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WO2012141275A1 - Composition adhésive durcissable par un rayonnement d'énergie active - Google Patents

Composition adhésive durcissable par un rayonnement d'énergie active Download PDF

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Publication number
WO2012141275A1
WO2012141275A1 PCT/JP2012/060084 JP2012060084W WO2012141275A1 WO 2012141275 A1 WO2012141275 A1 WO 2012141275A1 JP 2012060084 W JP2012060084 W JP 2012060084W WO 2012141275 A1 WO2012141275 A1 WO 2012141275A1
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WIPO (PCT)
Prior art keywords
meth
component
weight
energy ray
acrylate
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Ceased
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PCT/JP2012/060084
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English (en)
Japanese (ja)
Inventor
宏習 及川
佐内　康之
岡崎　栄一
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to JP2013509971A priority Critical patent/JPWO2012141275A1/ja
Publication of WO2012141275A1 publication Critical patent/WO2012141275A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C08F220/346—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links and further oxygen

Definitions

  • the present invention relates to an active energy ray-curable adhesive composition capable of bonding various substrates by irradiation with an active energy ray such as an electron beam or ultraviolet rays.
  • the composition of the present invention is suitably used for laminating and bonding thin-layer adherends such as plastic films or plastic sheets used as optical components (hereinafter, “films or sheets” are collectively referred to as “films”), Furthermore, it is suitably used for the production of various optical films or sheets used for liquid crystal display elements, EL (electroluminescence) display elements, projection display elements, plasma display elements, etc., and can be used in these technical fields. Is.
  • an ethylene-vinyl acetate copolymer is used in a laminating method in which a thin-layer adherend such as a plastic film or a thin-layer adherend such as a plastic film is bonded to a thin-layer adherend made of another material.
  • a solvent-type adhesive composition containing a polymer or a polyurethane-based polymer is applied to the first thin-layer adherend and dried, and then the second thin-layer adherend is applied to the first thin-layer adherend using a nip roller or the like.
  • the dry laminating method for pressure bonding is mainly performed.
  • the adhesive composition used in this method generally contains a large amount of a solvent in order to make the coating amount of the composition uniform, but for this reason, a large amount of solvent vapor is volatilized during drying, resulting in toxicity, work safety and Environmental pollution is a problem.
  • a solventless adhesive composition has been studied.
  • the solventless adhesive composition a two-component adhesive composition and an adhesive composition that is cured by an active energy ray such as an ultraviolet ray or an electron beam are widely used.
  • a so-called polyurethane adhesive composition is mainly used in which a polymer having a hydroxyl group at the terminal is a main agent and a polyisocyanate compound having an isocyanate group at the terminal is a curing agent.
  • the composition has the disadvantage that it takes too long to cure.
  • the active energy ray-curable adhesive composition is excellent in productivity because of its high curing rate, and has recently attracted attention.
  • liquid crystal display devices have been widely used as display elements for televisions, portable personal computers, mobile phones, word processors and the like as well as simple display devices in digital watches and various electric appliances.
  • an active energy ray-curable adhesive has been used for bonding various optical films used in the liquid crystal display element.
  • the adhesive composition used in the optical film is required to have a performance capable of maintaining the adhesive force under severe conditions under high temperature and high humidity conditions.
  • the present applicant has, as an active energy ray-curable adhesive composition having excellent adhesion at high temperatures and high humidity, a composition containing a urethane (meth) acrylate and a polymer having a glass transition temperature of 40 ° C. or higher.
  • Patent document 1 and the composition (patent document 2) containing the urethane (meth) acrylate and the (meth) acrylate which has a cyclic imide group are proposed.
  • the applicant of the present application is a composition comprising a urethane (meth) acrylate having a specific structure and a specific monofunctional (meth) acrylate having a cyclic structure as an adhesive, and an activity containing methacrylate at a specific ratio.
  • Patent Document 3 An energy ray curable adhesive composition (Patent Document 3) is proposed.
  • active energy ray-curable adhesive compositions using urethane (meth) acrylate and (meth) acrylamide compounds in combination are known (Patent Documents 4 to 6).
