CN103031104A - Resin composition for UV-curable adhesive, adhesive and laminate - Google Patents
Resin composition for UV-curable adhesive, adhesive and laminate Download PDFInfo
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- CN103031104A CN103031104A CN2012102843826A CN201210284382A CN103031104A CN 103031104 A CN103031104 A CN 103031104A CN 2012102843826 A CN2012102843826 A CN 2012102843826A CN 201210284382 A CN201210284382 A CN 201210284382A CN 103031104 A CN103031104 A CN 103031104A
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- tackiness agent
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- resin combination
- ultraviolet hardening
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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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- 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
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Adhesive Tapes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a resin composition for an UV-curable adhesive, an adhesive and a laminate. The problem to be solved by this invention is to provide the resin composition for UV-curable adhesive, which has excellent adhesion strength to a substrate formed by various materials without causing peeling with time and is excellent in moisture and heat resistance without causing decrease of adhesion strength even under hot humid condition. The present invention relates to a resin composition for UV-curable adhesive, which contains urethane (meth)acrylate resin (A) obtained by reacting polyol (a), polyisocyanate (b) with hydroxyl-containing (meth)acrylic acid-based compound, (meth)acrylic acid-based monomer (B) and photopolymerization initiator (C) and is characterized in that the polyol (a) is a polycarbonate polyol, the (meth)acrylic acid-based monomer (B) is a mixture of more than two kinds of (meth)acrylic acid-based monomers. Furthermore, the more than two kinds of (meth) acrylic acid-based monomers can form a copolymer having a glass transition temperature below 15[deg.C].
Description
Technical field
The present invention relates to ultraviolet hardening tackiness agent resin combination, tackiness agent and the multilayer body of clinging power excellence.
Background technology
In the optical correlation goods of representative, follow its multifunction take touch panel, liquid-crystal display, majority has used the material with various kinds, the optics of shape.
During the applying of optics as described above, used tackiness agent, thereby industrial community requires not rely on the material of part and tackiness agent with excellent clinging power all the time.
In addition, in the manufacturing occasion of above-mentioned optical correlation goods, in recent years, the productivity of end article improves becomes large problem.Because the tackiness agent that uses comprises the solvents such as solvent, water usually all the time, therefore after this tackiness agent being coated on substrate surface etc., the operation of removing solvent contained in this tackiness agent needs the plenty of time, becomes a reason of the production efficiency reduction that makes end article.
As the tackiness agent of the production efficiency that can improve said products, known ultraviolet hardening tackiness agent.Above-mentioned ultraviolet hardening tackiness agent has following characteristics usually: owing to do not contain the solvents such as solvent, water, so when forming adhering agent layer, the operation that does not need to remove these solvents.
As clinging power and the tackiness agent that can improve the production efficiency of end article compared with the past with the level that in the manufacturing of said products etc., can use, known a kind of adhesion agent composition for example, it is characterized in that, with respect to 100 parts of the monomers with unsaturated double-bond, comprise following the having amino-formate bond and be that high molecular body more than 20,000 is (for example, with reference to patent documentation 1 in the weight-average molecular weight that polymer ends has a unsaturated double-bond of above 200 mass parts of 5 mass parts.)。
Yet above-mentioned adhesion agent composition can not show practical sufficient clinging power sometimes according to the difference such as the material of base material, in the situation about particularly using under wet heat condition, has the significantly reduced problem of clinging power.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-104296 communique
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is, though provide for the base material that is consisted of by various materials have do not cause through the time level peeled off excellence clinging power and have the ultraviolet hardening tackiness agent resin combination of the humidity resistance of the excellence that clinging power does not also reduce in situation about using under the wet heat condition.
Be used for solving the means of problem
In the process that the inventor etc. further investigate in order to solve above-mentioned problem, be conceived to the combination of carbamate (methyl) acrylate resin and (methyl) acrylic monomer, be studied.
It found that, in the situation that the carbamate that will use polycarbonate polyol (methyl) acrylate resin and (methyl) acrylic monomer that can form the multipolymer of specific second-order transition temperature are used in combination, can obtain the tackiness agent of clinging power and humidity resistance excellence.
Namely, the invention provides ultraviolet hardening tackiness agent resin combination, tackiness agent and multilayer body, described ultraviolet hardening tackiness agent is characterised in that with resin combination, comprises: make polyvalent alcohol (a), polyisocyanates (b) and have (methyl) acrylic acid series compound (c) reaction of hydroxyl and carbamate (methyl) acrylate resin (A) that obtains; (methyl) acrylic monomer (B); And Photoepolymerizationinitiater initiater (C), above-mentioned polyvalent alcohol (a) is polycarbonate polyol, above-mentioned (methyl) acrylic monomer (B) is the mixture of (methyl) acrylic monomer more than 2 kinds, and, this more than 2 kinds (methyl) acrylic monomer can form the multipolymer of second-order transition temperature below 15 ℃.
The effect of invention
The tackiness agent that uses ultraviolet hardening tackiness agent of the present invention to obtain with resin combination possesses excellent clinging power and confining force and humidity resistance.
Can be suitable as the tackiness agent that uses in the optics by ultraviolet hardening tackiness agent of the present invention with the tackiness agent that resin combination forms.Particularly, can be suitable for the manufacturing of touch panel, liquid-crystal display, plasma display, organic EL etc.
Embodiment
At first, describe for the carbamate that uses among the present invention (methyl) acrylate resin (A).
As above-mentioned polyvalent alcohol (a), particularly in order to obtain to possess the tackiness agent of humidity resistance, must use polycarbonate polyol.
As above-mentioned polycarbonate polyol, for example, can use carbonic ether and/or phosgene and the polycarbonate polyol that has compound (a-1) reaction of 2 above active hydrogens and obtain described later.
As above-mentioned carbonic ether, can use such as methyl carbonate, methylcarbonate, ethyl-carbonate, diethyl carbonate, cyclic carbonate ester, diphenyl carbonate etc.
As can with above-mentioned carbonic ether, the compound with 2 above active hydrogens (a-1) of phosgene reaction, for example can use: ethylene glycol, glycol ether, triglycol, Tetraglycol 99,1, the 2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 1, the 4-butyleneglycol, 2, the 3-butyleneglycol, 1,5-PD, 1,5-hexylene glycol, 1, the 6-hexylene glycol, 2, the 5-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1, the 9-nonanediol, 1, the 10-decanediol, 1,11-undecane glycol, 1,12-dodecanediol, the 2-methyl isophthalic acid, ammediol, neopentyl glycol, 2-butyl-2-ethyl-1, ammediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-ethyl-1,3-PD, the 3-methyl isophthalic acid, the 5-pentanediol, 2-ethyl-1, the 3-hexylene glycol, the 2-methyl isophthalic acid, the 8-ethohexadiol, quinhydrones, Resorcinol, dihydroxyphenyl propane, Bisphenol F, 4, the dihydroxy compound of the lower molecular weights such as 4 '-biphenol; 1,2-cyclobutanediol, 1,3-encircles pentanediol, 1, the 4-cyclohexanediol, the ring heptanediol, the ring ethohexadiol, 1,4 cyclohexane dimethanol, the hydroxypropyl hexalin, three rings ［ 5,2,1,0,2,6 ］ decane-dimethanol, two ring ［ 4,3,0 ］-nonanediols, two cyclohexanediols, three rings ［ 5,3,1,1] dodecanediol, two rings ［ 4,3,0 ］ nonane dimethanol, three rings ［ 5,3,1,1 ］ dodecane-di-alcohol, hydroxypropyl three rings ［ 5,3,1,1] dodecanol, spiral shell ［ 3,4 ］ ethohexadiol, the butyl cyclohexanediol, 1,1 '-two cyclohexylene glycol, phloroglucitol, Hydrogenated Bisphenol A, the ester ring type polyvalent alcohols such as 1,3-diamantane glycol; The polyether glycols such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol; The polyester polyols such as poly-hexanodioic acid hexylene glycol ester, poly-succsinic acid hexylene glycol ester, polycaprolactone etc.
