CN102533205B - Resin composition for ultraviolet ray solidifying agglutinant, agglutinant, and laminating body - Google Patents

Resin composition for ultraviolet ray solidifying agglutinant, agglutinant, and laminating body Download PDF

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Publication number
CN102533205B
CN102533205B CN201110439919.7A CN201110439919A CN102533205B CN 102533205 B CN102533205 B CN 102533205B CN 201110439919 A CN201110439919 A CN 201110439919A CN 102533205 B CN102533205 B CN 102533205B
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methyl
tackiness agent
mentioned
ultraviolet hardening
resin combination
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CN102533205A (en
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纲岛启次
小西真理子
大地尉夫
田中浩二郎
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides resin composition for ultraviolet ray solidifying agglutinant, an agglutinant, and a laminating body, with the resin composition having excellent adhesive force and holding power. The resin composition for ultraviolet ray solidifying agglutinant comprises polyurethane (methyl) acrylate resin (A), (methyl) acrylic acid series monomer (B) and optical polymerization initiator (C) obtained by promoting the reaction of polyatomic (a), polyisocyanates (b), and (methyl) acrylic acid series composition (c) containing hydroxyl. The (methyl) acrylic acid series monomer (B) contains (methyl) acrylic acid series monomer (b-1) containing nitrogen, which, with vitrification temperature beyond 50 DEG C, is capable of forming homopolymer, and (methyl) acrylic acid series monomer (b-2) which, with glass transition temperature below minus 20 DEG C, is capable of forming homopolymer. The mass proportion of the (b-1) to (b-2) ranges from 20/80 to 60/40.