  • the laminate obtained by curing shrinkage may be warped (curl) in some cases.
  • heat generated from various driving devices and light sources may be concentrated on a part of the film laminate without being diffused due to thinning and miniaturization of display devices, and sunlight such as car navigation may be exposed to sunlight.
  • sunlight such as car navigation
  • the product is used outdoors, only a part of the product, not the entire product, may become excessively hot.
  • deflection occurs when heat concentrates on a part of the film laminate, resulting in problems such as reduced visibility and distortion of the resulting image. It has become to.
  • the present inventors have found an active energy ray-curable adhesive composition that has excellent adhesive strength, little warpage in the resulting laminate, and little film laminate deflection even under partially heated conditions. For this reason, we conducted an intensive study.
  • component (A) urethane (meth) acrylate [hereinafter referred to as “component (A)”.
  • Component (B) a compound represented by the following formula (1) [hereinafter referred to as “(meth) acrylamide (1)”) and a compound represented by the following formula (2) [hereinafter referred to as “(meth) acrylamide (2 ) ”And 95 to 5 parts by weight of (meth) acrylamide (1) and (meth) acrylamide (1) 5 with respect to 100 parts by weight of the total amount of (meth) acrylamide (1) and (2) A (meth) acrylamide compound comprising ⁇ 95 parts by weight [hereinafter referred to as “component (B)”.
  • Component (C) Compound having an ethylenically unsaturated group other than the components (A) and (B) [hereinafter referred to as “component (C)”.
  • a composition comprising: (A) to (C) component is included in the following proportion with respect to the total amount of components (A) to (C): Component (A): 5 to 50% by weight Component (B): 30 to 93% by weight Component (C): 2 to 65% by weight
  • An active energy ray-curable adhesive composition containing 2 to 30% by weight of a compound having a methacryloyl group in the total of components (A) to (C) [hereinafter simply referred to as “the adhesive composition of the present invention”] Or “the composition of the present invention”).
  • non-aromatic urethane (meth) acrylate is preferable.
  • urethane (meth) acrylate having a polycarbonate skeleton is preferable.
  • the component (A) is preferably a compound having a weight average molecular weight of 500 to 50,000.
  • the compound R 2 and R 3 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms are preferred.
  • the composition of the present invention preferably further contains (D) a photopolymerization initiator, and preferably contains 0.1 to 10 parts by weight of the component (D) with respect to 100 parts by weight of the composition. .
  • the composition of the present invention preferably has a cured product having a glass transition temperature of 60 to 180 ° C.
  • composition of the present invention can be preferably used for the production of a thin layer laminate, and a laminate composed of a substrate, a cured product of the composition of the present invention and another substrate is preferable. It is preferable that at least one of the substrates is a plastic substrate.
  • the composition of the present invention can be preferably used as an adhesive composition for a plastic substrate, can be preferably used as an adhesive composition for an optical material, and can be preferably used as an adhesive composition for an optical film laminate.
  • the present invention is a process of applying any one of the above compositions to the first substrate, Bonding the second substrate to the composition; It is a manufacturing method of the laminated body including the process of irradiating an active energy ray from the 1st base material or the 2nd base material side.
  • a 1st base material or a 2nd base material it is preferable that at least one is a plastic base material, it is preferable that it is an optical member, and it is preferable that it is an optical film.
  • the present invention also relates to a laminate composed of a first substrate, a cured product of the above-described composition, and a second substrate.
  • a first base material or the second base material at least one is preferably a plastic base material.
  • the active energy is excellent in adhesion to a substrate, particularly excellent in adhesion to a plastic substrate, and the resulting laminate has little warping with time, and further has little deflection after a heating test.
  • a wire curable adhesive composition can be provided. Therefore, the composition of the present invention is effective for the adhesion of thin-layer adherends such as plastic films used as various optical members by taking advantage of these characteristics, and particularly for the production of optical films used for liquid crystal display devices and the like. It can be suitably used.
