CN105722938A - Ultraviolet curable adhesive composition, adhesive film and method for producing adhesive film - Google Patents

Ultraviolet curable adhesive composition, adhesive film and method for producing adhesive film Download PDF

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Publication number
CN105722938A
CN105722938A CN201480062321.2A CN201480062321A CN105722938A CN 105722938 A CN105722938 A CN 105722938A CN 201480062321 A CN201480062321 A CN 201480062321A CN 105722938 A CN105722938 A CN 105722938A
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Prior art keywords
methyl
ultraviolet
acrylate
bonding film
mentioned
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Inventor
纲岛真理子
大地尉夫
纲岛启次
佐藤浩司
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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
    • C09J2475/00—Presence of polyurethane
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Abstract

The present invention addresses the problem of providing an ultraviolet curable adhesive composition which is capable of providing an adhesive film that has excellent cutting properties and resistance to wet heat whitening. The present invention provides an ultraviolet curable adhesive composition which is characterized by containing: a urethane (meth)acrylate (A) that is obtained by reacting a polyol (a1) that contains a polycarbonate polyol (a1-1), a polyisocyanate (a2) and a (meth)acrylic compound (a3) having an isocyanate group or a hydroxyl group; a (meth)acrylic compound (B) that has two or more (meth)acryloyl groups; a photopolymerization initiator (C); and an organic solvent (D). The present invention also provides a method for producing an adhesive film which is characterized in that an adhesive film is obtained by: applying the above-described ultraviolet curable adhesive composition to a base; then drying the organic solvent (C) so as to obtain an ultraviolet curable adhesive film; and subsequently bonding an adhesive layer of the ultraviolet curable adhesive film to the base and irradiating the ultraviolet curable adhesive film with ultraviolet light after the bonding.

Description

The manufacture method of ultraviolet-curing adhesive composition, bonding film and bonding film
Technical field
The present invention relates to the ultraviolet-curing adhesive composition of the bonding film that can obtain cutting property and wet-heat resisting albefaction excellence.
Background technology
Different from conventional solvent system binding agent, aqueous adhesive, ultraviolet-curing adhesive because need not the maturation time and high production rate can be expected, thus start to attract attention in the purposes such as laminating of optical component.
As above-mentioned ultraviolet-curing adhesive, it is known that such as use the binding agent that the non-solvent adhesive compositions containing urethane acrylate, acrylic monomers and Photoepolymerizationinitiater initiater obtains (referring for example to Japanese documentation 1.).
Above-mentioned binding agent can embody cohesive immediately after ultraviolet curing, thus high production rate is excellent, it addition, compared with the binding agent of conventional type, the thick-film of adhesive phase is more easy, thus has and can expect the advantages such as multifunction.
But, when by above-mentioned adhesive phase thick-film, the insufficient case of curable within film is a lot, has the problem producing cull at guillotine when cutting bonding film, or has the problems such as albefaction when being used in for a long time under wet heat condition.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-104296 publication
Summary of the invention
Invention to solve the technical problem that
The technical problem to be solved in the present invention is for providing the ultraviolet-curing adhesive composition of the bonding film that can obtain cutting property and wet-heat resisting albefaction excellence.
For solving the means of technical problem
The present invention provides ultraviolet-curing adhesive composition and the bonding film obtained by said composition, this ultraviolet-curing adhesive composition, it is characterized in that, containing carbamate (methyl) acrylate (A), there is (methyl) acrylic compounds (B) of (methyl) acryloyl group of more than 2, Photoepolymerizationinitiater initiater (C) and organic solvent (D), wherein, described carbamate (methyl) acrylate (A) is to make the polyhydric alcohol (a1) containing polycarbonate polyol (a1-1), polyisocyanates (a2) and have NCO or hydroxyl (methyl) acrylic compounds (a3) reaction and obtain.
Additionally, the present invention provides the manufacture method of a kind of bonding film, it is characterized in that, after above-mentioned ultraviolet-curing adhesive composition is coated on base material, organic solvent (C) is dried, obtain ultraviolet hardening bonding film, then, the adhesive layer of this ultraviolet hardening bonding film is attached at base material, afterwards, carry out ultraviolet radiation, thus obtaining bonding film.
Invention effect
Even if the bonding film obtained by the ultraviolet-curing adhesive composition of the present invention is cut, also without cull, cutting property excellence.Even if being not easy to cause albefaction it addition, be used under wet heat condition for a long time.And then, when using above-mentioned specific manufacture method, it is possible to obtain the bonding film that difference of height tracing ability is more excellent.
Therefore, the ultraviolet-curing adhesive composition of the present invention can be suitable as the binding agent used in optical component, it is particularly possible to is suitable for manufacturing the IT Related products such as contact panel, liquid crystal display, plasma scope, organic EL, PC, portable phone.
Detailed description of the invention
The ultraviolet-curing adhesive composition of the present invention contains carbamate (methyl) acrylate (A), there is (methyl) acrylic compounds (B) of (methyl) acryloyl group of more than 2, Photoepolymerizationinitiater initiater (C) and organic solvent (D), wherein, described carbamate (methyl) acrylate (A) is to make the polyhydric alcohol (a1) containing polycarbonate polyol (a1-1), polyisocyanates (a2) and have NCO or hydroxyl (methyl) acrylic compounds (a3) reaction and obtain.
As above-mentioned polycarbonate polyol (a1-1), for instance the polycarbonate polyol that carbonic ester and/or phosgene can be used and react with the compound of the hydroxyl with more than 2 and obtain.
As above-mentioned carbonic ester, it is possible to use such as methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate ester, diphenyl carbonate etc..These carbonic esters can be used alone, it is also possible to and use two or more.
Additionally, compound as the above-mentioned hydroxyl with more than 2, can use such as: ethylene glycol, diethylene glycol, triethylene glycol, TEG, 1, 2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, 2, 5-hexanediol, 1, 7-heptandiol, 1, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecane, 1, 12-dodecanediol, 2-methyl isophthalic acid, ammediol, neopentyl glycol, 2-butyl-2-ethyl-1, ammediol, 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl isophthalic acid, the aliphatic polyols such as 8-ethohexadiol；The ester ring type polyhydric alcohol such as 1,2-cyclobutanediol, 1,3-ring pentanediol, 1,4 cyclohexane dimethanol, ring heptandiol, ring ethohexadiol, hydroxypropyl Hexalin；The aromatic polyols etc. such as bisphenol-A, Bisphenol F, 4,4 '-bis-phenol.These compounds can be used alone, it is also possible to and use two or more.Compound as the above-mentioned hydroxyl with more than 2, from the aspect that can further improve cutting property, aliphatic polyol and/or ester ring type polyhydric alcohol are preferably used, more preferably use selected from 1,4-butanediol, 1, the compound of more than a kind in 5-pentanediol, 1,6-hexanediol, 1,4-CHDM.