As the hydroxyl value of above-mentioned polycarbonate polyol, consider from viewpoints such as clinging powers, be preferably 30～230mgKOH/g, more preferably 50～230mgKOH/g.In addition, the hydroxyl value of above-mentioned polycarbonate polyol represent according to JIS K0070 measure and value.
In addition, in the present invention, the composition of above-mentioned polycarbonate polyol is unimportant, and ultraviolet hardening tackiness agent of the present invention is very important with containing the carbonic acid ester bond structure in the resin combination.
As the content of ultraviolet hardening tackiness agent of the present invention with the carbonic acid ester bond structure in the resin combination, consider from the viewpoint of humidity resistance, be preferably 4～40 quality %, more preferably 6～32 quality %.
In addition, as above-mentioned polyvalent alcohol (a), as long as in the scope of not damaging effect of the present invention, then can and use polyether glycol, polyester polyol, polyacrylic polyvalent alcohol, polybutadiene polyol etc. with above-mentioned polycarbonate polyol.
As above-mentioned polyisocyanates (b), can be with for example xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, the aromatic diisocyanates such as naphthalene diisocyanate, 1, hexamethylene-diisocyanate, lysinediisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, HMDI, the vulcabond methylcyclohexane, tetramethylxylylene diisocyanate etc. contain that the vulcabond of aliphatics or aliphatics ring type structure etc. uses separately or more than 2 kinds and use.Wherein, the vulcabond that use contains aliphatics ring type structure considers it is preferred from the viewpoint that can have excellent clinging power and confining force concurrently and improve heat-resisting xanthochromia, more preferably use HMDI, isophorone diisocyanate, cyclohexyl diisocyanate, vulcabond methylcyclohexane.
As above-mentioned (methyl) acrylic acid series compound (c) with hydroxyl; use in order in above-mentioned carbamate (methyl) acrylate resin (A), to import (methyl) acryl, this compound have can with the hydroxyl of isocyanic ester radical reaction.
As above-mentioned (methyl) acrylic acid series compound with hydroxyl, for example can use, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, the own ester of vinylformic acid 6-hydroxyl etc. has (methyl) alkyl acrylate of hydroxyl, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate etc. has multifunctional (methyl) acrylate of hydroxyl, polyethylene glycol monoacrylate, polypropylene glycol mono acrylic ester etc.Wherein, consider from the viewpoint that depends on ultraviolet solidified nature, more preferably use the acrylic acid series compound with hydroxyl, easiness, the solidified nature that obtains from raw material and the viewpoint that can give good adhesion physical property are considered, are particularly preferably vinylformic acid 2-hydroxy methacrylate, vinylformic acid 4-hydroxyl butyl ester.
Manufacture method as above-mentioned carbamate (methyl) acrylate resin (A), can enumerate for example following method: under solvent-free condition, after in above-mentioned polyvalent alcohol (a) and above-mentioned (methyl) acrylic acid series compound (c) the adding reaction system, supply with above-mentioned polyisocyanates (b), mix the method that makes it react to make; Under solvent-free condition, make above-mentioned polyvalent alcohol (a) and above-mentioned polyisocyanates (b) reaction obtain the carbamate prepolymer that molecular end has isocyanate group, then, supply with above-mentioned (methyl) acrylic acid series compound (c), mix, make its method of reacting to make etc.Above-mentioned reaction is all being carried out under 20～120 ℃ the condition about roughly 30 minutes～24 hours.
The manufacturing of above-mentioned carbamate (methyl) acrylate resin (A) can be carried out in the presence of organic solvent, water-medium.In addition, can replace organic solvent, water-medium and in the presence of (methyl) described later acrylic monomer (B), make.Wherein, when making multilayer body, do not need to remove organic solvent, water-medium, can simplify manufacturing process, therefore preferably under solvent-free condition, carry out, or the viewpoint consideration of the inhibition of the viscosity from reaction system, preferably in the presence of (methyl) acrylic monomer (B), carry out.
The scope of the total amount of the hydroxyl that the hydroxyl that the reaction of above-mentioned polyalcohol (a) and above-mentioned polyisocyanates (b) and above-mentioned (methyl) acrylic acid series compound (c) has at above-mentioned polyalcohol (a) and above-mentioned (methyl) acrylic acid series compound (c) have and the equivalent ratio ［ total amount of NCO/hydroxyl ］=0.75～1.00 of the NCO that polyisocyanates (b) has is carried out, aspect the molecular weight of carbamate (methyl) acrylate (A) of controlling gained, be preferred, 0.79～0.95 scope more preferably.In addition, although surpass in 1 the situation and can react in above-mentioned equivalent ratio, in this case, preferably so that being purpose, the terminal isocyanate group inactivation of carbamate (methyl) acrylate resin (A) uses the alcohol such as methyl alcohol.In this case, total amount and the above-mentioned polyisocyanate-based equivalent ratio ［ total amount of isocyanate group/hydroxyl ］ of the hydroxyl that has of the hydroxyl that has of preferred above-mentioned polyvalent alcohol (a), hydroxyl that above-mentioned (methyl) acrylic acid series compound (c) has and alcohol are adjusted in the above-mentioned scope.
In addition, as so that the terminal isocyanate group inactivation of above-mentioned carbamate (methyl) acrylate resin (A) is purpose and the alcohol that can use, can use 1 functional alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, 1,2-propylene glycol, 1,3 butylene glycol etc. comprise 2 functional alcohol of primary hydroxyl and secondary hydroxyl etc.
In addition, when making carbamate (methyl) acrylate resin (A), can use as required stopper, urethane catalyzer etc.
As above-mentioned stopper, for example can use, 3,5-dual-tert-butyl-4-hydroxytoluene, quinhydrones, toluhydroquinone, Hydroquinone monomethylether (メ ト キ ノ Application), p-tert-butyl catechol methoxyphenol (パ ラ タ one シ ヤ Le Block チ Le カ テ コ one Le メ ト キ シ Off エ ノ one Le), 2,6-di-tertiary butyl methyl phenol, thiodiphenylamine, tetramethyl-thiuram disulfide, pentanoic, dinitrobenzene etc.
As above-mentioned urethane catalyzer, for example can use the nitrogenous compounds such as triethylamine, triethylenediamine, N-methylmorpholine, the metal-salts such as potassium acetate, Zinic stearas, stannous octoate, the organometallic compounds such as lauric acid two fourth tin etc.
Above-mentioned carbamate (methyl) acrylate resin (A) has (methyl) acryl that carries out radical polymerization by rayed, heating etc.The equivalent weight of above-mentioned (methyl) acryl is 4; 000～9,000 scope considers it is preferred from the viewpoint that can have excellent clinging power and confining force concurrently and can form the adhering agent layer that possesses the good transparency, more preferably 5; 000～8,000.In addition, the equivalent weight of above-mentioned (methyl) acryl represent with the total quality of above-mentioned polyvalent alcohol (a) and polyisocyanates (b) and (methyl) acrylic acid series compound (c) divided by the equivalent of (methyl) acryl that exists in above-mentioned carbamate (methyl) acrylate resin (A) value.In addition; in the present invention; so-called " (methyl) acrylic acid series compound "; refer to a side or two sides of methacrylic acid based compound and acrylic acid series compound, so-called " (methyl) acrylate " refers to a side or two sides of methacrylic ester and acrylate; so-called " (methyl) acryl "; refer to a side or two sides of methacryloyl and acryl, so-called " (methyl) vinylformic acid " refers to methacrylic acid and an acrylic acid side or two sides.
