is 42 mgKOH / g
- the content of dipentaerythritol pentaacrylate calculated from the area ratio of the liquid chromatography chart is 40.2%
- the content of dipentaerythritol hexaacrylate The amount was 50.7%
- the content of other high molecular weight components was 9.1%.
- the hydroxyl value of the (meth) acrylic ester of dipentaerythritol (B-1) calculated from the content ratio of each component was 47.9 mgKOH / g.
- the hydroxyl value of the product measured according to JIS K 0070 is 88 mgKOH / g
- the content of dipentaerythritol tetraacrylate calculated from the area ratio of the liquid chromatography chart is 7.2%
- the content of dipentaerythritol pentaacrylate The amount was 48.3%
- the content of dipentaerythritol hexaacrylate was 30.7%
- the content of other high molecular weight components was 13.8%.
- the hydroxyl value of the (meth) acrylic acid ester (B-2) of dipentaerythritol calculated from the content ratio of each component was 79.9 mgKOH / g.
- the hydroxyl value of the product measured according to JIS K 0070 is 130 mgKOH / g
- the content of dipentaerythritol tetraacrylate calculated from the area ratio of the liquid chromatography chart is 15%
- the content of dipentaerythritol pentaacrylate is
- the content of dipentaerythritol hexaacrylate was 60%
- the content of other high molecular weight components was 10%.
- the hydroxyl value of the (meth) acrylic ester of dipentaerythritol (B-3) calculated from the content ratio of each component was 111.2 mgKOH / g.
- the curable composition was applied onto a polyethylene terephthalate (PET) film (film thickness 80 ⁇ m) with a bar coater so that the film thickness after curing was 5 ⁇ m, and dried at 80 ° C. for 1 minute.
- a laminated film was obtained by passing and curing at a dose of 200 mJ / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere.
- Curling resistance test A 10 cm square coating film was cut out from the laminated film to obtain a test piece, and the floating of the test piece from the horizontal was measured, and the average value (mm) was evaluated. The smaller the value, the smaller the curl and the better the curl resistance.
- the laminated film was stored for 250 hours under conditions of room temperature 85 ° C. and humidity 85% RH. Thereafter, 100 grids were created by cutting a 10 ⁇ 10 grid pattern at intervals of 1 mm on the coated film side of the laminated film with a cutter knife. Next, after a cellophane tape was applied on the grid, a test for rapid peeling was performed, and the number of the 100 grids that were not peeled was evaluated. A: 95 or more B: 80 or more C: 60 or more D: Less than 60