Number-average molecular weight as above-mentioned polycarbonate polyol (a1-1), from the aspect that can further improve cutting property, wet-heat resisting albefaction and bonding physical property, it is preferably 500～5, the scope of 000, it is more preferably 600～3, the scope of the scope of 000, more preferably 700～2,000.Being explained, the number-average molecular weight of above-mentioned polycarbonate polyol (a1-1) represents the value utilizing gel permeation chromatography (GPC) method to obtain in following condition mensuration.
Determinator: high speed GPC device (TOSOH Co., Ltd's system " HLC-8220GPC ")
Post: re-use after the following post of TOSOH Co., Ltd is connected in series.
" TSKgelG5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: oxolane (THF)
Flow velocity: 1.0mL/ minute
Injection rate: 100 μ L (tetrahydrofuran solution of sample solution concentration 0.4 mass %)
Standard specimen: use following polystyrene standard to make standard curve.
(polystyrene standard)
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-500 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-1000 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-2500 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-5000 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-1 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-2 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-4 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-10 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-20 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-40 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-80 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-128 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-288 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-550 "
Consumption is made, from the aspect that can further improve cutting property and wet-heat resisting albefaction, in above-mentioned polyhydric alcohol (a1), it is preferred to the scope of 10～60 mass % as above-mentioned polycarbonate polyol (a1-1).
As above-mentioned polyhydric alcohol (a1), except above-mentioned polycarbonate polyol (a1-1), from the aspect that can further improve wet-heat resisting albefaction, cutting property and bonding physical property, it is preferable that possibly together with polyether polyol (a1-2).
As above-mentioned polyether polyol (a1-2), it is possible to use such as: make the product that the one kind or two or more addition polymerization in the alkylene oxides such as oxirane, expoxy propane, epoxy butane obtains to the compound of the above-mentioned hydroxyl with more than 2；The polytetramethylene glycol that tetrahydrofuran ring opening polymerization is obtained；The modified polytetramethylene glycol making oxolane and alkyl substituted tetrahydro furan copolymerization and obtain；The modified polytetramethylene glycol etc. making neopentyl glycol and oxolane copolymerization and obtain.These polyether polyol can be used alone, it is also possible to and use two or more.Wherein, from the aspect that can further improve bonding physical property, difference of height tracing ability and wet-heat resisting albefaction, it is preferred to use the polyether polyol of more than a kind in Polyethylene Glycol, polypropylene glycol and polytetramethylene glycol.
As the number-average molecular weight of above-mentioned polyether polyol (a1-2), from the aspect that can further improve bonding physical property and difference of height tracing ability, it is preferred to the scope of 200～5,000.Being explained, the number-average molecular weight of above-mentioned polyether polyol (a1-2) represents the value being measured in the same manner as the number-average molecular weight of above-mentioned polycarbonate polyol (a1-1) and obtain.
Mass ratio [(a1-1)/(a1-2)] as above-mentioned polycarbonate polyol (a1-1) Yu above-mentioned polyether polyol (a1-2), from cutting property, bonding physical property and the aspect of wet-heat resisting albefaction, it is preferred to the scope of 10/90～90/10, be more preferably 20/80～60/40 scope.
Above-mentioned polyhydric alcohol (a1) is containing above-mentioned polycarbonate polyol (a1-1), and preferably possibly together with above-mentioned polyether polyol (a1-2), it is also possible to contain other polyhydric alcohol as required.
As other polyhydric alcohol above-mentioned, it is possible to use such as PEPA, polybutadiene polyol, hydrogenated butadiene polymer polyhydric alcohol, two polyalcohols, polyacrylic polyols etc..These polyhydric alcohol can be used alone, it is also possible to and use two or more.
As above-mentioned polyisocyanates (a2), it is possible to use such as: the aromatic polyisocyanate of XDI, phenylene diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate etc.；The aliphatic such as hexamethylene diisocyanate, lysinediisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate or ester ring type polyisocyanates etc..These polyisocyanates can be used alone, it is also possible to and use two or more.Wherein, from can further improve cutting property and the aspect of bonding physical property, ester ring type polyisocyanates is preferably used, more preferably the polyisocyanates of more than a kind be selected from HMDI, isophorone diisocyanate, cyclohexane diisocyanate and methylcyclohexane diisocyanate is used.
Above-mentioned (methyl) acrylic compounds (a3) with NCO or hydroxyl is the compound used for the purpose of introducing (methyl) acryloyl group in carbamate (methyl) acrylate (A).
As (methyl) acrylic compounds with NCO that can act as above-claimed cpd (a3), such as 2-(methyl) acryloyloxyethyl isocyanate, 2-(2-(methyl) acryloyloxyethoxy) ethyl isocyanate, 1,1-double; two ((methyl) acryloyloxymethyl) ethyl isocyanates etc. can be used.These compounds can be used alone, it is also possible to and use two or more.Wherein, from the aspect of the easiness obtaining raw material, it is preferred to use 2-(methyl) acryloyloxyethyl isocyanate, from the aspect of curable, 2-acryloyloxyethyl isocyanate is more preferably used.
As (methyl) acrylic compounds with hydroxyl that can act as above-claimed cpd (a3), it is possible to use such as: (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxybutyl, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid own ester of 6-hydroxyl, hydroxyethyl acrylamide etc. have (methyl) alkyl acrylate of hydroxyl；Trimethylolpropane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc. have multifunctional (methyl) acrylate of hydroxyl；Polyethylene glycol monoacrylate, polypropylene glycol mono acrylic ester etc..These compounds can be used alone, it is also possible to and use two or more.Wherein, from the aspect of the easiness obtaining raw material, curable and bonding physical property, it is preferred to use there is (methyl) alkyl acrylate of hydroxyl, more preferably use acrylic acid 2-hydroxy methacrylate, acrylic acid 4-hydroxybutyl.
Manufacture method as carbamate (methyl) acrylate (A) when using (methyl) acrylic compounds with NCO as above-claimed cpd (a3), such as following method etc. can be used: under solvent-free, put into above-mentioned polyhydric alcohol (a1) and above-mentioned polyisocyanates (a2) makes it react and obtains the carbamate prepolymer with hydroxyl, then, supply has above-mentioned (methyl) acrylic compounds (a3) of NCO, and make it mix, reaction, thus manufacturing carbamate (methyl) acrylate (A).Any of the above-described reaction all can be enumerated and such as carry out when 20～120 DEG C 30 minutes～24 hours.