  • acrylate and / or methacrylate is represented by (meth) acrylate
  • acryloyl group and / or methacryloyl group is represented by (meth) acryloyl group
  • acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid.
  • the active energy ray-curable adhesive composition of the present invention contains the components (A), (B) and (C) as essential components.
  • each component will be described.
  • As the components (A) to (C), each compound described later can be used alone, or two or more compounds can be used in combination.
  • a component is urethane (meth) acrylate.
  • various urethane (meth) acrylates can be used, and specific examples include urethane (meth) acrylates having a polyester skeleton, a polyether skeleton, or a polycarbonate skeleton.
  • a urethane (meth) acrylate having a polyester skeleton or a polycarbonate skeleton is preferable, and a urethane having a polycarbonate skeleton (more preferably a urethane ( (Meth) acrylate.
  • any of oligomers and polymers can be used, preferably having a weight average molecular weight of 500 to 50,000, more preferably 3,000 to 50,000, and particularly preferably 10,000 to 40,000.
  • the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.
  • examples of the component (A) include a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and the polyol and the organic polyisocyanate reaction product include a hydroxyl group-containing (meth) acrylate.
  • a compound obtained by reacting is preferred.
  • the component (A) is preferably a urethane (meth) acrylate having two (meth) acryloyl groups (hereinafter also referred to as a bifunctional urethane (meth) acrylate), and is a polyester, polyether or polycarbonate skeleton. More preferred is a bifunctional urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a reaction product of a diol having an organic diisocyanate.
  • a diol having a polyester skeleton As the polyol, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton are preferable.
  • the polyol having a polyester skeleton include an esterification reaction product of a diol component such as a low molecular weight diol or polycaprolactone diol and an acid component such as a dibasic acid or an anhydride thereof.
  • the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol and 1,6-hexanediol.
  • Examples of the dibasic acid or an anhydride thereof include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
  • Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polyetramethylene glycol.
  • Examples of the polycarbonate polyol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a carbonic acid dialkyl ester such as ethylene carbonate and carbonic acid dibutyl ester.
  • Organic polyisocyanates include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, hydrogenated tolylene diisocyanate, hydrogenated 4 , 4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate interadduct, 4,4'-dicyclohexylmethane diisocyanate , Trimethylolpropane tris (tolylene diisocyanate) adduct, isophorone diisocyanate and the like.
  • the organic polyisocyanate is preferably an organic diisocyan
  • hydroxyl group-containing (meth) acrylates examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and hydroxy Hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate; polyol-containing polyol poly (meth) acrylates such as pentaerythritol tri, di or mono (meth) acrylate, and trimethylolpropane di or mono (meth) acrylate Can be mentioned.
  • hydroxyl group-containing (meth) acrylate hydroxyalkyl (meth) acrylate is preferable.
  • A As a component, what was obtained by the manufacturing method of said 1) is preferable.
  • urethanization catalyst examples include tin-based catalysts such as dibutyltin dilaurate, iron-based catalysts such as tris (acetylacetonato) iron, and zinc-based catalysts such as bis (acetylacetonato) zinc.
  • tin-based catalysts such as dibutyltin dilaurate
  • iron-based catalysts such as tris (acetylacetonato) iron
  • zinc-based catalysts such as bis (acetylacetonato) zinc.
  • a non-aromatic urethane (meth) acrylate is preferable in that the adhesive strength under high humidity is particularly excellent and the cured adhesive is less colored over time.
  • the non-aromatic urethane (meth) acrylate include urethane (meth) acrylate produced from a non-aromatic polyol and a non-aromatic polyisocyanate.
  • Non-aromatic polyols include non-aromatic polyester polyols and polycarbonate polyols, and preferably non-aromatic polycarbonate polyols.
  • component (B) component contains (meth) acrylamide (1) and (meth) acrylamide (2), and (meth) acrylamide (1) and (2) with respect to a total amount of 100 parts by weight, ) A (meth) acrylamide compound comprising 5 to 95 parts by weight of acrylamide (1) and 95 to 5 parts by weight of (meth) acrylamide (2).