As above-mentioned carbamate (methyl) acrylate resin (A), consider from the viewpoint that can have excellent clinging power and confining force concurrently and can give good coating operability, preferred carbamate (methyl) acrylate resin (A) with weight-average molecular weight of 5,000～50,000 that uses, more preferably have 7,000～25,000 weight-average molecular weight is particularly preferably 10,000～23,000 scope.In addition, the value of the weight-average molecular weight of above-mentioned carbamate (methyl) acrylate resin (A) for using gel permeation chromatography (GPC) to convert and obtain by vinylbenzene.
Next, describe for (methyl) acrylic monomer (B) that uses among the present invention.
Above-mentioned (methyl) acrylic monomer has mixed (methyl) acrylic monomer more than 2 kinds, and, this more than 2 kinds (methyl) acrylic monomer can form the multipolymer of second-order transition temperature (Tg) below 15 ℃.
In addition, so-called above-mentioned second-order transition temperature is that expression makes the each other second-order transition temperature in the situation of copolymerization of (methyl) acrylic monomer all the time, rather than ultraviolet hardening tackiness agent of the present invention is with the second-order transition temperature of resin combination.
In addition, as above-mentioned second-order transition temperature, consider from the viewpoint that can further improve humidity resistance and clinging power, more preferably-50 ℃ below 15 ℃, more preferably-40 ℃ below 10 ℃, more more preferably-35 ℃ below 0 ℃, be particularly preferably more than-35 ℃ below-15 ℃.
In addition, in order to form the multipolymer of second-order transition temperature below 15 ℃, above-mentioned (methyl) acrylic monomer (B) preferably combination use can form second-order transition temperature be the homopolymer below 15 ℃ (methyl) acrylic monomer (x) more than a kind with can form more than a kind of (methyl) acrylic monomer (y) that second-order transition temperature is higher than 15 ℃ homopolymer.
In addition, as above-mentioned (methyl) acrylic monomer (B), can give good clinging power with mass ratio (y) for the scope use of (x)/(y)=90/10～40/60 at above-mentioned (x), be preferred therefore.In addition, 85/15～45/55 scope more preferably, more preferably 80/20～40/60 scope is considered from the viewpoint that can further improve humidity resistance, is particularly preferably 60/40～55/45 scope.
Selected about (methyl) acrylic monomer (B) of forming the multipolymer of above-mentioned second-order transition temperature below 15 ℃, when being used in combination above-mentioned (methyl) acrylic monomer (x) and (methyl) acrylic monomer (y), the Tg of the multipolymer (multipolymer) that is made of n kind monomer uses the formula (1) of Fox shown below and calculates and obtain.
1/Tg＝Σ(Wn/Tgn)(1)
Tg; The calculating Tg (K) of multipolymer (copolymer)
Wn; The weight ratio of monomer n (% by weight)
Tgn; The Tg of the homopolymer of monomer n (K)
The Tg (Tgn) of the homopolymer that uses in the formula of above-mentioned Fox (1) uses Polymer Handbook (4th ed.) and (methyl) acrylic monomer manufacturers homepage record value.
As forming (methyl) acrylic monomer (x) that above-mentioned second-order transition temperature is the homopolymer below 15 ℃, for example can enumerate, methyl acrylate (Tg:10 ℃), ethyl propenoate (24 ℃), propyl acrylate (37 ℃), isopropyl acrylate (6 ℃), butyl acrylate (49 ℃), sec-butyl acrylate (22 ℃), isobutyl acrylate (24 ℃), vinylformic acid 2-ethyl butyl ester (50 ℃), vinylformic acid n-pentyl ester (57 ℃), Ethyl acrylate (57 ℃), 2-EHA (50 ℃), vinylformic acid heptyl ester (60 ℃), Octyl acrylate (65 ℃), vinylformic acid 2-monooctyl ester (45 ℃), vinylformic acid ester in the ninth of the ten Heavenly Stems (58 ℃), vinylformic acid dodecane ester (3 ℃), vinylformic acid 3-methoxyl group butyl ester (56 ℃), vinylformic acid 2-methoxyl group ethyl ester (50 ℃), vinylformic acid 3-methoxyl group propyl ester (75 ℃), vinylformic acid 2-methoxyl group butyl ester (32 ℃), vinylformic acid 3-methyl butyl ester (45 ℃), benzyl acrylate (6 ℃), methacrylic acid pentyl ester (5 ℃), N-Hexyl methacrylate (5 ℃), 2-Ethylhexyl Methacrylate (10 ℃) (more than, reprint the Tg value from Polmer Handbook (4th ed.)), vinylformic acid 2-hydroxy methacrylate (HEA;-15 ℃), vinylformic acid 2-hydroxy propyl ester (HPA;-7 ℃), vinylformic acid 4-hydroxyl butyl ester (4HBA;-32 ℃), Isooctyl acrylate monomer (IOAA;-58 ℃), vinylformic acid Lauryl Ester (LA; 15 ℃), stearyl acrylate base ester (STA;-58 ℃), vinylformic acid tetrahydro furfuryl ester (Viscoat#150;-12 ℃), benzyl acrylate (Viscoat#160; 6 ℃), vinylformic acid ethyl carbitol ester (Viscoat#190;-67 ℃), vinylformic acid phenoxy ethyl (Viscoat#192;-22 ℃) (more than, Osaka organic chemistry industry (strain) system is from reprinting the Tg value with the HP of society), methoxy polyethylene glycol acrylate (9 moles of EO, AM-90G;-71 ℃), phenoxy group polyethylene glycol acrylate (AMP-20GY;-8 ℃) (more than, Xin Zhong village chemical industry (strain) system is from reprinting the Tg value with the HP of society), vinylformic acid isopentyl ester (IAA;-45 ℃), vinylformic acid oxyethyl group-glycol ether ester (EC-A;-70 ℃) (more than, common prosperity society chemistry (strain) system is from reprinting the Tg value with the HP of society) etc., these monomers can be used alone or in combination with two or more kinds.Wherein, preferred methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, vinylformic acid 2-methoxyl group ethyl ester, vinylformic acid 2-hydroxy methacrylate, the vinylformic acid 4-hydroxyl butyl ester of using, particularly using butyl acrylate, 2-EHA owing to can give excellent tackiness, is particularly preferred therefore.
As (methyl) acrylic monomer (y) that can form above-mentioned second-order transition temperature and be higher than 15 ℃ homopolymer, for example can enumerate, vinylformic acid peopentyl ester (22 ℃), cyclohexyl acrylate (19 ℃), aliphatic acrylate (35 ℃), isobornyl acrylate (94 ℃), phenyl acrylate (57 ℃), acrylamide (165 ℃), benzyl methacrylate (54 ℃), methyl methacrylate (105 ℃), β-dimethyl-aminoethylmethacrylate (65 ℃), propyl methacrylate (35 ℃), isopropyl methacrylate (81 ℃), butyl methacrylate (20 ℃), Propenoic acid, 2-methyl, isobutyl ester (53 ℃), the secondary butyl ester (60 ℃) of methacrylic acid, Tert-butyl Methacrylate (118 ℃), cyclohexyl methacrylate (83 ℃), 2-hydroxyethyl methacrylate (85 ℃), isobornyl methacrylate (110 ℃) (more than, reprint the Tg value from Polmer Handbook (4th ed.)), tert-butyl acrylate (TBA; 41 ℃) (more than, Osaka organic chemistry industry (strain) system is from reprinting the Tg value with the HP of society), vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester (M-600A; 17 ℃) (more than, common prosperity society chemistry (strain) system is from reprinting the Tg value with the HP of society), DMAA (DMAA; 119 ℃), acryloyl morpholine (ACMO; 145 ℃), dimethylaminopropyl acrylamide (DMAPAA; 134 ℃), N-isopropylacrylamide (NIPAM; 134 ℃), diethyl acrylamide (DEAA; 81 ℃), hydroxyethyl acrylamide (HEAA; 98 ℃) (more than, (strain) emerging people's system is from reprinting the Tg value with the HP of society) etc., these monomers can be used alone or in combination with two or more kinds.Wherein, using cyclohexyl acrylate, isobornyl acrylate, acryloyl morpholine owing to can have excellent bonding force and confining force concurrently, is particularly preferred therefore.