Manufacture method as above-mentioned carbamate (methyl) acrylate (A) when using (methyl) acrylic compounds with hydroxyl as above-claimed cpd (a3), such as following method etc. can be used: under solvent-free, after putting into above-mentioned polyhydric alcohol (a1) and above-mentioned (methyl) acrylic compounds (a3) in reaction system, supply above-mentioned polyisocyanates (a2), and make it mix, react, thus manufacture carbamate (methyl) acrylate (A)；Or, make above-mentioned polyhydric alcohol (a1) react with above-mentioned polyisocyanates (a2) under solvent-free and obtain the carbamate prepolymer with NCO, then, supply has above-mentioned (methyl) acrylic compounds (a3) of hydroxyl, and make it mix, react, thus manufacture carbamate (methyl) acrylate (A).Above-mentioned arbitrary reaction all can be enumerated and such as carry out when 20～120 DEG C 30 minutes～24 hours.
The manufacture of above-mentioned carbamate (methyl) acrylate (A) can carry out under the existence of organic solvent described later (C).
When using (methyl) acrylic compounds with hydroxyl as above-claimed cpd (a3), above-mentioned polyhydric alcohol (a1), the reaction of above-mentioned polyisocyanates (a2) and above-mentioned (methyl) acrylic compounds (a3) is when the scope that equivalents ratio [total amount of NCO/hydroxyl] is 0.75～1 of the NCO that total amount and the polyisocyanates (a2) of the hydroxyl that the hydroxyl that above-mentioned polyhydric alcohol (a1) has and above-mentioned (methyl) acrylic compounds (a3) have has carries out, control gained carbamate (methyl) acrylate (A) molecular weight in be preferred, it is more preferably the scope of 0.79～0.995.It addition, it can also be made to react when above-mentioned equivalents ratio is more than 1, but, now for the purpose making the NCO of carbamate (methyl) acrylate (A) inactivate, it is preferred to use alcohol such as methanol.
Additionally, when using (methyl) acrylic compounds with isocyanates as above-claimed cpd (a3), above-mentioned polyhydric alcohol (a1), the reaction of above-mentioned polyisocyanates (a2) and above-mentioned (methyl) acrylic compounds (a3) is when the scope that equivalents ratio [total amount/hydroxyl of NCO] is 0.75～1 of the summation of the NCO that the hydroxyl that above-mentioned polyhydric alcohol (a1) has has with polyisocyanates (a2) and (methyl) acrylic compounds (a3) carries out, control gained carbamate (methyl) acrylate (A) molecular weight in be preferred, it is more preferably the scope of 0.79～0.995.It addition, it can also be made to react when above-mentioned equivalents ratio is more than 1, now for the purpose making the NCO of carbamate (methyl) acrylate (A) inactivate, it is preferred to use alcohol such as methanol.
It addition, when manufacturing carbamate (methyl) acrylate (A), it is possible to use polymerization inhibitor, urethanation catalyst etc. as required.
As above-mentioned polymerization inhibitor, such as 3 can be used, 5-di-t-butyl-4-hydroxy-methylbenzene, hydroquinone, methylnaphthohydroquinone, hydroquinone monomethyl ether ((methoquinone)), p-tert-butyl catechol methoxyphenol, 2,6-di-tertiary butyl methyl phenol, phenothiazine, tetramethylthiuram disulfide, diphenylamines, dinitro benzene etc..These polymerization inhibitors can be used alone, it is also possible to and use two or more.
As above-mentioned urethanation catalyst, it is possible to use such as: nitrogen-containing compounds such as triethylamine, triethylenediamine, N-methylmorpholines；The slaines such as potassium acetate, zinc stearate, tin octoate；The organo-metallic compounds etc. such as dibutyl tin laurate, four acetylacetone,2,4-pentanedione zirconiums.These urethanation catalyst can be used alone, it is also possible to and use two or more.
Above-mentioned carbamate (methyl) acrylate (A) is to have to be irradiated by light or heat and make its material carrying out radical polymerization (methyl) acryloyl group.(methyl) acryloyl group equivalent as above-mentioned carbamate (methyl) acrylate (A); from the aspect that can further improve cutting property, bonding physical property and difference of height tracing ability; it is preferably 1; 000～50; the scope of 000g/eq., it is more preferably 3; 000～25, the scope of 000g/eq..Being explained, above-mentioned (methyl) acryloyl group equivalent represents the gross mass value divided by the equivalent gained of (methyl) acrylic existed in above-mentioned carbamate (methyl) acrylate (A) of above-mentioned polyhydric alcohol (a1), polyisocyanates (a2) and (methyl) acrylic compounds (a3).
It is explained, in the present invention, " (methyl) acrylic compounds " refers to the one or both in methacrylic compounds and acrylic compounds, " (methyl) acrylate " is the one or both in methacrylate and acrylate, " (methyl) acryloyl group " refers to the one or both in methylacryloyl and acryloyl group, " (methyl) acrylic acid " is the one or both in methacrylic acid and acrylic acid, " (methyl) acrylic monomers " refers to the one or both in methacrylic acid monomer and acrylic monomers.
Mass ratio as the amino-formate bond in above-mentioned carbamate (methyl) acrylate (A), from the aspect that can further improve cutting property, bonding physical property and difference of height tracing ability, in the total amount of carbamate (methyl) acrylate (A), it is preferred to the scope of 4～20 mass %, be more preferably the scope of 5～15 mass %.Being explained, the carbamate bond amount of above-mentioned carbamate (methyl) acrylate (A) represents in above-mentioned raw materials the shared carbamate bond structure mass ratio relative to above-mentioned polyhydric alcohol (a1), the gross mass of above-mentioned polyisocyanates (a2) and above-mentioned (methyl) acrylic compounds (a3).
Weight average molecular weight as above-mentioned carbamate (methyl) acrylate (A), from the aspect that can further improve cutting property, bonding physical property and difference of height tracing ability, it is preferably 5,000～100, the scope of 000, it is more preferably 15, the scope of 000～50,000.Being explained, the weight average molecular weight of above-mentioned carbamate (methyl) acrylate (A) represents the value being measured in the same manner as the number-average molecular weight of above-mentioned polycarbonate polyol (a1-1) and obtain.