  • the adhesion to the substrate can be improved and the glass transition temperature of the composition cured product can be increased. Can be prevented.
  • (Meth) acrylamide (1) is a compound represented by the following formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 and R 3 represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 ⁇ 20, R 2 and R 3 in one molecule These may be the same group or different groups.
  • the hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group, which may be linear or branched.
  • the alkyl group may be an alkyl group further having a hydroxyl group, an aromatic group, and a diaminoalkyl group.
  • Specific examples of the alkyl group include a methyl group, a propyl group, a butyl group, a butyl group, and a hexyl group.
  • Examples of the alkyl group having a hydroxyl group include a hydroxymethyl group and a hydroxyethyl group.
  • Examples of the alkyl group having an aromatic group include a benzyl group.
  • Examples of the alkyl group having a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
  • Examples of the dialkylaminoalkyl group include N, N-dimethylaminoethyl group and N, N-dimethylaminopropyl group. Among these, an alkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
  • (meth) acrylamide (1) include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N -Sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- Dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl ( (Meth) acrylamide, N, N-diisopropyl (meth) ac Rua
  • the component (B) is used in combination with (meth) acrylamide (1) represented by the following formula (2) in addition to (meth) acrylamide (1), so that the erodibility to the substrate is not inhibited. And the bending of the obtained laminated body under a heating condition can be reduced.
  • R 4 represents a hydrogen atom or a methyl group.
  • (meth) acrylamide (2) examples include acryloylmorpholine and methacryloylmorpholine.
  • the proportion of (meth) acrylamide (1) and (2) in the component (B) is (meth) acrylamide (1) 5 to 95 with respect to 100 parts by weight of the total amount of (meth) acrylamide (1) and (2). It is composed of 95 to 5% by weight of (meth) acrylamide (2) by weight, preferably 10 to 90% by weight of (meth) acrylamide (1) and 90 to 10% by weight of (meth) acrylamide (2).
  • the proportion of (meth) acrylamide (1) is less than 5% by weight or the proportion of (meth) acrylamide (2) exceeds 95% by weight, the adhesive strength is lowered.
  • the proportion of (meth) acrylamide (1) exceeds 95% by weight or the proportion of (meth) acrylamide (2) is less than 5% by weight, the deflection of the laminate obtained under heating conditions will be It gets bigger.
  • Component (C) is a compound having an ethylenically unsaturated group other than the components (A) and (B).
  • various compounds can be used as long as they are compounds other than the components (A) and (B).
  • Examples of the monomer monomer include compounds having one (meth) acryloyl group.
  • Examples of the compound include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • Alkyl (meth) acrylates Alkyl (meth) acrylates; aromatic group-containing (meth) acrylates such as benzyl (meth) acrylate; alicyclic groups such as isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentanyl (meth) acrylate Containing (meth) acrylates; and hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate
  • N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam can be used.
  • Examples of the compound having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate.
  • Alkylene glycol di (meth) acrylate Alkylene glycol di (meth) acrylate; glycol di (meth) acrylate such as 1,6-hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate; bisphenol A di (meth) acrylate or a halogen nucleus substitution product thereof And bisphenol-type di (meth) acrylates such as bisphenol F di (meth) acrylate or a halogen nucleus substitution product thereof; dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane Poly (poly) acrylates such as li (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol
  • oligomer examples include polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate.
  • polyester (meth) acrylate oligomer examples include a dehydration condensate of a polyester polyol and (meth) acrylic acid.
  • examples of the polyester polyol include a reaction product of a carboxylic acid with a polyol or an anhydride thereof.
  • Polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neo Low molecular weight polyols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, and their alkylene oxide adducts Etc.
  • Low molecular weight polyols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanedio
  • dibasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid or anhydrous Thing etc.
  • polyester poly (meth) acrylates other than these include compounds described on pages 74 to 76 of the above-mentioned document “UV / EB Curing Material”.
  • Epoxy (meth) acrylate oligomer Epoxy (meth) acrylate is a compound obtained by addition reaction of (meth) acrylic acid to an epoxy resin, as described on pages 74 to 75 of the above-mentioned document “UV / EB Curing Material”. Compounds.