In addition, as above-mentioned (methyl) acrylic monomer (B) that uses in the present invention, as long as be the scope that scope below 15 ℃ designed and do not damage effect of the present invention at the calculating Tg that makes the multipolymer that is formed by them, then can also use except above-mentioned (x) with (y) other vinyl monomer.
Usage quantity as above-mentioned (methyl) acrylic monomer (B), consider from the viewpoint that can have excellent clinging power and confining force concurrently, with respect to above-mentioned carbamate (methyl) acrylate resin (A) 100 mass parts, preferably use in the scope of 30～200 mass parts, the scope of 40～150 mass parts more preferably is particularly preferably the scope of 50～130 mass parts.
Next, describe for the Photoepolymerizationinitiater initiater that uses among the present invention (C).
Above-mentioned Photoepolymerizationinitiater initiater (C) produces free radical by rayed, heating etc., causes the radical polymerization of above-mentioned carbamate (methyl) acrylate resin (A), above-mentioned (methyl) acrylic monomer (B).
As above-mentioned Photoepolymerizationinitiater initiater, for example can use, 4-phenoxy group dichloroacetophenone, 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-(methylthio group) phenyl ］-2-morpholino-1-acetone, 2, the 2-dimethoxy-acetophenones such as 2-phenyl methyl phenyl ketone; The bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, bitter almond oil camphor diisopropyl ether, benzoin iso-propylether, bitter almond oil camphor ethyl isobutyl ether; Benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl esters, 4-phenyl benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 '-methyldiphenyl thioether, 3, the 3 '-dimethyl-benzophenones such as 4-methoxy benzophenone; Thioxanthone, CTX, 2,4-two clopenthixal ketones, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2, the thioxanthene ketones such as 4-di-isopropyl thioxanthone; 4,4 '-dimethylamino thioxanthone (another name=ミ ネ ラ one ズ ケ ト Application), 4, the Anthraquinones such as 4 '-diethylamino benzophenone, α-acyl group oxime ester, benzil (ベ Application ジ Le), toluyl manthanoate (" Vicure 55 "), 2-ethyl-anthraquinone; The acylphosphine oxide classes such as 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide (" Lucirin TPO "), two (2,4,6-Three methyl Benzene formyl)-phenyl phosphine oxides (" IRGACURE819 "); 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone ［ " BTTB " of Japanese grease (strain) system ］, acrylated benzophenone etc.
As above-mentioned Photoepolymerizationinitiater initiater, from can have excellent clinging power and confining force concurrently and can prevent adhering agent layer through the time variable color, can improve with the present invention the consistency, the viewpoint consideration of solidified nature of specific (methyl) acrylic monomer of using, preferred 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the 1-hydroxycyclohexylphenylketone, 2 of using, 4,6-Three methyl Benzene formyl diphenyl phosphine oxide, two (2,4,6-Three methyl Benzene formyl)-phenyl phosphine oxide.
The usage quantity of above-mentioned Photoepolymerizationinitiater initiater (C) is preferably used in the scope of 0.1～20 mass parts, more preferably the scope of 0.5～15 mass parts with respect to above-mentioned carbamate (methyl) acrylate resin (A) 100 mass parts.
In addition, in the situation that the tackiness agent that uses ultraviolet hardening tackiness agent of the present invention to obtain with resin combination uses in optics, in ultraviolet hardening adhesion agent composition of the present invention, further contain fast light stablizer (D) and consider it is preferred from the viewpoint that can improve light fastness stability.
The fast light stablizer of above-mentioned what is called (D) is to catch deteriorated by light and the material free radical that produces for example can use the radical scavengers such as mercaptan system, thioether system, hindered amine based compound; And UV light absorber such as benzophenone series, benzoic ether based compound etc., these fast light stablizers can use separately or more than 2 kinds and use.Wherein, from keep have excellent clinging power and confining force concurrently and can further improve with the present invention the consistency of specific (methyl) acrylic monomer of using and the viewpoint consideration of light fastness stability, preferably use the hindered amine based compound.
As above-mentioned hindered amine based compound, for example can use, hexanaphthene and peroxidation N-butyl 2,2,6,6-tetramethyl--4-piperylhydrazine-2,4,6-trichlorine 1,3, the reaction product of 5-triazine and 2-monoethanolamine reaction product (trade(brand)name: Tinuvin (registered trademark) 152 (BASF Japan (strain) system)), sebacic acid two (2,2,6,6-tetramethyl--1-(octyl group oxygen base)-4-piperidyl) ester (trade(brand)name: Tinuvin (registered trademark) 123 (BASF (strain) system)), 1, the reaction product of 1-dimethyl ethyl hydroperoxide and octane etc. has the hindered amine compound of amino ether, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl--4-piperidyl) tetramethyleneimine-2, the N-acetyl such as 5-diketone (trade(brand)name: Hostavin (registered trademark) 3058 (Clariant Japan (strain) system)) are hindered amine compound, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate (trade(brand)name: Sanol LS765 (BASF Japan (strain) system)), two (1,2,2,6,6,-pentamethyl--4-piperidyl) { ［ 3,5-two (1, the 1-dimethyl ethyl)-and the 4-hydroxy phenyl ］ methyl } butyl malonic acid ester (trade(brand)name: Tinuvin (registered trademark) 144 (BASF Japan (strain) system)), Succinic acid dimethylester and 4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidines ethanol (trade(brand)name: Tinuvin (registered trademark) 622LD (BASF Japan (strain) system)), propanedioic acid ［ { 4-p-methoxy-phenyl } methylene radical ］-two (1,2,2,6,6-pentamethyl--4-piperidyl) the N-alkyl of ester (trade(brand)name: Hostavin (registered trademark) PR-31 (Clariant Japan (strain) system)) is hindered amine compound etc.Wherein, from have excellent clinging power and confining force concurrently and keep humidity resistance and can further improve with the present invention the consistency of specific (methyl) acrylic monomer of using and the viewpoint of light fastness stability consider that particularly preferably use has the hindered amine compound of amino ether.
The usage quantity of above-mentioned fast light stablizer (D) uses from the viewpoint of the heat-resisting xanthochromia that can give the tackiness agent tunicle to consider it is preferred with respect to above-mentioned carbamate (methyl) acrylate resin (A) 100 mass parts in the scope of 0.01～10 mass parts, more preferably the scope of 0.1～5 mass parts.
In addition, in the situation that the tackiness agent that is formed with resin combination by ultraviolet hardening tackiness agent of the present invention uses in optics, in ultraviolet hardening adhesion agent composition of the present invention, further contain antioxidant (E) and consider it is preferred from the viewpoint that can improve heat-resisting xanthochromia.
Above-mentioned so-called antioxidant (E), can enumerate the hindered phenol based compound (secondary antioxidant) of catching the free radical that is produced by thermal degradation when and the phosphorus system that decomposes the superoxide that is produced by thermal degradation when, chalcogenide compound (secondary antioxidant) etc., these antioxidants can use separately or and use.