(methyl) acrylic compounds は (B) of above-mentioned (methyl) acryloyl group with more than 2 is giving necessary composition in excellent wet-heat resisting albefaction.As above-mentioned (methyl) acrylic compounds (a3), it is possible to use such as: ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, tetramethylene glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, hexamethylene glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two (trimethylolpropane) two (methyl) acrylate, two (trimethylolpropane) three (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, dipentaerythritol two (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, aliphatic multifunctional (methyl) acrylate such as dipentaerythritol six (methyl) acrylate；Three (2-(methyl) acryloyl-oxyethyl) isocyanuric acid ester etc. has multifunctional (methyl) acrylate etc. of isocyanuric acid ester skeleton.These (methyl) acrylic compounds can be used alone, it is also possible to and use two or more.Wherein, from the aspect that can further improve wet-heat resisting albefaction, it is preferably used selected from multifunctional (methyl) acrylate of aliphatic and has with more than a kind in multifunctional (methyl) acrylate of multifunctional (methyl) acrylate backbone of isocyanuric acid ester skeleton, more preferably using (methyl) acrylic compounds of more than a kind be selected from tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate and three (2-(methyl) acryloyl-oxyethyl) isocyanuric acid ester.Being explained, above-mentioned in the present invention " multifunctional " refers to have more than 2, preferably 2～8, more preferably 2～6 (methyl) acryloyl groups.
Content as above-mentioned (methyl) acrylic compounds (B), from the aspect that can further improve wet-heat resisting albefaction, relative to above-mentioned carbamate (methyl) acrylate (A) 100 mass parts, it is preferred to the scope of 1～30 mass parts, be more preferably the scope of 5～20 mass parts.
Above-mentioned Photoepolymerizationinitiater initiater (C) be irradiated by light or heating etc. and produce free radical and cause the material of radical polymerization of above-mentioned carbamate (methyl) acrylate (A).
As above-mentioned Photoepolymerizationinitiater initiater (C), can use such as: the acetophenone compounds such as 4-phenoxydichloroacetophenone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone, 2-methyl-[4-(methyl mercapto) phenyl]-2-morpholino-1-acetone, 2,2-dimethoxy-2-phenyl acetophenone；The benzoin compounds such as benzoin, benzoin methylether, benzoin diisopropyl ether, benzoin iso-propylether, benzoin isobutyl ether；Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 ' benzophenone cpd such as-methyldiphenyl thioether, 3,3 '-dimethyl-4-methoxy benzophenone；The thioxanthone compounds such as thiaxanthone, CTX, 2,4-bis-clopenthixal ketone, 2-methyl thiaxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropylthioxanthone；4; Michler ' sketone (Michler's keton)), the anthraquinone compounds such as 4,4 '-lignocaine benzophenone, α-acyl group oxime ester, benzil, methyl benzoylformate (" Vicure55 "), 2-ethyl-anthraquinone 4 '-dimethylamino thiaxanthone (another name:；The acylphosphine oxide compounds such as 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide, double; two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide；3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, acrylated benzophenone etc..These Photoepolymerizationinitiater initiaters can be used alone, it is also possible to and use two or more.
As above-mentioned Photoepolymerizationinitiater initiater (C); from the aspect that can further improve bonding physical property and curable; be preferably used selected from 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2; 4,6-trimethyl benzoyl diphenyl base phosphine oxides and double; two (2,4; 6-trimethylbenzoyl) Photoepolymerizationinitiater initiater of in phenyl phosphine oxide more than a kind; more preferably TMDPO.
Consumption is made as above-mentioned Photoepolymerizationinitiater initiater (C), from the aspect that can further improve curable, relative to above-mentioned carbamate (methyl) acrylate (A) 100 mass parts, it is preferred to the scope of 0.1～20 mass parts, be more preferably the scope of 0.2～15 mass parts.
As above-mentioned organic solvent (D), it is possible to use such as toluene, ethyl acetate, butyl acetate, butanone, hexane, acetone, Ketohexamethylene, propione, acetonitrile, propionitrile, isopropyl cyanide, valeronitrile, dimethyl sulfoxide, dimethylformamide etc..These organic solvents can be used alone, it is also possible to and use two or more.
Consumption is made, from the aspect that can further improve drying property and screening characteristics, in ultraviolet-curing adhesive composition, it is preferred to below 60 mass %, be more preferably the scope of 5～50 mass % as above-mentioned organic solvent (D).
The ultraviolet-curing adhesive composition of the present invention contains above-mentioned carbamate (methyl) acrylate (A), above-mentioned (methyl) acrylic compounds (B), above-mentioned Photoepolymerizationinitiater initiater (C) and above-mentioned organic solvent (D) as essential component, it is also possible to contain other additives as required.
As other additives above-mentioned, it is possible to use such as silane coupler, antioxidant, light stabilizer, antirust agent, thixotropy conferring agents, sensitizer, polymerization inhibitor, levelling agent, viscosifier, antistatic additive, fire retardant etc..These additives can be used alone, it is also possible to and use two or more.Wherein, when being used for after wet-heat resisting by the ultraviolet-curing adhesive composition of the present invention requiring the purposes of high binding, it is preferable that containing silane coupler (E).It addition, when the ultraviolet-curing adhesive composition of the present invention being used for the purposes of requirement wet-heat resisting xanthochromia, it is preferable that containing antioxidant (F) and light stabilizer (G).
As above-mentioned silane coupler (E), it is possible to use such as: 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl ジ Ethoxysilane, 3-glycidoxypropyl dimethoxysilane etc. have the silane coupler of epoxy radicals；2-(3, 4-epoxycyclohexyl) ethyl triethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyl-methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl-methyl diethoxy silane, 2-(3, 4-epoxycyclohexyl) propyl trimethoxy silicane, 2-(3, 4-epoxycyclohexyl) hydroxypropyl methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) propyl-triethoxysilicane, 2-(3, 4-epoxycyclohexyl) hydroxypropyl methyl diethoxy silane etc. has the silane coupler of alicyclic epoxy group；Vinyl trichlorosilane, vinyltrimethoxy silane, VTES, to styryl trimethoxy silane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl trimethoxy silane, 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi trimethoxy silane, oxyalkylsiloxane oligomer etc..These silane couplers can be used alone, it is also possible to and use two or more.Wherein, from the aspect that can further improve the bonding force after wet-heat resisting, the silane coupler with epoxy radicals and/or the silane coupler with alicyclic epoxy group are preferably used, more preferably use selected from 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, the silane coupler of in 3-glycidoxypropyltrime,hoxysilane and 3-glycidoxypropyl group triethoxysilane more than a kind.
As use above-mentioned silane coupler (E) time make consumption, from the aspect that can further improve the bonding force after wet-heat resisting, relative to above-mentioned carbamate (methyl) acrylate (A) 100 mass parts, it is preferred to the scope of 0.01～10 mass parts, be more preferably the scope of the scope of 0.05～5 mass parts, more preferably 0.05～1 mass parts.