  • the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
  • aromatic epoxy resin examples include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or an alkylene oxide adduct thereof; phenol novolac type epoxy resin and cresol novolac type Examples thereof include novolak-type epoxy resins such as epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.
  • aliphatic epoxy resin examples include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc.
  • Diglycidyl ethers of polyalkylene glycols diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; di- or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adducts; Of polyhydric alcohols such as di-, tri- or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts Ether; hydrogenated bisphenol A and di- or polyglycidyl ethers of alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.
  • the compounds described on pages 3 to 6 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin can be mentioned.
  • epoxy compounds having a triazine nucleus as a skeleton for example, TEPIC (Nissan Chemical Co., Ltd.), Denacol EX-310 (Nagase Kasei Co., Ltd.), etc. can be mentioned.
  • the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.
  • Polyether (meth) acrylate oligomers include polyalkylene glycol (meth) diacrylate, including polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di ( And (meth) acrylate.
  • polymer polymer a (meth) acrylic polymer having a (meth) acryloyloxy group, a (meth) acrylic polymer having a functional group, a (meth) acryloyl group introduced into the side chain, Examples thereof include compounds described on pages 78 to 79 of “UV / EB Curing Material”.
  • the compound of component (C) is preferably selected so that the glass transition temperature of the cured product of the composition described below falls within a preferred range.
  • the monomer which has one (meth) acryloyl group is preferable at the point which adhesiveness is favorable also in an above described compound.
  • the component (C) is preferably a compound having a glass transition temperature (hereinafter referred to as “Tg”) of the homopolymer of 0 to 200 ° C., more preferably 60 to 180 ° C.
  • Tg dicyclopentanyl acrylate
  • dicyclopentanyl methacrylate 175 ° C.
  • isobornyl acrylate 94 ° C.
  • isobornyl methacrylate 180 ° C.
  • Tg means a temperature at which the main peak of the loss tangent (tan ⁇ ) of the viscoelastic spectrum of the cured product measured at 1 Hz is maximized.
  • the proportions of the components (A), (B) and (C) are 5 to 50% by weight of component (A) with respect to the total amount of components (A) to (C), (B ) Component 30 to 93% by weight and (C) component 2 to 65% by weight, preferably (A) component 15 to 40% by weight, (B) component 30 to 85% by weight and (C) component 2 to 55%. % By weight.
  • the proportion of the component (A) is less than 5% by weight, the adhesive strength is lowered, and when it is more than 50% by weight, the deflection of the laminate obtained under heating conditions is increased.
  • the adhesive strength is reduced in any case.
  • the amount of component (C) is more than 65% by weight, the adhesive strength is reduced.
  • the adhesive strength can be made excellent.
  • the composition of the present invention needs to contain 2 to 30% by weight of the compound having a methacryloyl group in the total of the components (A) to (C), preferably 5 to 30% by weight, Preferably, it is 5 to 25% by weight.
  • the amount is less than 2% by weight, warping may occur at the time of bonding, and when it is more than 30% by weight, the curability may be delayed and the productivity may be lowered.
  • What is necessary is just to select the compound which has the said methacryloyl group suitably from above-mentioned (A), (B) and (C) component.
  • the compound having a methacryloyl group it is convenient and preferable to select a compound having a methacryloyl group from the component (C).
  • Component (D) includes benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenyl Acetophenones such as acetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2 -Anthraquinones such as methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanth
  • photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiation accelerator.
  • the preferred blending ratio of component (D) is 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the composition.
  • ⁇ -hydroxyacetophenones and phosphine oxides are preferred because the cured product is less colored over time.
  • composition of the present invention contains an antioxidant, an ultraviolet absorber, HALS (hindered amine light stabilizer), etc. in an amount of up to 5 parts by weight per 100 parts by weight of the total of components (A) to (C).
  • HALS hindered amine light stabilizer
  • a leveling agent for making the coating film thickness uniform and an antifoaming agent for suppressing foaming can be added.