As above-mentioned hindered phenol based compound, for example can use, triglycol-two-［ 3-(the 3-tertiary butyl-5-methyl-4 hydroxy phenyl) propionic ester ］ (trade(brand)name: IRGANOX (registered trademark) 245 (BASFJapan (strain) system)), ［ 3-(3 for tetramethylolmethane four, 5-two-tert-butyl-hydroxy phenyl) propionic ester (trade(brand)name: IRGANOX (registered trademark) 1010 (BASF Japan (strain) system)), ［ 3-(3 for octadecyl, 5-two-tert-butyl-hydroxy phenyl) propionic ester (trade(brand)name: IRGANOX (registered trademark) 1076 (BASFJapan (strain) system)), ［ 3-(3 for the sulfo-di ethylene bis, 5-two-tert-butyl-hydroxy phenyl) propionic ester ］ (trade(brand)name: IRGANOX (registered trademark) 1035 (BASF Japan (strain) system), phenylpropionic acid-3, two (1,1-the dimethyl ethyl)-4-hydroxyl-C of 5-
7-C
9Side chain alkyl ester (trade(brand)name: IRGANOX (registered trademark) 1135 (BASF Japan (strain) system)), 4, two (dodecyl thiomethyl) ortho-cresol (trade(brand)name: the IRGANOX (registered trademark) 1726 (BASF Japan (strain) system) of 6-, N-phenylaniline and 2,4, the reaction product of 4-2,4,4-Trimethyl-1-pentene (trade(brand)name: IRGANOX (registered trademark) 5057 (BASF Japan (strain) system)), the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate (trade(brand)name: Sumilizer (registered trademark) GM (Sumitomo Chemical (strain) system)), 3, two ［ the 2-(3-(tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1 of 9-, the 1-dimethyl ethyl ］ 2,4,8,10-four oxaspiros (55) undecane (trade(brand)name: Sumilizer (registered trademark) GA-80 (Sumitomo Chemical (strain) system)), 2,6-two-tert-butyl-4-methyl-Phenol (trade(brand)name: Nocrac 200 (the emerging chemical industry of imperial palace (strain) system)), 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) (trade(brand)name: Nocrac NS-6 (the emerging chemical industry of imperial palace (strain) system)), 2,5-, two-amyl hydroquinone (trade(brand)name: Nocrac DAH (the emerging chemical industry of imperial palace (strain) system) etc.
As above-mentioned phosphorus series compound, for example can use, triphenylphosphine, two ［ 2,4-two (1, the 1-dimethyl ethyl)-and the 6-aminomethyl phenyl ］ ethide phosphite ester, the triphenyl phosphorous acid ester, trisnonylphenyl phosphite, three (2,4-dibutyl phenyl) phosphorous acid ester, three (2,4-dibutyl-5-aminomethyl phenyl) phosphorous acid ester, three (the 2-tertiary butyl-4-(3-butyl-4-hydroxy-5-methyl base thiophenyl)-5-aminomethyl phenyl) phosphorous acid ester, the tridecyl phosphorous acid ester, octyl group phenylbenzene phosphorous acid ester, the single phenyl phosphites of two (decyls), two (tridecyl) pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, two (2,4-dibutyl phenyl) pentaerythritol diphosphites, two (2,6-dibutyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4,6-tributyl phenyl) pentaerythritol diphosphites, two (2, the 4-dicumylphenyl) pentaerythritol diphosphites, four (tridecyl) isopropylidene xenol diphosphites, four (tridecyl)-4, two (2-butyl-5-methylphenol) diphosphites of 4 '-positive butylidene, six (tridecyl)-1,1,3-three (2-methyl-4-hydroxyl-5-butyl phenyl) butane GW-540, four (2,4-dibutyl phenyl) biphenylene two phosphinates, 9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2,2 '-methylene-bis (4, the 6-butyl phenyl)-2-ethylhexyl phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-butyl phenyl)-the octadecyl phosphorous acid ester, 2,2 '-ethylenebis (4,6-dibutyl phenyl) fluorophosphites, three (2-((2,4,8,10-tetrabutyl dibenzo (d, f) (1,3,2) two
Phosphorus suberane-6-yl) oxygen base) ethyl) phosphorous acid ester of amine, 2-ethyl-2-butyl propylene glycol and 2,4,6-tributyl phenol etc.
As above-mentioned chalcogenide compound, for example can use, two dodecyls-3,3 '-thiopropionate, dilauryl-3,3 '-thiodipropionate, dilauryl sulfo-dithionite, double tridecyl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate, four-methylene radical-3-lauryl thiopropionate methane, distearyl-3,3 '-methyl-3,3 '-thiodipropionate, lauryl stearyl-3,3 '-thiodipropionate, two ［ 2-methyl-4-(3-alkyl sulfo-propionyloxy)-5-tert-butyl-phenyl ］ sulfide, β-lauryl thiopropionate, 2-mercaptobenzimidazole, 2-sulfydryl-5-tolimidazole, two octadecyls-3,3 '-thiodipropionate etc.
Wherein, from have excellent clinging power and confining force concurrently and keep humidity resistance and can further improve with the present invention the consistency of specific (methyl) acrylic monomer of using and the viewpoint consideration of heat-resisting xanthochromia, the preferred phosphorus series compound that uses, particularly preferably use triphenylphosphine, two ［ 2,4-two (1, the 1-dimethyl ethyl)-and the 6-aminomethyl phenyl ］ ethide phosphite ester, tetramethylolmethane four ［ 3-(3,5-, two-tert-butyl-hydroxy phenyl) propionic ester.
The usage quantity of above-mentioned antioxidant (E) uses from the viewpoint of the good heat-resisting xanthochromia that can give the tackiness agent tunicle to consider it is preferred with respect to above-mentioned carbamate (methyl) acrylate resin (A) 100 mass parts in the scope of 0.01～10 mass parts, more preferably the scope of 0.1～5 mass parts.
In addition, the tackiness agent that is formed with resin combination by ultraviolet hardening tackiness agent of the present invention in the situation that optics particularly uses in the manufacturing of touch panel, from prevent as the electrically conducting transparent material indium tin oxide (below, referred to as ITO.) the viewpoint of metallic corrosion (rust-preventing characteristic) consider, preferably in ultraviolet hardening adhesion agent composition of the present invention, further contain rust-preventive agent (F).
As above-mentioned rust-preventive agent (F), for example can use, three azole compounds, organic carboxyl acid amine salt, nitrous acid amine salt, phosphate amine salt, amine carbonate, heterocyclic amine etc., these rust-preventive agent can use separately or and use.From having excellent clinging power and confining force concurrently and keeping humidity resistance and can not damage the consistency of specific (methyl) acrylic monomer that uses light fastness stability, heat-resisting xanthochromia, further raising and the present invention and the viewpoint consideration of rust-preventing characteristic, preferably use three azole compounds.
As above-mentioned three azole compounds, for example can use, 1-(two (2-ethylhexyl) amino methyl) benzotriazole, Methylbenzotriazole, dimethylbiphenyl triazole, ethyl benzotriazole, ethyl-methyl benzotriazole, diethyl benzo triazole, unsubstituting phenenyl and triazole, 5-methyl isophthalic acid H-benzotriazole, N, the triazole compounds shown in two (2-ethylhexyl)-(4 or the 5)-methyl isophthalic acid H-benzotriazoles of N--1-methylamine, the following general formula (1) etc.
(in the formula, R1 and R2 represent alkyl, the alkenyl of carbonatoms 3～20, the cycloalkyl of carbonatoms 5～12, the aralkyl of carbonatoms 7～13, the aryl of carbonatoms 6～10, the hydroxyl of hydrogen atom, carbonatoms 1～20 independently of one another.)
Triazole compounds as shown in the above-mentioned general formula (1) can be fit to use N, two (2-ethylhexyl)-［ (1,2, the 4-triazol-1-yl) methyl ］ amine of N-etc.