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
Description
カラム ; 東ソー株式会社製ガードカラムHXL-H
+東ソー株式会社製 TSKgel G5000HXL
+東ソー株式会社製 TSKgel G4000HXL
+東ソー株式会社製 TSKgel G3000HXL
+東ソー株式会社製 TSKgel G2000HXL
検出器 ; RI(示差屈折計)
データ処理:東ソー株式会社製 SC-8010
測定条件: カラム温度 40℃
溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 ;ポリスチレン
試料 ;樹脂固形分換算で0.4質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
[測定条件]
装置:株式会社島津製作所製「LCMS-2010EV」
データ処理:株式会社島津製作所製「LCMS Solution」
カラム:東ソー株式会社製「ODS-100V」(2.0mmID×150mm、3μm)40℃
溶離液:水/アセトニトリル、0.4mL/分
検出器:PDA、MS
試料調整:1.資料50mgをアセトニトリル(LC用)10mlに溶解
2.30秒間ボルテックスで撹拌
3.30分間静置
4.0.2μmろ過フィルターに通液し測定試料とした
面積比の計算:UV波長210nmで算出
で表される化合物等のモノ(メタ)アクリレート化合物:前記各種のモノ(メタ)アクリレート化合物の分子構造中に(ポリ)オキシエチレン鎖、(ポリ)オキシプロピレン鎖、(ポリ)オキシテトラメチレン鎖等の(ポリ)オキシアルキレン鎖を導入した(ポリ)オキシアルキレン変性体;前記各種のモノ(メタ)アクリレート化合物の分子構造中に(ポリ)ラクトン構造を導入したラクトン変性体等が挙げられる。
で表されるビカルバゾール化合物、下記構造式(5-1)又は(5-2)
で表されるフルオレン化合物等の芳香族ジ(メタ)アクリレート化合物;前記各種の芳香族ポリ(メタ)アクリレート化合物の分子構造中に(ポリ)オキシエチレン鎖、(ポリ)オキシプロピレン鎖、(ポリ)オキシテトラメチレン鎖等の(ポリ)オキシアルキレン鎖を導入した(ポリ)オキシアルキレン変性体;前記各種の芳香族ポリ(メタ)アクリレート化合物の分子構造中に(ポリ)ラクトン構造を導入したラクトン変性体等が挙げられる。
カラム ; 東ソー株式会社製ガードカラムHXL-H
+東ソー株式会社製 TSKgel G5000HXL
+東ソー株式会社製 TSKgel G4000HXL
+東ソー株式会社製 TSKgel G3000HXL
+東ソー株式会社製 TSKgel G2000HXL
検出器 ; RI(示差屈折計)
データ処理:東ソー株式会社製 SC-8010
測定条件: カラム温度 40℃
溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 ;ポリスチレン
試料 ;樹脂固形分換算で0.4質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
[測定条件]
装置:株式会社島津製作所製「LCMS-2010EV」
データ処理:株式会社島津製作所製「LCMS Solution」
カラム:東ソー株式会社製「ODS-100V」(2.0mmID×150mm、3μm)40℃
溶離液:水/アセトニトリル、0.4mL/分
検出器:PDA、MS
試料調整:1.資料50mgをアセトニトリル(LC用)10mlに溶解
2.30秒間ボルテックスで撹拌
3.30分間静置
4.0.2μmろ過フィルターに通液し測定試料とする
面積比の計算:UV波長210nmで算出
攪拌装置、冷却管、滴下ロートおよび窒素導入管を備えた反応装置に、メチルイソブチルケトンを33.3質量部仕込み、攪拌しながら系内温度が110℃になるまで加熱した。ついで、メタクリル酸グリシジル100質量部、t-ブチルパーオキシ-2-エチルヘキサノエート(日油株式会社製「パーブチルO」)4質量部、メチルイソブチルケトン36質量部からなる混合液を4時間かけて滴下した。滴下後、110℃で10時間撹拌を続け、不揮発分60質量%のアクリル樹脂中間体(1)溶液を得た。アクリル樹脂中間体(1)のエポキシ基当量は148g/当量であった。
攪拌装置、冷却管、滴下ロートおよび窒素導入管を備えた反応装置に、メチルイソブチルケトンを33.3質量部仕込み、攪拌しながら系内温度が110℃になるまで加熱した。ついで、メタクリル酸グリシジル80質量部、メタクリル酸メチル20質量部、t-ブチルパーオキシ-2-エチルヘキサノエート(日油株式会社製「パーブチルO」)4質量部、メチルイソブチルケトン36質量部からなる混合液を4時間かけて滴下した。滴下後、110℃で10時間撹拌を続け、不揮発分60質量%のアクリル樹脂中間体(2)溶液を得た。アクリル樹脂中間体(2)のエポキシ基当量は185g/当量であった。