  • the production method of the composition of the present invention is not particularly limited, and the essential component of the present invention, or the essential component and other components as necessary are stirred or mixed by a commonly used method. Is obtained. In this case, heating or heating can be performed as necessary.
  • the composition of the present invention can be preferably used as a solvent-free composition containing no organic solvent. As a result, a large amount of solvent vapor is volatilized during the drying of the organic solvent, and the problems of toxicity, work safety and environmental pollution can be avoided, and further, the heat energy used for drying is not required.
  • the product can be manufactured at a low cost.
  • a cured product having a Tg of 60 to 180 ° C. is preferable.
  • the Tg is 60 ° C. or higher, the adhesive strength at the time of the heat resistance test is excellent, and when the Tg is 180 ° C. or lower, the initial peel strength is sufficiently obtained.
  • composition of the present invention can be used for adhesion of various substrates.
  • the substrate include plastic, metal, paper, and the like, and can be suitably used for adhesion of plastic.
  • a conventional method may be used, and examples thereof include a method of irradiating active energy rays after coating on a substrate.
  • the active energy rays include visible light, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferable because inexpensive devices can be used.
  • Various light sources can be used as the light source when cured by ultraviolet rays, and examples thereof include a pressurized or high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, and an LED.
  • an electron beam (EB) irradiation device that can be used, such as a Cockloft-Waltsin type, a bandegraph type, and a resonance transformer type device. Is preferably one having an energy of 50 to 1,000 eV, more preferably 100 to 300 eV.
  • the composition of the present invention can be preferably used for the production of a laminate, and may be carried out in accordance with a method usually performed in the production of a laminate. For example, there is a method in which the composition is applied to a first substrate, a second substrate is bonded thereto, and then an active energy ray is irradiated from the surface of any substrate.
  • the laminate produced in this manner is composed of a substrate, a cured product of the composition of the present invention, and another substrate. In this case, it is preferable that at least one of the substrates is a plastic substrate.
  • the composition of the present invention can be preferably used as an adhesive composition for optical materials, and can be preferably used as an adhesive composition for optical film lamination.
  • a laminate can be produced according to the same method as described above, using a thin layer adherend used as an optical member as the substrate.
  • the thin-layer adherend used as an optical member is mainly a plastic film and needs to be able to transmit active energy rays.
  • the film thickness depends on the thin-layer adherend to be used and the application.
  • the thickness is preferably 1 mm or less.
  • the plastic in the plastic film include polyvinyl chloride resin, polyvinylidene chloride, cellulosic resin, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene resin (ABS resin), polyamide, polyester, polycarbonate, polyurethane, polyvinyl alcohol, Examples thereof include ethylene-vinyl acetate copolymer and chlorinated polypropylene.
  • a material whose surface is subjected to treatment such as metal vapor deposition.
  • a coating method for the thin-layer adherend a conventionally known method may be followed. Natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, Examples of the method include a reverse roll, an air blade, a curtain flow coater, and a gravure coater.
  • the coating thickness of the composition of the present invention may be selected according to the thin layer adherend to be used and the application, but is preferably 0.1 to 1,000 ⁇ m, more preferably 1 to 50 ⁇ m. is there.
  • the laminate film or sheet obtained from the adhesive composition of the present invention has excellent adhesive strength under high temperature conditions, a polarizing film, a retardation film, a prism sheet, a brightness enhancement film, a conductive film, and the like used for liquid crystal display devices and the like are used. It can be suitably used for an optical film or sheet such as a light plate or a diffusion plate.
  • each number in the components (A) to (D) means the number of parts, and each abbreviation has the following meaning.
  • UN9200A Polycarbonate urethane acrylate having a non-aromatic polycarbonate skeleton, weight average molecular weight of about 20,000 [Negami Kogyo Co., Ltd.