As above-mentioned three azole compounds, can use " IRGAMET (registered trademark) 30 ", the commercially available products such as " IRGAMET (registered trademark) 38S " (more than, BASF Japan (strain) system).
The usage quantity of above-mentioned rust-preventive agent (F) uses the viewpoint that never makes the reduction of adhesion physical property and can give good rust-preventing characteristic to consider it is preferred with respect to above-mentioned carbamate (methyl) acrylate resin (A) 100 mass parts in the scope of 0.001～5 mass parts, more preferably the scope of 0.01～2 mass parts.
Next, describe with resin combination for ultraviolet hardening tackiness agent of the present invention.
Ultraviolet hardening tackiness agent of the present invention can be made by following method with resin combination: for example, after separately making carbamate (methyl) acrylate resin (A), will (methyl) acrylic monomer (B), fast light stablizer (D), antioxidant (E), the rust-preventive agent (F) of Photoepolymerizationinitiater initiater (C) and necessity method of mixing; Perhaps, (methyl) acrylic monomer (B) part or all in the presence of, make carbamate (methyl) acrylate resin (A), with methods such as fast light stablizer (D), antioxidant (E), the rust-preventive agent (F) of polymerization starter (C) and necessity mix.
The ultraviolet hardening tackiness agent that is obtained by aforesaid method is not particularly limited with resin combination, but from good coating and the good viewpoint of operation of the tackiness agent solution when applying consider, be preferably 500～20,000mPas, be preferably 1,000～10,000mPas.In addition, above-mentioned viscosity table is shown in 25 ℃ of values of utilizing Brookfield viscometer to measure and obtain.
In addition, except above-mentioned substance, can also contain other additive in the ultraviolet hardening tackiness agent usefulness resin combination of the present invention.
As above-mentioned other additive, for example can use the thixotroping imparting agent, sensitizing agent, gravity alloy material, solidifying agent, curing catalyst, flow agent, tackifier, wax, thermo-stabilizer, white dyes, whipping agent, thermoplastic resin, thermosetting resin, organic solvent, conductive agent, static inhibitor, the water vapour permeability improving agent, water repllents, the hollow foam, the compound that contains crystal water, fire retardant, water-retaining agent, moisture adsorbent, reodorant, suds-stabilizing agent, defoamer, mould inhibitor, sanitas, algaecide, anti-hard caking agent, the hydrolysis preventing agent, organic and inorganic water-soluble compound etc.
As above-mentioned sensitizing agent, for example can use, biphenyl, Isosorbide-5-Nitrae-dimethylnaphthalene, 9-Fluorenone, fluorenes, phenanthrene, benzo [9,10] phenanthrene, anthracene, 9,10-diphenylanthrancene, 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dipropoxy anthracene, 9,10-dibutoxy anthracene, benzophenone, 4,4 '-dimethoxy-benzophenone, methyl phenyl ketone, 4-methoxyacetophenone, phenyl aldehyde etc.
As above-mentioned solidifying agent, can use the zoarium that adds to be derived by tolylene diisocyanate, hexamethylene diisocyanate etc., and tripolymer (ㄡ レ one ト body) etc. is the polyisocyanate compound of representative, the multi-functional epoxy compound, melamine compound, metallo-chelate etc.
In addition, ultraviolet hardening tackiness agent of the present invention can be with above-mentioned carbamate (methyl) acrylate resin (A) with resin combination, above-mentioned (methyl) acrylic monomer (B), dissolvings such as above-mentioned Photoepolymerizationinitiater initiater (C) and above-mentioned other additive or be dispersed in organic solvent, form in the solvents such as water-medium, but dissolving or disperse above-mentioned carbamate (methyl) acrylate resin (A) in above-mentioned (methyl) acrylic monomer (B), when above-mentioned Photoepolymerizationinitiater initiaters (C) etc. are made multilayer body at the applying base material, do not need to remove the operation of solvent contained in the tackiness agent, can improve the production efficiency of above-mentioned multilayer body, be preferred therefore.
Ultraviolet hardening tackiness agent of the present invention can make by the irradiation of ultraviolet homenergic ray to solidify with resin combination and carry out.
As the method that ultraviolet hardening tackiness agent of the present invention is solidified with resin combination, for example, can be cured by the ultraviolet ray of shining regulation with known ultraviolet illumination injection devices such as xenon lamp, xenon-mercuryvapour lamp, metal halide lamp, high pressure mercury vapour lamp, Cooper-Hewitt lamps.
Preferably, above-mentioned ultraviolet irradiation is preferably 0.05～5J/cm
2, 0.1～3J/cm more preferably
2, be particularly preferably 0.3～1.5J/cm
2Scope.In addition, the value that obtains in the wavelength region may mensuration of 300～390nm to use UV Checker UVR-N1 (GS yuasa (strain) system) of ultraviolet irradiation amount is as benchmark.
In addition, contain with resin combination in the situation of above-mentioned other additive at ultraviolet hardening tackiness agent of the present invention, as required can be by further promoting to solidify about 40～80 ℃, heating behind the above-mentioned ultraviolet irradiation.
Therefore the tackiness agent that is formed with resin combination by ultraviolet hardening tackiness agent of the present invention can be suitable as the tackiness agent that uses owing to have excellent clinging power and confining force concurrently in optics.Particularly, can be suitable for the manufacturing of touch panel, liquid-crystal display, plasma display, OLED display etc.
As the use form that is fit to of the tackiness agent that is formed with resin combination by ultraviolet hardening tackiness agent of the present invention, for example can enumerate:
In touch panel, make plastic basis material, flexible printing base material, glass baseplate or evaporation has the Graphene as the electrically conducting transparent material, the base material of ITO etc. to fit on these base materials tackiness agent;
In liquid-crystal display, the tackiness agent that the transparent substrate that is made of glass, plastics etc. and the outermost polarization plates that consists of liquid crystal panel are fitted;
In liquid-crystal display, the tackiness agent that uses in the space that is called as air gap that between the transparency protected base material that is consisted of by glass, plastics etc. and liquid crystal panel, arranges.
The tackiness agent that is formed with resin combination by ultraviolet hardening tackiness agent of the present invention is in above-mentioned touch panel, as making plastic basis material, the flexible printing base material, glass baseplate or on these base materials evaporation Graphene as the electrically conducting transparent material is arranged, the tackiness agent of the applyings such as the base material of ITO and in the situation about using, adopt following form: using the tackiness agent that is formed with resin combination by ultraviolet hardening tackiness agent of the present invention on the two sides of the adhesive coating that forms at least lamination by being selected from by plastic basis material, the flexible printing base material, glass baseplate and the substrate layer that evaporation has the base material in the group that the base material of ITO (indium tin oxide) forms to form on these base materials.
Here, above-mentioned layer (i) can be used by ultraviolet hardening tackiness agent of the present invention and form with the tackiness agent that resin combination forms, although its thickness is according to the use field of touch panel etc. and different, but be preferably the roughly thickness of 10～500 μ m because of the slimming of liquid-crystal display, more preferably the thickness of 50～500 μ m.
Above-mentioned layer (ii) can be formed by the a kind of base material that is selected from by in plastic basis material, flexible printing base material, glass baseplate and evaporation is comprised of the base material of ITO on these base materials the group, at the same or different base material of the two sides of above-mentioned layer (i) use.
As above-mentioned plastic basis material, can use the film of nesa coating of the base material, PC (polycarbonate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), MODIFIED PP E (polyphenylene oxide), PET (polyethylene terephthalate), COP (cyclic olefin polymer), TAC (triacetyl cellulose), antireflection film or sheet, anti-soil film or the sheet that are formed by acrylic resin etc., formation touch panel of normal operation or sheet etc.