As above-mentioned antioxidant (F), it is possible to use catch hindered phenol compound (main anti-oxidant) and the phosphorus compound decomposed by the peroxide produced by heat deterioration, the sulphur compound (secondary antioxidant) etc. of the free radical produced by heat deterioration.
As above-mentioned hindered phenol compound, can use such as: triethylene glycol double; two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], tetramethylolmethane four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 3-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid stearyl, the double; two [3-(3 of sulfo-diethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester], benzenpropanoic acid-3, double; two (1,1-the dimethyl ethyl)-4-hydroxyl-C of 5-7-C9Pendant alkyl group ester, 4, double, two (dodecylthiomethyl) orthoresol of 6-, N-phenylaniline and 2, 4, the product of 4-trimethylpentene, the acrylic acid 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base benzyl)-4-methyl phenyl ester, 3, double, two [the 2-(3-(tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1 of 9-, 1-dimethyl ethyl] 2, 4, 8, 10-tetra-oxaspiro [5.5] hendecane, 2, 6-di-tert-butyl-4-methy phenol, 2, 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 2, 5-bis-tertiary pentyl hydroquinone etc..These compounds can be used alone, it is also possible to and use two or more.
As above-mentioned phosphorus compound, it is possible to use such as: triphenylphosphine, double, two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester, triphenyl phosphite, trisnonylphenyl phosphite, three (2,4-dibutylphenyl) phosphite ester, three (2,4-dibutyl-5-aminomethyl phenyl) phosphite ester, three (the 2-tert-butyl group-4-(3-butyl-4-hydroxy-5-methyl base thiophenyl)-5-aminomethyl phenyl) phosphite ester, three (2,4-di-tert-butyl-phenyl) phosphite ester, tridecyl phosphite, octyl diphenyl phosphite ester, two (decyl) single phenyl phosphites, two (tridecyl) pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, double, two (2,4-dibutylphenyl) pentaerythritol diphosphites, double, two (2,6-dibutyl-4-aminomethyl phenyl) pentaerythritol diphosphites, double, two (2,4,6-tributyl phenyl) pentaerythritol diphosphites, double, two (2,4-dicumylphenyl) pentaerythritol diphosphites, four (tridecyl) isopropylidenediphenol diphosphites, four (tridecyls)-4,4 '-double, two (2-butyl-5-methylphenol) diphosphites of positive butylidene, six (tridecyl)-1,1,3-three (2-methyl-4-hydroxyl-5-butyl phenyl) butane triphosphite ester, four (2,4-dibutylphenyl) biphenylen, 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide, 2,2 '-di-2-ethylhexylphosphine oxide (4,6-butyl phenyl)-2-ethylhexyl phosphite ester, 2,2 '-di-2-ethylhexylphosphine oxide (4,6-butyl phenyl) octadecyl phosphite ester, 2,2 '-ethylenebis (4,6-dibutylphenyl) fluorophosphites, three (2-[(2,4,8,10-tetrabutyl dibenzo [d, f] [1,3,2] dioxaphosphepin cycloheptadiene-6-base) oxygen base] ethyl) amine, the phosphite ester etc. of 2-ethyl-2-butyl propylene glycol and 2,4,6-tributyl phenol.These compounds can be used alone, it is also possible to and use two or more.
As above-mentioned sulphur compound, can use such as:: 3, the double, two dodecyl ester of 3 '-propane thioic acid, 3, 3 '-dilauryl thiodipropionate, sulfo-dithionic acid two lauryl, 3, 3 '-thio-2 acid two (tridecyl) ester, 3, 3 '-thio-2 acid two myristin, 3, 3 '-distearylthiodi-propionate, four-methylene-3-lauryl thiopropionate methane, 3, 3 '-methyl-3, 3 '-distearylthiodi-propionate, 3, 3 '-thio-2 acid lauryl stearyl, double, two [2-methyl-4-(3-alkyl sulfo-propionyloxy)-5-tert-butyl-phenyl] sulfide, β-lauryl thiopropionate, 2-mercaptobenzimidazole, 2-sulfydryl-5-tolimidazole, 3, 3 '-thio-2 acid two (octadecyl) ester etc..These compounds can be used alone, it is also possible to and use two or more.
Wherein, from the aspect that can further improve bonding force and wet-heat resisting xanthochromia, phosphorus compound is preferably used, more preferably use selected from triphenylphosphine, double; two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester and three (2,4-di-tert-butyl-phenyl) antioxidant of in phosphite ester more than a kind, it is particularly preferred to use triphenylphosphine, double; two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester.
As use above-mentioned antioxidant (F) time make consumption, from the aspect that can further improve wet-heat resisting xanthochromia, relative to above-mentioned carbamate (methyl) acrylate (A) 100 mass parts, it is preferred to the scope of 0.01～10 mass parts.
Above-mentioned light stabilizer (G) is the material catching the free radical produced by light deterioration, it is possible to use such as: the free radical scavengers such as mercaptan compound, sulfide compound, hindered amine compound；The UV absorbent such as benzophenone cpd, benzoic acid ester compounds etc..These light stabilizers can be used alone, it is also possible to and use two or more.Wherein, from the aspect that can further improve wet-heat resisting xanthochromia, it is preferred to use hindered amine compound.
As above-mentioned hindered amine compound, it is possible to use such as: hexamethylene and peroxidating N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichlorines 1,3, the product of 5-triazine and 2-ethylaminoethanol product, decanedioic acid double; two (2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) ester, 1,1-dimethyl ethyl hydrogen peroxide and octane product etc. there is the hindered amine compound of amino ether；The N-acetyl base system hindered amine compounds such as N-acetyl group-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione；Decanedioic acid double; two (1,2,2,6,6-pentamethyl-4-piperidyl) ester, double; two (1,2,2,6,6,-pentamethyl-4-piperidyl) { [3, double; two (1,1-the dimethyl ethyl)-4-hydroxy phenyl of 5-] methyl butylmalonic acid ester, dimethyl succinate 1-(2-hydroxyethyl)-4-hydroxyl-2,2,6,6-tetramethyl piperidine condensation polymer, malonic acid [{ 4-methoxyphenyl } methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidyl) the N-alkyl hindered amine compound etc. of ester.These compounds can be used alone, it is also possible to and use two or more.
As use above-mentioned light stabilizer (G) time make consumption, from the aspect that can further improve wet-heat resisting xanthochromia, relative to above-mentioned carbamate (methyl) acrylate (A) 100 mass parts, it is preferred to the scope of 0.01～10 mass parts.