  • Tg After injecting the obtained composition into a polyethylene terephthalate (PET) film into a rubber mold having a thickness of 1 mm and laminating with a PET film thereon, 120 W / cm, at a position 30 cm from the bottom of a concentrating metal halide lamp, A cured product was obtained by repeatedly passing under the lamp 10 times under the condition of a conveyor speed of 10 m / min. The obtained cured product was measured with a dynamic viscoelasticity measuring apparatus (EXSTAR DMS6100 manufactured by SII Nanotechnology Co., Ltd.), and the loss tangent (tan ⁇ ) of the viscoelastic spectrum of the cured product measured at 1 Hz. Tg was measured from the temperature at which the main peak of the maximum.
  • EXSTAR DMS6100 dynamic viscoelasticity measuring apparatus manufactured by SII Nanotechnology Co., Ltd.
  • PC film Iupilon FE-2000: manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • a 50 ⁇ m-thick PC film was bonded to this by a nip roll, and this was done 3 times under the lamp at 120 W / cm, 30 cm from the bottom of the concentrating metal halide lamp at a conveyor speed of 10 m / min. Passing repeatedly, the films were bonded together to produce a laminated film.
  • the obtained specimen was allowed to stand in a constant temperature and humidity (23 ° C., 50% RH) room for a whole day and night, and then the peel strength and the warpage during bonding were evaluated.
  • compositions of Examples 1 to 6 were all excellent in peel strength, free from warpage during bonding, and free from deflection after the heating test.
  • the composition of Comparative Example 1 containing no component (B) had excellent peel strength and no warpage during bonding, but a large deflection occurred after the heating test.
  • the composition of Comparative Example 2 that does not contain acrylamide (1), which is an essential component of the component (B) of the present invention has a large decrease in peel strength, although there was no warpage at the time of bonding or deflection after a heating test. have done.
  • Comparative Example 3 which contains the components (A) to (C) but does not contain any compound having a methacryloyl group, has excellent peel strength and no deflection after the heating test, Warping has occurred.
  • the composition of Comparative Examples 4 and 5 which does not contain acrylamide (2) in the component (B) was obtained after a more severe heating test at 120 ° C., although it had excellent peel strength and no warpage during bonding. A large deflection has occurred in the laminate.
  • the adhesive composition of the present invention excellent adhesive strength can be maintained even at high temperatures, and there is little coloration over time, and between thin-layer adherends such as plastic films used as various optical members. It is effective for laminating and can be suitably used for the production of an optical film particularly used for a liquid crystal display device or the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention a pour but de procurer une composition adhésive durcissable sous l'action d'un rayonnement à énergie active permettant une adhérence à un substrat excellente, avec laquelle il y a peu de gauchissement au cours du temps du stratifié résultant, et avec laquelle il y a peu de pliage après un test thermique. A cet effet, selon l'invention, la composition adhésive durcissable sous l'action d'un rayonnement à énergie active est une composition comprenant (A) un uréthane (méth)acrylate, (B) un composé (méth)acrylamide qui contient un composé représenté par la formule (1) et un composé représenté par la formule (2) dans des quantités, pour un total de 100 parties en poids (parties ci-après), qui se situent entre respectivement 5 et 95 parties et 95 et 5 parties, et (C) un composé ayant des groupes à insaturation éthylénique autres que les composants (A) et (B), le rapport de composants (A) à (C) pour la quantité totale de composants (A) à (C) étant de 5 à 50 % en poids (% ci-après) de composant (A), 30 à 93 % de composant (B) et 2 à 65 % de composant (C) et le rapport de composés ayant des groupes (méth)acryloyle étant de 2 à 30 % du total de composants (A) à (C).