攪拌装置、冷却管、滴下ロートおよび窒素導入管を備えた反応装置に、メチルイソブチルケトンを40質量部仕込み、攪拌しながら系内温度が110℃になるまで加熱した。ついで、メタクリル酸グリシジル60質量部、メタクリル酸メチル40質量部、t-ブチルパーオキシ-2-エチルヘキサノエート(日油株式会社製「パーブチルO」)8質量部、メチルイソブチルケトン32質量部からなる混合液を4時間かけて滴下した。滴下後、110℃で10時間撹拌を続け、不揮発分60質量%のアクリル樹脂中間体(3)溶液を得た。アクリル樹脂中間体(3)のエポキシ基当量は256g/当量であった。
攪拌装置、冷却管、滴下ロートおよび窒素導入管を備えた反応装置に、メチルイソブチルケトンを46.6質量部仕込み、攪拌しながら系内温度が110℃になるまで加熱した。ついで、メタクリル酸グリシジル40質量部、メタクリル酸メチル60質量部、t-ブチルパーオキシ-2-エチルヘキサノエート(日油株式会社製「パーブチルO」)2質量部、メチルイソブチルケトン18質量部からなる混合液を4時間かけて滴下した。滴下後、110℃で10時間撹拌を続け、不揮発分60質量%のアクリル樹脂中間体(4)溶液を得た。アクリル樹脂中間体(4)のエポキシ当量は362g/当量であった。
攪拌装置、冷却管、滴下ロートおよび窒素導入管を備えた反応装置に、メチルイソブチルケトンを73質量部仕込み、攪拌しながら系内温度が110℃になるまで加熱した。ついで、メタクリル酸50質量部、メタクリル酸メチル50質量部、t-ブチルパーオキシ-2-エチルヘキサノエート(日油株式会社製「パーブチルO」)9質量部、メチルイソブチルケトン35質量部からなる混合液を4時間かけて滴下した。滴下後、110℃で10時間撹拌を続け、不揮発分60質量%のアクリル樹脂中間体(5)溶液を得た。アクリル樹脂中間体(5)の酸価は300mgKOH/gであった。
温度計、攪拌器、及びコンデンサーを備えたフラスコに、アクリル酸400質量部、ジペンタエリスリトール180質量部、硫酸15質量部、塩化第二銅1.5質量部、トルエン300質量部を仕込んだ。撹拌しながら105℃まで加熱し、系中を還流させながら105℃で18時間反応させた。反応中に生成した水は71.8質量部であった。反応混合物にトルエン425質量部を追加し、蒸留水200質量部で溶液を洗浄した。更に、20%水酸化ナトリウム水溶液を添加して反応混合物を中和し、蒸留水100質量部で洗浄した。樹脂固形分に対して500ppm量のハイドロキノンモノメチルエーテルを添加した後、トルエンを留去し、ジペンタエリスリトールの(メタ)アクリル酸エステル化物(B-1)を含む生成物を得た。JIS K 0070に準じて測定した生成物の水酸基価は42mgKOH/g、液体クロマトグラフィーチャートの面積比から算出されるジペンタエリスリトールペンタアクリレートの含有量は40.2%、ジペンタエリスリトールヘキサアクリレートの含有量は50.7%、その他高分子量成分の含有量は9.1%であった。また、各成分の含有量比から算出されるジペンタエリスリトールの(メタ)アクリル酸エステル化物(B-1)の水酸基価は47.9mgKOH/gであった。
温度計、攪拌器、及びコンデンサーを備えたフラスコに、アクリル酸300質量部、ジペンエリスリトール180質量部、硫酸15質量部、塩化第二銅1.5質量部、トルエン300質量部を仕込んだ。撹拌しながら105℃まで加熱し、系中を還流させながら同温度で12時間反応させた。反応中に生成した水は68.5質量部であった。反応混合物にトルエン425質量部を追加し、蒸留水200質量部で溶液を洗浄した。更に、20%水酸化ナトリウム水溶液を添加して反応混合物を中和し、蒸留水100質量部で洗浄した。樹脂固形分に対して500ppm量のハイドロキノンモノメチルエーテルを添加した後、トルエンを留去し、ジペンタエリスリトールの(メタ)アクリル酸エステル化物(B-2)を含む生成物を得た。JIS K 0070に準じて測定した生成物の水酸基価は88mgKOH/g、液体クロマトグラフィーチャートの面積比から算出されるジペンタエリスリトールテトラアクリレートの含有量は7.2%、ジペンタエリスリトールペンタアクリレートの含有量は48.3%、ジペンタエリスリトールヘキサアクリレートの含有量は30.7%、その他高分子量成分の含有量は13.8%であった。また、各成分の含有量比から算出されるジペンタエリスリトールの(メタ)アクリル酸エステル化物(B-2)の水酸基価は79.9mgKOH/gであった。
温度計、攪拌器、及びコンデンサーを備えたフラスコに、アクリル酸250質量部、ジペンエリスリトール180質量部、硫酸15質量部、塩化第二銅1.5質量部、トルエン300質量部を仕込んだ。撹拌しながら105℃まで加熱し、系中を還流させながら105℃で9時間反応させた。反応中に生成した水は68.5質量部であった。反応混合物にトルエン425質量部を追加し、蒸留水200質量部で溶液を洗浄した。更に、20%水酸化ナトリウム水溶液を添加して反応混合物を中和し、蒸留水100質量部で洗浄した。樹脂固形分に対して500ppm量のハイドロキノンモノメチルエーテルを添加した後、トルエンを留去し、ジペンタエリスリトールの(メタ)アクリル酸エステル化物(B-3)を含む生成物を得た。JIS K 0070に準じて測定した生成物の水酸基価は130mgKOH/g、液体クロマトグラフィーチャートの面積比から算出されるジペンタエリスリトールテトラアクリレートの含有量は15%、ジペンタエリスリトールペンタアクリレートの含有量は60%、ジペンタエリスリトールヘキサアクリレートの含有量は15%、その他高分子量成分の含有量は10%であった。また、各成分の含有量比から算出されるジペンタエリスリトールの(メタ)アクリル酸エステル化物(B-3)の水酸基価は111.2mgKOH/gであった。