As the viscosity of the ultraviolet-curing adhesive composition of the present invention, from the aspect of screening characteristics and operability, it is preferred to 500～30, the scope of 000mPa s, it is more preferably 1,000～20, the scope of 000mPa s.Being explained, above-mentioned viscosity represents 25 DEG C of values obtained by Brookfield viscometer mensuration.
It follows that the manufacture method of the bonding film of the present invention is illustrated.
Above-mentioned bonding film is to obtain by experiencing the operation making compositions solidify operation dry for the organic solvent (C) in above-mentioned ultraviolet-curing adhesive composition and irradiation ultraviolet radiation.
Additionally, manufacture method as above-mentioned bonding film, from the aspect obtaining the excellent bonding film of difference of height tracing ability, it is preferred to use following method: after above-mentioned ultraviolet-curing adhesive composition is coated on base material, organic solvent (C) is dried, obtain ultraviolet hardening bonding film, then, the adhesive layer of this ultraviolet hardening bonding film is attached at base material, afterwards, carry out ultraviolet radiation, thus obtaining bonding film.According to the method, when the above-mentioned ultraviolet hardening bonding film before ultraviolet curing uses the base material with differences of height such as printing differences of height as the base material attached afterwards, above-mentioned ultraviolet hardening bonding film can be attached in this difference of height part unoccupied place of not leaving a blank, therefore can obtain the bonding film that difference of height tracing ability is excellent.
It is explained, in the present invention, the state before dried for organic solvent and ultraviolet curing is called " ultraviolet hardening bonding film ", the state after ultraviolet curing is called " bonding film ".
As above-mentioned base material, it is possible to use such as: plastic basis material, flexible print substrates, glass baseplate, these base materials are implemented base material that the demoulding processes, be deposited with the base material etc. of ITO (tin indium oxide).It is explained, identical base material can be used respectively on the two sides of adhesive layer, it is possible to use different base materials.
As above-mentioned plastic basis material, it is possible to use such as: the plastic foil that obtains as raw material using acrylic resin, PC (Merlon), PBT (polybutylene terephthalate (PBT)), PPS (polyphenylene sulfide), MODIFIED PP E (polyphenylene oxide), PET (polyethylene terephthalate), COP (cyclic olefin polymer), TAC (tri acetyl cellulose) etc., antireflection film, anti-soil film, composition contact panel the film etc. of nesa coating.
As the method that above-mentioned ultraviolet-curing adhesive composition is coated on above-mentioned base material, the method such as using coating machine (applicator), roll coater, scraper for coating agent, gravure coater etc. to be coated can be enumerated.After above-mentioned coating, the duplexer of gained being loaded drying machine etc., the scope temperature 50～130 DEG C makes it dry 1～30 minute, makes organic solvent (C) dry, thus obtaining the ultraviolet hardening bonding film before ultraviolet curing.
As above-mentioned ultraviolet hardening bonding film, from the aspect that can further improve difference of height tracing ability, its storage elastic modelling quantity when 60 DEG C is preferably 5 × 10 when measuring with frequency 1Hz4Below Pa, it is more preferably 1 × 103～5 × 104The scope of Pa.Being explained, the assay method of the storage elastic modelling quantity of above-mentioned ultraviolet hardening bonding film is recorded in embodiment.
It addition, as above-mentioned ultraviolet hardening bonding film, from the aspect that can also improve cutting property and difference of height tracing ability further, its storage elastic modelling quantity when 30 DEG C is preferably 5 × 10 when measuring with frequency 1Hz4More than Pa, it is more preferably 5 × 104～5 × 106The scope of Pa.
Both can also be made to crimp after the ultraviolet hardening bonding film of gained is attached at above-mentioned base material and implement steam pressure (autoclave) as required to process.
Afterwards, carrying out ultraviolet radiation, thus obtaining bonding film, as the above-mentioned method carrying out ultraviolet radiation, the method such as using the known ultraviolet illumination injection devices such as xenon lamp, xenon-mercury lamp, metal halide lamp, high voltage mercury lamp, low pressure mercury lamp can be enumerated.
As above-mentioned ultraviolet irradiation amount, it is preferred to 0.05～5J/cm2, be more preferably 0.1～3J/cm2, be particularly preferably 0.3～1.5J/cm2Scope.Being explained, ultraviolet irradiation amount is using the value that uses GS-YUASA Co., Ltd. UV detector " UVR-N1 " and measure in the wavelength region of 300～390nm as benchmark.
Thickness as the bonding film obtained by above method, it is possible to the purposes according to using suitably is determined, it is preferred to the scope of substantially 10～500 μm.
It addition, as above-mentioned bonding film, from the aspect that can further improve cutting property, its storage elastic modelling quantity when 30 DEG C is preferably 1 × 10 when measuring with frequency 1Hz4More than Pa, it is more preferably 1 × 104～5.0 × 107The scope of Pa.Being explained, the assay method of the storage elastic modelling quantity of above-mentioned bonding film is recorded in embodiment.
It addition, as above-mentioned bonding film, from the aspect that can further improve difference of height tracing ability, its storage elastic modelling quantity when 100 DEG C is preferably 1 × 10 when measuring with frequency 1Hz4More than Pa, it is more preferably 1 × 104～5 × 105The scope of Pa.Being explained, the assay method of the storage elastic modelling quantity of above-mentioned bonding film is recorded in embodiment.
Above, even if the bonding film that the ultraviolet-curing adhesive composition using the present invention obtains is cut, also without cull, cutting property excellence.It addition, when using above-mentioned specific manufacture method, it is possible to obtain the bonding film that difference of height tracing ability is more excellent.
Therefore, the ultraviolet-curing adhesive composition of the present invention can be suitable as the binding agent used in optical component, is especially suitable for manufacturing the IT Related products such as contact panel, liquid crystal display, plasma scope, organic EL, PC, portable phone.
Embodiment
Hereinafter, the present invention will be described in more detail to use embodiment.