As the method for making above-mentioned multilayer body, for example, at the surface coating ultraviolet hardening tackiness agent resin combination of the present invention that is selected from by the base material in the plastic basis material that forms above-mentioned substrate layer, flexible printing base material, glass baseplate or evaporation is comprised of the base material of ITO on these base materials the group, after carrying out above-mentioned ultraviolet irradiation, immediately at of the same race or other the above-mentioned base material of this coated face mounting, after the placement, can obtain multilayer body of the present invention.In addition, be in the situation of photopermeability at above-mentioned base material, at the surface of above-mentioned base material coating ultraviolet hardening tackiness agent resin combination of the present invention, after this coated face loads of the same race or other above-mentioned base material, carry out above-mentioned ultraviolet irradiation from above-mentioned base material, thereby can obtain multilayer body of the present invention.
In addition, contain with resin combination in the situation of above-mentioned other additive at ultraviolet hardening tackiness agent of the present invention, can after carrying out above-mentioned ultraviolet irradiation as required, about 40～80 ℃, heat as required.
Embodiment
Below, be described more specifically the present invention by embodiment, but scope of the present invention is not only limited to these embodiment.
In addition, among the present invention, as long as no specializing, " part " is " mass parts ", and " % " is " quality % ".
［ synthesis example 1 ］
＜carbamate (methyl) acrylate resin (A-1) synthetic＞
In the reaction vessel that possesses stirrer, reflux cooling pipe, nitrogen ingress pipe, thermometer, add polycarbonate polyol (" ETERNACOLL UH-100; the emerging product of space section (strain) system; hydroxyl value 112mgKOH/g ") 456.4 mass parts, vinylformic acid 2-hydroxy methacrylate 11.0 mass parts, 2,6-two-tertiary butyl-cresols 1.7 mass parts, p methoxy phenol 0.3 mass parts.Intensification is added isophorone diisocyanate 100.0 mass parts after making the interior temperature of reaction vessel reach 40 ℃.Add therein two neodecanoic acid dioctyl tins, 0.06 mass parts, be warming up to 80 ℃ through 1 hour.Then, kept 12 hours at 80 ℃, confirms that whole isocyanate group disappears after, cooling is as (A-1) and the acquisition urethane acrylate resin.The equivalent weight of the acryl of the urethane acrylate resin of gained (A-1) is 6,000, and weight-average molecular weight is 17,000.
［ comparing synthesis example 1 ］
Synthetic (A-2) of＜carbamate (methyl) acrylate resin＞
In the reaction vessel that possesses stirrer, reflux cooling pipe, nitrogen ingress pipe, thermometer, add polytetramethylene glycol (weight-average molecular weight 1000) 164.3 mass parts, 1,4-butyleneglycol 28.6 mass parts, vinylformic acid 2-hydroxy methacrylate 4.9 mass parts, 2,6-two-tertiary butyl-cresols 1.7 mass parts, p methoxy phenol 0.3 mass parts.Intensification is added isophorone diisocyanate 101.6 mass parts after making the interior temperature of reaction vessel reach 40 ℃.Add therein two neodecanoic acid dioctyl tins, 0.06 mass parts, be warming up to 80 ℃ through 1 hour.Then, kept 12 hours at 80 ℃, confirms that whole isocyanate group disappears after, cooling is as (A-2) and the acquisition urethane acrylate resin.The equivalent weight of the acryl of the urethane acrylate resin of gained (A-2) is 7,000, and weight-average molecular weight is 12,000.
The adjustment of＜ultraviolet hardening tackiness agent usefulness resin combination＞
80 ℃ of interpolations of temperature are stirred until become even by carbamate (methyl) acrylate resin (A-1) 100 mass parts, butyl acrylate 65 mass parts, cyclohexyl acrylate 45 mass parts that synthesis example 1 obtains in container in the container that possesses stirrer, reflux cooling pipe, thermometer.Then, be cooled to room temperature, under agitation add successively 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide 3 mass parts, sebacic acid two (2,2,6,6-tetramethyl--1-(octyl group oxygen base)-4-piperidyl) ester (" Tinuvin (registered trademark) 123 ", BASF Japan (strain) system) 1 mass parts, two (2-ethylhexyl) aminomethyl-1,2s of triphenylphosphine 1 mass parts and 1-, 2,4-triazole (" IRGAMET (registered trademark) 30 ", BASF Japan (strain) system) 0.1 mass parts stirs until become even.Then, by 200 order metal mesh filters, obtain ultraviolet hardening tackiness agent resin combination.
［ embodiment 2～6, comparative example 1 ］
Beyond the kind of employed (methyl) acrylic monomer and usage quantity changed, obtain similarly to Example 1 ultraviolet hardening tackiness agent resin combination shown in table 1～2.
［ comparative example 2 ］
80 ℃ of interpolations of temperature are stirred until become even by carbamate (methyl) acrylate resin (A-2) 100 mass parts, butyl acrylate 45 mass parts, cyclohexyl acrylate 45 mass parts of relatively synthesis example 1 acquisition in container in the container that possesses stirrer, reflux cooling pipe, thermometer.Then, be cooled to room temperature, under agitation add successively 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide 3 mass parts, sebacic acid two (2,2,6,6-tetramethyl--1-(octyl group oxygen base)-4-piperidyl) ester (" Tinuvin (registered trademark) 123 ", BASF Japan (strain) system) 1 mass parts, two (2-ethylhexyl) aminomethyl-1,2s of triphenylphosphine 1 mass parts and 1-, 2,4-triazole (" IRGAMET (registered trademark) 30 ", BASF Japan (strain) system) 0.1 mass parts stirs until become even.Then, by 200 order metal mesh filters, obtain ultraviolet hardening tackiness agent resin combination.
［ measuring method of weight-average molecular weight ］
The weight-average molecular weight of the polytetramethylene glycol that uses in embodiment and/or the comparative example and carbamate (methyl) acrylate resin is measured under the following conditions by gel permeation chromatography (GPC) method.
Determinator: high speed GPC device (TOSOH Co., Ltd's system " HLC-8220GPC ")
Post: be connected in series the following post of TOSOH Co., Ltd's system and use.
" TSKgel G5000 " (7.8mmI.D. * 30cm) * 1
" TSKgel G4000 " (7.8mmI.D. * 30cm) * 1
" TSKgel G3000 " (7.8mmI.D. * 30cm) * 1
" TSKgel G2000 " (7.8mmI.D. * 30cm) * 1
Detector: RI (differential refractometer)
Column temperature: 40 ℃
Elutriant: tetrahydrofuran (THF) (THF)
Flow velocity: 1.0mL/ minute
Sample size: 100 μ L (tetrahydrofuran solution of sample solution concentration 0.4 quality %)
Standard test specimen: use following polystyrene standard to make typical 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 "
［ making method of adhesive film ］
The mode that becomes 175 μ m with the postradiation thickness of UV on the surface on the surface of the polyethylene terephthalate film (demoulding PET50) of the thickness 50 μ m that the demoulding is processed is coated with the ultraviolet hardening tackiness agent resin combination that is obtained by embodiment and comparative example, at this coated face applying and above-mentioned different demoulding PET50.
Next, come irradiation ultraviolet radiation by the upside from above-mentioned demoulding PET50 with the UV irradiating unit, make 2 demoulding PET50 across adhering agent layer and the adhesive film of lamination one-tenth.The accumulated light of the wavelength 300～390nm of above-mentioned ultraviolet irradiation after seeing through above-mentioned demoulding PET50 becomes 1J/cm
2Condition under carry out.
In addition, the ultraviolet hardening tackiness agent that is obtained by comparative example 1 owing to can not make adhesive film, so can not carry out later evaluation with resin combination.