表1、2に示す割合で各成分を混合し、メチルエチルケトンを用いて不揮発分を30質量%に調整して硬化性組成物を得た。得られた硬化性組成物について下記の要領で各種評価試験を行った。結果を表1、2に示す。
※(A-1)~(A-5):製造例1~5で得た(メタ)アクリロイル基含有アクリル樹脂(A-1)~(A-5)
※(B-1)~(B-3):製造例6~8で得たジペンタエリスリトールの(メタ)アクリル酸エステル化物(B-1)~(B-3)
※PETA:東亜合成株式会社製「M-305」ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートとを質量比6/4で含有するペンタエリスリトールのアクリル酸エステル化物
※光重合開始剤:BASF社製「イルガキュア#184」
硬化性組成物の(メタ)アクリロイル基含有化合物成分の合計における(メタ)アクリロイル基含有量を、各成分の反応原料仕込み比、及び配合割合を元に算出した。
前記硬化性組成物をポリエチレンテレフタレート(PET)フィルム(膜厚80μm)上に硬化後の膜厚が5μmとなるようにバーコーターで塗布し、80℃で1分乾燥させた。窒素雰囲気下で高圧水銀灯を用いて200mJ/cm2の照射量で通過させて硬化させることにより、積層フィルムを得た。
前記積層フィルムについて、JIS K5600-5-4に準拠し、塗膜面側の鉛筆硬度を500g荷重条件下で測定した。1つの硬度につき5回測定を行い、傷が付かなかった測定が4回以上あった硬度を硬化塗膜の硬度とした。
A:2H以上
B:2H未満
スチールウール(日本スチールウール株式会社製「ボンスター#0000」)0.5gで直径2.4センチメートルの円盤状の圧子を包み、該圧子に500g重の荷重をかけて、積層フィルムの塗装表面を10往復させる磨耗試験を行った。磨耗試験前後の積層フィルムのヘーズ値をスガ試験機株式会社製「ヘーズコンピュータHZ-2」を用いて測定し、それらの差の値(dH)で評価した。
A:1.0以下
B:3.0以下
C:10以下
D:10以上
マンドレル試験機(TP技研社製「屈曲試験機」)を用いて前記積層フィルムを試験棒に巻きつけ、ヒビや剥がれが生じるか否かを目視確認する試験を行い、ヒビや剥がれが生じない試験棒の最小径を評価結果とした。試験棒は直径2mmのものから10mmまで1mm刻みのものを用いた。
前記積層フィルムから10cm四方の塗膜を切り出して試験片を得、該試験片について4角の水平からの浮きを測定し、その平均値(mm)で評価した。値が小さいほどカールが小さく、耐カール性に優れる。
積層フィルムを室温85℃、湿度85%RH条件下に250時間保管した。その後、積層フィルムの塗膜面側に1mm間隔で10×10の碁盤目状にカッターナイフで切れ目を入れて100個の碁盤目を作成した。次いで、碁盤目上にセロハンテープを貼りつけた後、急速に剥がす試験を行い、100個の碁盤目のうち剥がれなかったものの数で評価した。
A:95個以上
B:80個以上
C:60個以上
D:60個未満
Claims (7)
- (メタ)アクリロイル基含有アクリル樹脂(A)と、ジペンタエリスリトールの(メタ)アクリル酸エステル化物(B)とを含有する硬化性組成物であって、
前記ジペンタエリスリトールの(メタ)アクリル酸エステル化物(B)の水酸基価が、40~140mgKOH/gの範囲であることを特徴とする硬化性組成物。 - 前記(メタ)アクリロイル基含有アクリル樹脂(A)の反応原料の80質量%以上が芳香環を含有しない(メタ)アクリレートモノマーである請求項1記載の硬化性組成物。
- 前記(メタ)アクリロイル基含有アクリル樹脂(A)、及び前記ジペンタエリスリトールの(メタ)アクリル酸エステル化物(B)の合計の含有量が、前記硬化性組成物が含有する(メタ)アクリロイル基含有化合物成分の合計中70質量%以上である請求項1記載の硬化性組成物。
- (メタ)アクリロイル基含有化合物成分の合計における(メタ)アクリロイル基含有量が3.8~8.5mmol/gの範囲である請求項1記載の硬化性組成物。
- 前記(メタ)アクリロイル基含有アクリル樹脂(A)と前記ジペンタエリスリトールの(メタ)アクリル酸エステル化物(B)との質量比[(A)/(B)]が30/70~99/1の範囲である請求項1記載の硬化性組成物。
- 請求項1~5の何れか一つ記載の硬化性組成物からなる塗膜。
- 請求項6記載の塗膜からなる層を有する積層フィルム。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201880039327.6A CN110741025B (zh) | 2017-06-15 | 2018-06-07 | 固化性组合物和层叠薄膜 |
JP2019525360A JPWO2018230427A1 (ja) | 2017-06-15 | 2018-06-07 | 硬化性組成物及び積層フィルム |
KR1020197034545A KR102482177B1 (ko) | 2017-06-15 | 2018-06-07 | 경화성 조성물 및 적층 필름 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-117728 | 2017-06-15 | ||