[synthesis example 1]
The synthesis > of < urethane acrylate (A-1)
The reaction vessel possessing blender, reflux condensing tube, nitrogen ingress pipe, thermometer adds polypropylene glycol (number-average molecular weight；2,000, following, it is abbreviated as " PPG2000 ".) 46.4 mass parts, polycarbonate polyol (make Ube Industries, Ltd's system " ETERNACOLLUM-90 (3/1) ", 1,4-dimethanol--cyclohexane, 1,6-hexanediol and the product of dimethyl carbonate, number-average molecular weight 900, following, it is abbreviated as " UM-90 ".) 38.1 mass parts, acrylic acid 2-hydroxy methacrylate (following, be abbreviated as " HEA ".) 0.8 mass parts, 2,6-di-tertiary butyl methyl phenol 0.3 mass parts, p methoxy phenol 0.05 mass parts.In reaction vessel, temperature is to after 40 DEG C, add isophorone diisocyanate (following, be abbreviated as " IPDI ".) 14.7 mass parts.Then, add two neodecanoic acid dioctyl tin 0.1 mass parts, be warming up to 80 DEG C with 1 hour.Afterwards, keep 12 hours at 80 DEG C, after confirming whole NCO disappearances, to its cooling, obtain urethane acrylate (A-1).The equivalent of the acryloyl group of the urethane acrylate (A-1) of gained is 15,000 (be rounded up to significant digits 2 figure place.The molecular weight of acrylic acid 2-hydroxy methacrylate is 116.1.Hereinafter, synonym.), weight average molecular weight be 26,000.
[synthesis example 2]
The synthesis > of < urethane acrylate (A-2)
The reaction vessel possessing blender, reflux condensing tube, nitrogen ingress pipe, thermometer adds 33.7 mass parts PPG2000, polytetramethylene glycol (number-average molecular weight；650, following, it is abbreviated as " PTMG650 ".) 28.1 mass parts, Polyethylene Glycol (number-average molecular weight 400, following, be abbreviated as " PEG400 ".) 16.0 mass parts, HEA0.55 mass parts, 2,6-di-tertiary butyl methyl phenol 0.3 mass parts, p methoxy phenol 0.05 mass parts.In reaction vessel, temperature is to after 40 DEG C, adding 22.2 mass parts IPDI.Then, add two neodecanoic acid dioctyl tin 0.1 mass parts, be warming up to 80 DEG C with 1 hour.Afterwards, keep 12 hours at 80 DEG C, after confirming whole NCO disappearances, to its cooling, obtain urethane acrylate (A-2).The equivalent of the acryloyl group of the urethane acrylate (A-2) of gained is 21,000, weight average molecular weight is 28,000.
[embodiment 1]
The preparation > of < ultraviolet-curing adhesive composition
Will be provided with blender, reflux condensing tube, thermometer reaction vessel be warming up in container temperature 80 DEG C, add above-mentioned urethane acrylate (A-1) 100 mass parts, ethyl acetate 67 mass parts, stirring reaches uniformly to it.Afterwards, be cooled to room temperature, be under agitation sequentially added into pentaerythritol triacrylate and tetramethylol methane tetraacrylate mixture (Toagosei Co., Ltd's system " ARONIXM-305 ", following, be abbreviated as " (B-1) ".) 10 mass parts, TMDPO (following, be abbreviated as " (C-1) ".) 0.5 mass parts, decanedioic acid double; two (2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) ester 0.5 mass parts, triphenylphosphine 0.5 mass parts, stirring reaches uniformly to it.Afterwards, with 200 order metal mesh filters, ultraviolet-curing adhesive composition is obtained.
[embodiment 2]
Except replacing above-mentioned (B-1) to use three (2-acryloyl-oxyethyl) isocyanuric acid ester (below, to be abbreviated as " (B-2) ".) beyond, obtain ultraviolet-curing adhesive composition in the same manner as embodiment.
[comparative example 1]
Will be provided with blender, reflux condensing tube, thermometer reaction vessel be warming up in container temperature 80 DEG C, add above-mentioned urethane acrylate (A-2) 100 mass parts, ethyl acetate 67 mass parts, stirring reaches uniformly to it.Afterwards; it is cooled to room temperature; under agitation add 2 successively; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide 0.5 mass parts, decanedioic acid double; two (2,2,6; 6-tetramethyl-1-(octyloxy)-4-piperidyl) ester 0.5 mass parts, triphenylphosphine 0.5 mass parts, stirring reach uniformly to it.Afterwards, with 200 order metal mesh filters, ultraviolet-curing adhesive composition is obtained.
[comparative example 2]
Beyond above-mentioned M-305, obtain ultraviolet-curing adhesive composition similarly to Example 1.
[manufacture method of ultraviolet hardening bonding film]
The surface of the polyethylene terephthalate film (demoulding PET50) of the thickness 50 μm processed through the demoulding on surface reaches the ultraviolet-curing adhesive oil/fat composition obtained in coating Examples and comparative example in the way of in the of 100 μm by the dried thickness of organic solvent, make it dry 5 minutes in 80 DEG C of drying machines, obtain ultraviolet hardening bonding film.
[evaluation methodology of cutting property]
Above-mentioned ultraviolet hardening bonding film is fitted in demoulding PET50 further.Then, 1J/cm is reached with the accumulated light of the wavelength in UV-A region2Mode carry out ultraviolet radiation, obtain the duplexer with bonding film.Utilize guillotine to cut the duplexer of gained, visualization at the blade of guillotine with or without cull.It is explained, is " T " by the average evaluation to cull unconfirmed, will confirm that the average evaluation of cull is for " F ".
[evaluation methodology of difference of height tracing ability]
Above-mentioned ultraviolet hardening bonding film fits in the polyethylene terephthalate film (PET100) of thickness 100 μm, and being produced on single-sided lamination has the bonding film of PET100.Cut into vertical 50mm, horizontal 40mm, made test film.Additionally, the another framework being cut vertical 40mm, horizontal 30mm, wide 5mm by PET50.The framework of this thickness 50 μm is positioned on glass plate, from the upper side by 2kg roller × 2 time reciprocal by above-mentioned test film to attach in the way of making PET100 and the framework of test film clamping above-mentioned thickness 50 μm.By its 50 DEG C, 0.5MPa when steam pressure process 20 minutes.Afterwards, the accumulated light of the wavelength in the UV-A region after casting from glass plate side with glass plate reaches 1J/cm2Mode carry out ultraviolet radiation, obtain the duplexer with bonding film.The duplexer of gained is placed 24 hours under 80 DEG C of environment, the inboard portion of the framework that visualization thickness is 50 μm, evaluate the tracing ability of the difference of height to 50 μm in such a way.
" A ": do not have floating from difference of height, and bubble-free is mixed into.
" B ": do not have floating from difference of height, but determines that there is part bubble to be mixed into.
" C ": have significant bubble to be mixed into.
[assay method of the storage elastic modelling quantity of ultraviolet hardening bonding film (before ultraviolet radiation)]
The adhesive layer of above-mentioned ultraviolet hardening bonding film is carried out under shading in the way of thickness reaches 1mm overlap, makes test film.According to JISK7198-1991, use ARES determination of viscoelasticity device (TAInstrumentsJapan Co., Ltd. system), measure the storage elastic modelling quantity of gained test film when programming rate 2 DEG C/min, mensuration frequency 1Hz, temperature range 0～100 DEG C, strain 0.5%.