［ measuring method of clinging power ］
Peel off a side's who consists of above-mentioned adhesive film demoulding PET50, the polyethylene terephthalate (PET75) of coating thickness 75 μ m is made adhesive sheet on this adhering agent layer surface.Above-mentioned adhesive sheet is cut into the width of 25mm, the test film that uses in the mensuration as clinging power.
To peel off test film behind the opposing party's the demoulding PET50 from above-mentioned test film, (surface finishing BA is (after cold rolling at the SUS304 stainless steel plate, bright heat treatment)), polycarbonate (PC) plate, PET plate are (with PET film (" Lumirror T60 ", east beautiful (strain) system) form at above-mentioned SUS304 stainless steel plate with sticking double faced adhesive tape), on the sheet glass (JIS R 3202), under 23 ℃, the atmosphere of 50%RH, back and forth stick on each adherend with 2kg roller * 2.Paste after 1 hour under 23 ℃, the atmosphere of 50%RH and measure 180 degree stripping strengths, as clinging power.
［ measuring method of confining force ］
The stainless steel plate of the test film that the method that the test film that uses in the measuring method that adopts with above-mentioned clinging power is same is made after with respect to minute surface precision work carries out lamination in the mode that its bond area becomes 25mm * 25mm, back and forth they fitted by the 2kg roller being carried out 2 under 23 ℃, 50%RH atmosphere.
Next, under 70 ℃ of atmosphere, be the loading that 0 ° of direction (shear direction) applies 1kg with respect to above-mentioned stainless steel plate to the test film that is pasted on above-mentioned stainless steel plate, measure the time till above-mentioned test film comes off from stainless steel plate, should the hold-time as confining force.In addition, even in situation about also keeping after 24 hours, will be made as the hold-time more than 24 hours, measure the offset amplitude of the initial paste position of distance, in the lump record.
［ measuring method of humidity resistance ］
Peel off a side's who consists of the adhesive film that obtains in above-mentioned ［ making method of adhesive film ］ demoulding PET50, the polyethylene terephthalate (PET75) of coating thickness 75 μ m is made adhesive sheet on this adhering agent layer surface.Above-mentioned adhesive sheet is cut into the width of 25mm, as the employed test film of the mensuration of humidity resistance.
In addition, making adherend is sheet glass (JIS R 3202), back and forth sticks on the adherend with 2kg roller * 2.It was placed respectively 250 hours under 60 ℃ * 90%RH and 85 ℃ * 85%RH atmosphere.Then, under the atmosphere of 23 ℃ * 50%RH, measure 180 degree stripping strengths, as damp and hot rear clinging power.
In addition, humidity resistance is by judging with respect to the clinging power of sheet glass and the difference of above-mentioned damp and hot rear clinging power of obtaining in above-mentioned ［ measuring method of clinging power ］.
[table 1]
[table 2]
［ embodiment 7 ］
(manufacturing of multilayer body)
Ultraviolet hardening tackiness agent resin combination for obtaining among the embodiment 1 similarly operates with above-mentioned ［ making method of adhesive film ］, obtains the adhesive film of thickness 175 μ m.Then, peel off a side demoulding PET50 film, fit in polycarbonate membrane.
Then, peel off the opposing party's demoulding PET film, fit in sheet glass, obtain multilayer body.
As can be known, the tackiness agent that uses ultraviolet hardening tackiness agent of the present invention to obtain with resin combination has excellent clinging power, confining force and humidity resistance.
On the other hand, be as (methyl) acrylic monomer in the comparative example 1, use to obtain the mode of (methyl) acrylic monomer that second-order transition temperature is 23 ℃ multipolymer, but can not get tackiness agent.
In addition, comparative example 2 is the mode of having used the urethane acrylate resin of polyether glycol, but humidity resistance is bad.
Claims (14)
1. ultraviolet hardening tackiness agent resin combination, it is characterized in that, contain: make polyvalent alcohol (a), polyisocyanates (b) and have (methyl) acrylic acid series compound (c) reaction of hydroxyl and carbamate (methyl) acrylate resin (A) that obtains; (methyl) acrylic monomer (B); And Photoepolymerizationinitiater initiater (C),
Described polyvalent alcohol (a) is polycarbonate polyol, described (methyl) acrylic monomer (B) is the mixture of (methyl) acrylic monomer more than 2 kinds, and, this more than 2 kinds (methyl) acrylic monomer can form the multipolymer of second-order transition temperature below 15 ℃.
2. ultraviolet hardening tackiness agent resin combination according to claim 1, described (methyl) acrylic monomer (B) for can form second-order transition temperature be the homopolymer below 15 ℃ (methyl) acrylic monomer (x) more than a kind with the mixture more than a kind of (methyl) acrylic monomer (y) that can form second-order transition temperature and be higher than 15 ℃ homopolymer.
3. ultraviolet hardening tackiness agent resin combination according to claim 2, described (methyl) acrylic monomer (x) is the scope of (x)/(y)=90/10～40/60 with the mass ratio of described (methyl) acrylic monomer (y).
4. ultraviolet hardening tackiness agent resin combination according to claim 2, described (methyl) acrylic monomer (B) for be selected from the group that is formed by methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, vinylformic acid 2-methoxyl group ethyl ester, vinylformic acid 2-hydroxy methacrylate and vinylformic acid 4-hydroxyl butyl ester more than a kind with the mixture more than a kind that is selected from the group that is formed by cyclohexyl acrylate, isobornyl acrylate and acryloyl morpholine.
5. the described ultraviolet hardening tackiness agent of according to claim 1～4 each resin combination, the weight-average molecular weight of described carbamate (methyl) acrylate resin (A) are 5,000～50,000 scope.
6. the described ultraviolet hardening tackiness agent of according to claim 1～5 each resin combination, described Photoepolymerizationinitiater initiater (C) is for being selected from by 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide and two (2,4,6-Three methyl Benzene formyl)-in the group that phenyl phosphine oxide forms more than a kind.
7. the described ultraviolet hardening tackiness agent of according to claim 1～6 each resin combination, it further contains fast light stablizer (D).
8. the described ultraviolet hardening tackiness agent of according to claim 1～7 each resin combination, it further contains antioxidant (E).
9. the described ultraviolet hardening tackiness agent of according to claim 1～8 each resin combination, it further contains rust-preventive agent (F).
10. ultraviolet hardening tackiness agent resin combination according to claim 7, described fast light stablizer (D) is the hindered amine based compound.
11. ultraviolet hardening tackiness agent resin combination according to claim 8, described antioxidant (E) is phosphorus series compound.
12. ultraviolet hardening tackiness agent resin combination according to claim 9, described rust-preventive agent (F) is three azole compounds.
13. a tackiness agent is characterized in that, each described ultraviolet hardening tackiness agent of right to use requirement 1～12 obtains with resin combination.
14. multilayer body, it is characterized in that, be right to use require 13 described tackiness agents and on the two sides of the adhesive coating that forms at least lamination be selected from by the base material in plastic basis material, flexible printing base material, glass baseplate and evaporation is comprised of the base material of indium tin oxide on these base materials the group and form.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-171870 | 2011-08-05 | ||
| JP2011171870A JP5834606B2 (en) | 2011-08-05 | 2011-08-05 | UV-curable adhesive resin composition, adhesive and laminate |
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| CN103031104A true CN103031104A (en) | 2013-04-10 |
| CN103031104B CN103031104B (en) | 2016-03-02 |
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| Country | Link |
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| JP (1) | JP5834606B2 (en) |
| KR (1) | KR102004863B1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103031104B (en) | 2016-03-02 |
| KR102004863B1 (en) | 2019-07-29 |
| TW201311846A (en) | 2013-03-16 |
| JP2013035920A (en) | 2013-02-21 |
| JP5834606B2 (en) | 2015-12-24 |
| KR20130016053A (en) | 2013-02-14 |
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