JP2017117728 | 2017-06-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018230427A1 true WO2018230427A1 (ja) | 2018-12-20 |
Family
ID=64659803
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/021823 WO2018230427A1 (ja) | 2017-06-15 | 2018-06-07 | 硬化性組成物及び積層フィルム |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPWO2018230427A1 (ja) |
KR (1) | KR102482177B1 (ja) |
CN (1) | CN110741025B (ja) |
WO (1) | WO2018230427A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6947269B1 (ja) * | 2020-09-18 | 2021-10-13 | 荒川化学工業株式会社 | 環状オレフィン樹脂用コーティング剤、コーティング剤キット、硬化物、及び積層物 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112480804A (zh) * | 2020-10-30 | 2021-03-12 | 中山市鑫峰光固化材料有限公司 | 一种水性uv光固化聚氨酯涂料及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62275167A (ja) * | 1986-02-18 | 1987-11-30 | Mitsubishi Rayon Co Ltd | 活性エネルギ−線硬化型塗料 |
JPH06287470A (ja) * | 1993-04-05 | 1994-10-11 | Mitsubishi Petrochem Co Ltd | 耐摩耗性被覆組成物 |
JPH0741695A (ja) * | 1993-07-30 | 1995-02-10 | Mitsubishi Chem Corp | 耐摩耗性被覆組成物 |
JPH07286115A (ja) * | 1994-04-18 | 1995-10-31 | Mitsubishi Chem Corp | 耐摩耗性被覆組成物 |
JP2009237151A (ja) * | 2008-03-26 | 2009-10-15 | Fujifilm Corp | カラーフィルタ用着色硬化性組成物、及びカラーフィルタ |
WO2016190426A1 (ja) * | 2015-05-28 | 2016-12-01 | 大日本印刷株式会社 | 転写箔 |
WO2017047817A1 (ja) * | 2015-09-17 | 2017-03-23 | 東レ株式会社 | 平版印刷用インキ、平版インキ用ワニスおよびそれを用いた印刷物の製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4015471B2 (ja) * | 2001-06-28 | 2007-11-28 | 大日本印刷株式会社 | 光硬化性樹脂組成物、微細凹凸パターン転写箔、光学物品、スタンパー及び微細凹凸パターンの形成方法 |
JP5408640B2 (ja) * | 2006-09-04 | 2014-02-05 | 日東電工株式会社 | 紫外線硬化型粘着剤組成物、紫外線硬化型粘着シート及びその製造方法 |
WO2009133760A1 (ja) * | 2008-04-30 | 2009-11-05 | Dic株式会社 | 活性エネルギー線硬化型水性樹脂組成物、活性エネルギー線硬化型塗料、硬化塗膜の形成方法及び物品 |
JP5136195B2 (ja) * | 2008-05-14 | 2013-02-06 | 東洋インキScホールディングス株式会社 | 導電性組成物、およびそれを用いてなる導電膜、ならびに該導電膜を有する積層体 |
JP5569726B2 (ja) | 2010-03-29 | 2014-08-13 | Dic株式会社 | 活性エネルギー線硬化型樹脂組成物及びフィルム基材 |
JP2013023525A (ja) * | 2011-07-19 | 2013-02-04 | Arakawa Chem Ind Co Ltd | 活性エネルギー線硬化型帯電防止性組成物および光学フィルム |
WO2015198788A1 (ja) * | 2014-06-26 | 2015-12-30 | Dic株式会社 | 活性エネルギー線硬化型樹脂組成物、塗料、塗膜、及び積層フィルム |
JP6862733B2 (ja) * | 2015-09-24 | 2021-04-21 | 荒川化学工業株式会社 | 光学用活性エネルギー線硬化型樹脂組成物及び光学用フィルム |
-
2018
- 2018-06-07 CN CN201880039327.6A patent/CN110741025B/zh active Active
- 2018-06-07 JP JP2019525360A patent/JPWO2018230427A1/ja active Pending
- 2018-06-07 KR KR1020197034545A patent/KR102482177B1/ko active IP Right Grant