[assay method of the storage elastic modelling quantity of bonding film (after ultraviolet radiation)]
Utilize above-mentioned [evaluation methodology of cutting property] that the bonding film of gained carries out overlap in the way of thickness reaches 1mm, make test film.Use ARES determination of viscoelasticity device (TAInstrumentsJapan Co., Ltd. system), when programming rate 2 DEG C/min, mensuration frequency 1Hz, temperature range 0～100 DEG C, strain 0.5%, the test film of gained is measured.
[evaluation methodology of wet-heat resisting albefaction]
Above-mentioned ultraviolet hardening bonding film fits in the polyethylene terephthalate film (PET100) of thickness 100 μm, and being produced on single-sided lamination has the bonding film of PET100.Cut into vertical 50mm, horizontal 40mm, peel off demoulding PET50, be attached at glass plate, make test film.The accumulated light of the wavelength in the UV-A region after passing through from the glass plate side of gained test film with glass plate reaches 1J/cm2Mode carry out ultraviolet radiation, obtain the duplexer with bonding film.After being used electricity Shi Industrial Co., Ltd scopometer of Japan " NDH5000 " measuring mist degree (mist degree 1), 85 DEG C, place 100 hours under the environment of humidity 85%, 23 DEG C, taking-up under the environment of humidity 50%.After taking-up, electricity Shi Industrial Co., Ltd scopometer of Japan " NDH5000 " was used to measure the mist degree (mist degree 2) of bonding film within 10 minutes according to JISK7361-1-1997.Being explained, be " T " by the average evaluation that difference is less than 1% of above-mentioned mist degree 1 with mist degree 2, the average evaluation more than 1% is " F ".
[table 1]
Table 1 Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2
Carbamate (methyl) acrylate (A) (A-1) (A-1) (A-2) (A-1)
Polycarbonate polyol (a1 1) UM-90 UM-90 UM-90
Polyether polyol (a1 2) PPG2000 PPG2000 PPG2000 PPG2000
PTMG650
PEG400
(a1 1)/(a1 2) mass ratio 45/55 45/55 0/100 45/55
Polyisocyanates (a2) IPDI IPDI IPDI IPDI
(methyl) acrylic compounds (a3) HEA HEA HEA HEA
(methyl) acryloyl group equivalent (g/eq.) 15000 15000 21000 15000
(methyl) acrylic compounds (B) (B-1) (B-2)
Photoepolymerizationinitiater initiater (B) (C-1) (C-1) (C-1) (C-1)
Organic solvent (D) Ethyl acetate Ethyl acetate Ethyl acetate Ethyl acetate
Ultraviolet hardening bonding film
Storage elastic modelling quantity (Pa) when 30 DEG C 1.4×105 1.8×105 1×104Below 3.3×105
Storage elastic modelling quantity (Pa) when 60 DEG C 5.5×103 8.7×103 1×104Below 2.3×104
Bonding film
Storage elastic modelling quantity (Pa) when 30 DEG C 1.2×106 9.3×106 3.3×104 4.6×105
Storage elastic modelling quantity (Pa) when 100 DEG C 7.6×105 4.1×105 4.1×103 2.3×105
Cutting property T T F T
Wet-heat resisting albefaction T T T F
Difference of height tracing ability A A A A
Visible: the cutting property of bonding film of the present invention of embodiment 1 and 2, wet-heat resisting albefaction and difference of height tracing ability are excellent.
On the other hand, comparative example 1 is the mode not using polycarbonate polyol (a1-1) and (methyl) acrylic compounds (B), and cutting property is bad.
Comparative example 2 is the mode not using (methyl) acrylic compounds (B), and wet-heat resisting albefaction is bad.

Claims (12)

1. a ultraviolet-curing adhesive composition, it is characterized in that, it contains carbamate (methyl) acrylate (A), there is (methyl) acrylic compounds (B) of (methyl) acryloyl group of more than 2, Photoepolymerizationinitiater initiater (C) and organic solvent (D), described carbamate (methyl) acrylate (A) is to make the polyhydric alcohol (a1) containing polycarbonate polyol (a1-1), polyisocyanates (a2) and have NCO or hydroxyl (methyl) acrylic compounds (a3) reaction and obtain.
2. ultraviolet-curing adhesive composition according to claim 1, wherein, described polyhydric alcohol (a1) is possibly together with polyether polyol (a1-2).
3. ultraviolet-curing adhesive composition according to claim 2, wherein, described polycarbonate polyol (a1-1) is the scope of 10/90～90/10 with mass ratio (a1-1)/(a1-2) of shown polyether polyol (a1-2).
4. ultraviolet-curing adhesive composition according to claim 1, wherein, (methyl) acryloyl group equivalent of described carbamate (methyl) acrylate (A) is 1,000～50, the scope of 000g/eq..
5. ultraviolet-curing adhesive composition according to claim 1, wherein, the content of described (methyl) acrylic compounds (B) is relative to the scope that described carbamate (methyl) acrylate (A) 100 mass parts is 1～30 mass parts.
6. ultraviolet-curing adhesive composition according to claim 1, wherein, described (methyl) acrylic compounds (B) is selected from multifunctional (methyl) acrylate of aliphatic and has with more than a kind in multifunctional (methyl) acrylate of multifunctional (methyl) acrylate backbone of isocyanuric acid ester skeleton.
7. a bonding film, it is characterised in that its be the ultraviolet-curing adhesive composition according to any one of claim 1～6 is coated on base material and it is dried, ultraviolet radiation and obtain.
8. bonding film according to claim 7, its storage elastic modelling quantity when 30 DEG C with frequency 1Hz measure time for 1 × 104More than Pa.
9. bonding film according to claim 7, its storage elastic modelling quantity when 100 DEG C with frequency 1Hz measure time for 1 × 104More than Pa.
10. the manufacture method of a bonding film, it is characterized in that, after ultraviolet-curing adhesive composition according to any one of claim 1～6 is coated on base material, organic solvent (C) is dried, obtains ultraviolet hardening bonding film, then, the adhesive layer of this ultraviolet hardening bonding film is attached at base material, afterwards, carry out ultraviolet radiation, thus obtaining bonding film.
11. the manufacture method of bonding film according to claim 10, wherein, the base material of the adhesive layer attaching described ultraviolet hardening bonding film has difference of height.
12. the manufacture method of bonding film according to claim 10, wherein, the described ultraviolet hardening bonding film storage elastic modelling quantity when 60 DEG C with frequency 1Hz measure time for 5 × 104Below Pa.
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