PCT/JP2012/060084 2011-04-13 2012-04-12 Composition adhésive durcissable par un rayonnement d'énergie active Ceased WO2012141275A1 (fr)

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JP2014111733A (ja) * 2012-11-06 2014-06-19 Sanyo Chem Ind Ltd ディスプレイ用粘着剤組成物
JP2015004047A (ja) * 2013-05-22 2015-01-08 東洋インキＳｃホールディングス株式会社 樹脂組成物、活性エネルギー線重合性接着剤、及び積層体
JP2016102918A (ja) * 2014-11-28 2016-06-02 住友化学株式会社 偏光板
JP2016102919A (ja) * 2014-11-28 2016-06-02 住友化学株式会社 偏光板
JPWO2014069134A1 (ja) * 2012-10-31 2016-09-08 昭和電工株式会社 重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法
TWI586777B (zh) * 2012-10-24 2017-06-11 Toagosei Co Production method of active energy ray hardening type adhesive preparation and laminate
JP2017210578A (ja) * 2016-05-27 2017-11-30 協立化学産業株式会社 硬化性樹脂組成物
JP2017210607A (ja) * 2016-05-19 2017-11-30 日本合成化学工業株式会社 活性エネルギー線硬化性接着剤組成物およびこれを用いてなるアクリル系樹脂部材用接着剤組成物
JP2017214550A (ja) * 2016-05-27 2017-12-07 日本合成化学工業株式会社 ポリカーボネート系部材用活性エネルギー線硬化性接着剤組成物およびこれを用いてなるポリカーボネート系部材用接着剤
WO2019189566A1 (fr) * 2018-03-28 2019-10-03 クラレノリタケデンタル株式会社 Composition de résine photodurcissable
JP7073252B2 (ja) 2016-03-31 2022-05-23 昭和電工マテリアルズ株式会社 感光性樹脂組成物、感光性樹脂フィルム、硬化物の製造方法、積層体、及び電子部品

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JP2007177169A (ja) * 2005-12-28 2007-07-12 Okura Ind Co Ltd 光硬化型接着剤組成物及びそれを用いた積層フィルム
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Publication number Priority date Publication date Assignee Title
TWI586777B (zh) * 2012-10-24 2017-06-11 Toagosei Co Production method of active energy ray hardening type adhesive preparation and laminate
JPWO2014069134A1 (ja) * 2012-10-31 2016-09-08 昭和電工株式会社 重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法
JP2014111733A (ja) * 2012-11-06 2014-06-19 Sanyo Chem Ind Ltd ディスプレイ用粘着剤組成物
JP2015004047A (ja) * 2013-05-22 2015-01-08 東洋インキＳｃホールディングス株式会社 樹脂組成物、活性エネルギー線重合性接着剤、及び積層体
JP2016102918A (ja) * 2014-11-28 2016-06-02 住友化学株式会社 偏光板
JP2016102919A (ja) * 2014-11-28 2016-06-02 住友化学株式会社 偏光板
JP7073252B2 (ja) 2016-03-31 2022-05-23 昭和電工マテリアルズ株式会社 感光性樹脂組成物、感光性樹脂フィルム、硬化物の製造方法、積層体、及び電子部品
JP2017210607A (ja) * 2016-05-19 2017-11-30 日本合成化学工業株式会社 活性エネルギー線硬化性接着剤組成物およびこれを用いてなるアクリル系樹脂部材用接着剤組成物
WO2017203783A1 (fr) * 2016-05-27 2017-11-30 協立化学産業株式会社 Composition de résine durcissable
JP2017214550A (ja) * 2016-05-27 2017-12-07 日本合成化学工業株式会社 ポリカーボネート系部材用活性エネルギー線硬化性接着剤組成物およびこれを用いてなるポリカーボネート系部材用接着剤
CN108884199A (zh) * 2016-05-27 2018-11-23 协立化学产业株式会社 固化性树脂组合物
KR20190013760A (ko) * 2016-05-27 2019-02-11 교리쯔 가가꾸 산교 가부시키가이샤 경화성 수지 조성물
CN108884199B (zh) * 2016-05-27 2021-04-16 协立化学产业株式会社 固化性树脂组合物
KR102261679B1 (ko) * 2016-05-27 2021-06-08 교리쯔 가가꾸 산교 가부시키가이샤 경화성 수지 조성물
JP2017210578A (ja) * 2016-05-27 2017-11-30 協立化学産業株式会社 硬化性樹脂組成物
WO2019189566A1 (fr) * 2018-03-28 2019-10-03 クラレノリタケデンタル株式会社 Composition de résine photodurcissable
US11365280B2 (en) 2018-03-28 2022-06-21 Kuraray Noritake Dental Inc. Photocurable resin composition

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