- 2018-06-07 WO PCT/JP2018/021823 patent/WO2018230427A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62275167A (ja) * | 1986-02-18 | 1987-11-30 | Mitsubishi Rayon Co Ltd | 活性エネルギ−線硬化型塗料 |
JPH06287470A (ja) * | 1993-04-05 | 1994-10-11 | Mitsubishi Petrochem Co Ltd | 耐摩耗性被覆組成物 |
JPH0741695A (ja) * | 1993-07-30 | 1995-02-10 | Mitsubishi Chem Corp | 耐摩耗性被覆組成物 |
JPH07286115A (ja) * | 1994-04-18 | 1995-10-31 | Mitsubishi Chem Corp | 耐摩耗性被覆組成物 |
JP2009237151A (ja) * | 2008-03-26 | 2009-10-15 | Fujifilm Corp | カラーフィルタ用着色硬化性組成物、及びカラーフィルタ |
WO2016190426A1 (ja) * | 2015-05-28 | 2016-12-01 | 大日本印刷株式会社 | 転写箔 |
WO2017047817A1 (ja) * | 2015-09-17 | 2017-03-23 | 東レ株式会社 | 平版印刷用インキ、平版インキ用ワニスおよびそれを用いた印刷物の製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6947269B1 (ja) * | 2020-09-18 | 2021-10-13 | 荒川化学工業株式会社 | 環状オレフィン樹脂用コーティング剤、コーティング剤キット、硬化物、及び積層物 |
JP2022051220A (ja) * | 2020-09-18 | 2022-03-31 | 荒川化学工業株式会社 | 環状オレフィン樹脂用コーティング剤、コーティング剤キット、硬化物、及び積層物 |
Also Published As
Publication number | Publication date |
---|---|
KR20200019609A (ko) | 2020-02-24 |
CN110741025A (zh) | 2020-01-31 |
KR102482177B1 (ko) | 2022-12-29 |
JPWO2018230427A1 (ja) | 2020-07-16 |
CN110741025B (zh) | 2022-06-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7338154B2 (ja) | 活性エネルギー線硬化型樹脂組成物及び積層体 | |
CN113661064B (zh) | 活性能量射线固化性树脂组合物、固化物、层叠体及物品 | |
CN110741025B (zh) | 固化性组合物和层叠薄膜 | |
JP2023143911A (ja) | 活性エネルギー線硬化性樹脂組成物、積層フィルム、その製造方法、及び加飾フィルムの製造方法 | |
JP7024729B2 (ja) | 活性エネルギー線硬化型樹脂組成物及び積層フィルム | |
TW201819439A (zh) | 活性能量線硬化型樹脂組成物及積層膜 | |
JP6919308B2 (ja) | (メタ)アクリロイル基含有樹脂及び積層フィルム | |
JP7003453B2 (ja) | ウレタン(メタ)アクリレート樹脂 | |
JP7346817B2 (ja) | 積層体及びその用途 | |
JP7364098B2 (ja) | アクリル(メタ)アクリレート樹脂、活性エネルギー線硬化性樹脂組成物、硬化物及び物品 | |
TWI842870B (zh) | 活性能量線硬化性樹脂組成物、硬化物、積層體及具有積層體之物品 | |
TW202313873A (zh) | 無機微粒子分散體、活性能量線硬化性組成物、硬化物、積層體及物品 | |
JP7013682B2 (ja) | ウレタン(メタ)アクリレート樹脂 | |
JP7495016B2 (ja) | 活性エネルギー線硬化性樹脂組成物、硬化塗膜及び物品 | |
JP2018135452A (ja) | 活性エネルギー線硬化型樹脂組成物及び積層フィルム | |
TW202239794A (zh) | 活性能量線硬化性樹脂組成物、硬化物及物品 | |
JP2015071666A (ja) | 硬化性樹脂組成物、硬化物、積層体、ハードコートフィルム及びフィルム積層体 |
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: 18818380 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20197034545 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2019525360 Country of ref document: JP Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18818380 Country of ref document: EP Kind code of ref document: A1 |