Description

Ultraviolet hardening tackiness agent resin combination, tackiness agent and duplexer
Technical field
The present invention relates to clinging power, the ultraviolet hardening tackiness agent resin combination of confining force excellence, tackiness agent and duplexer.
Background technology
In the optical correlation goods being representative with touch-screen, liquid-crystal display, along with multifunction, a large amount of uses have the optics of various material, shape.
When the laminating of optics as described above, use tackiness agent all the time, but the tackiness agent that industrial community requires the material of no matter parts, how shape all has excellent clinging power.
In addition, in the manufacture of above-mentioned optical correlation goods, in recent years, the productivity of end article improves and becomes large problem.This is because, the tackiness agent all the time used comprises solvent, water equal solvent usually, therefore, after this tackiness agent being coated on substrate surface etc., the operation removing solvent contained in this tackiness agent needs for a long time, becomes the reason that the production efficiency of end article is reduced.
As the tackiness agent of production efficiency that can improve said products, known ultraviolet hardening tackiness agent.Above-mentioned ultraviolet hardening tackiness agent, usually not containing the solvent such as solvent, water, therefore has the feature that the operation that not need when forming adhering agent layer to remove these solvents is such.
As there is the clinging power of the level that can use in the manufacture of said products etc. and the tackiness agent that can improve the production efficiency of end article compared with the past, known such as a kind of adhesion agent composition, it is characterized in that, relative to the monomer 100 parts with unsaturated double-bond, comprise below more than 5 mass parts 200 mass parts there is urethane bonds and the high molecular body in polymer ends with the weight-average molecular weight more than 20,000 of unsaturated double-bond (for example, referring to patent documentation 1.)
But, above-mentioned adhesion agent composition can not show practical sufficient clinging power sometimes according to differences such as the materials of base material, in addition, according to material, the shape of base material, cause sometimes through time peel off, base material is relative to the skew of the power of the transverse direction parallel with above-mentioned substrate surface.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-104296 publication
Summary of the invention
Invent problem to be solved
The problem that the present invention will solve be to provide have concurrently to the base material of various material, shape all do not cause through time the clinging power of excellence of level peeled off and the ultraviolet hardening tackiness agent resin combination of confining force.
For solving the method for problem
The present inventor etc. conduct in-depth research to solve above-mentioned problem, are wherein conceived to (methyl) acrylic monomer combinationally used with urethane (methyl) acrylate resin, are studied.
But, when using single (methyl) acrylic acid series composition as (methyl) acrylic monomer, the tackiness agent having clinging power and confining force concurrently can not be obtained.
Therefore, the present inventor etc. are conceived to the control of the cohesive force caused by the second-order transition temperature of (methyl) acrylic monomer, conduct in-depth research.
Found that, (methyl) acrylic monomer that (methyl) acrylic monomer containing nitrogen with specific second-order transition temperature is combinationally used with (methyl) acrylic monomer with specific second-order transition temperature, when combinationally using with urethane (methyl) acrylate resin, can obtain having excellent clinging power and the tackiness agent of confining force concurrently, thus complete the present invention.
Namely, the invention provides a kind of ultraviolet hardening tackiness agent resin combination, it is the ultraviolet hardening tackiness agent resin combination containing urethane (methyl) acrylate resin (A), (methyl) acrylic monomer (B) and Photoepolymerizationinitiater initiater (C), described urethane (methyl) acrylate resin (A) makes polyvalent alcohol (a), polyisocyanates (b) and obtains containing the reaction of hydroxyl (methyl) acrylic compounds (c)
It is characterized in that, described (methyl) acrylic monomer (B) containing second-order transition temperature more than 50 DEG C can be formed homopolymer containing (methyl) acrylic monomer (b-1) of nitrogen and (methyl) acrylic monomer (b-2) that can form homopolymer of second-order transition temperature less than-20 DEG C, the mass ratio of described (b-1) and described (b-2) is (b-1)/(b-2)=20/80 ~ 60/40.
The effect of invention
Ultraviolet hardening tackiness agent resin combination of the present invention is containing urethane (methyl) acrylate resin (A), the ultraviolet hardening tackiness agent resin combination of (methyl) acrylic monomer (B) and Photoepolymerizationinitiater initiater (C), described urethane (methyl) acrylate resin (A) makes polyvalent alcohol (a), polyisocyanates (b) and (methyl) acrylic compounds (c) containing hydroxyl react and obtain, described (methyl) acrylic monomer (B) (methyl) acrylic monomer (b-1) containing nitrogen that can form homopolymer containing second-order transition temperature more than 50 DEG C, with (methyl) acrylic monomer (b-2) that can form homopolymer of second-order transition temperature less than-20 DEG C, above-mentioned (b-1) is (b-1)/(b-2)=20/80 ~ 60/40 with the mass ratio of above-mentioned (b-2), thus can provide and have excellent clinging power and the tackiness agent of confining force concurrently.The tackiness agent comprising ultraviolet hardening tackiness agent resin combination of the present invention can be suitable as the tackiness agent used in optics.Particularly, can be suitable for manufacturing liquid crystal touch screen, liquid-crystal display, plasma display, organic EL etc.
Embodiment
Ultraviolet hardening tackiness agent resin combination of the present invention contains above-mentioned urethane (methyl) acrylate resin (A), above-mentioned (methyl) acrylic monomer (B), above-mentioned Photoepolymerizationinitiater initiater (C) and other additive as required.
Above-mentioned ultraviolet hardening tackiness agent resin combination can be by above-mentioned urethane (methyl) acrylate resin (A), above-mentioned (methyl) acrylic monomer (B), above-mentioned Photoepolymerizationinitiater initiater (C) and additive etc. are dissolved or dispersed in organic solvent, obtain in the solvents such as water-medium, but dissolve in above-mentioned (methyl) acrylic monomer (B) or disperse above-mentioned urethane (methyl) acrylate resin (A), above-mentioned Photoepolymerizationinitiater initiater (C) etc. and the composition obtained, when manufacturing duplexer making base material fit, do not need the operation removing solvent contained in tackiness agent, thus the production efficiency of above-mentioned duplexer can be improved, therefore be preferred.
Next, the urethane used in the present invention (methyl) acrylate resin (A) is described.
Above-mentioned urethane (methyl) acrylate resin (A) makes polyvalent alcohol (a), polyisocyanates (b) and obtains containing the reaction of hydroxyl (methyl) acrylic compounds (c).
Above-mentioned urethane (methyl) acrylate resin (A) has (methyl) acryl being carried out radical polymerization by rayed, heating etc.The equivalent weight of above-mentioned (methyl) acryl is in the scope of 4000 ~ 9000; from having excellent clinging power and confining force concurrently; and it is preferred that the viewpoint that can form the adhering agent layer possessing good transparency is set out, and is more preferably 5000 ~ 8000.In addition, the equivalent weight of above-mentioned (methyl) acryl represents the value total quality of above-mentioned polyvalent alcohol (a), polyisocyanates (b) and (methyl) acrylic compounds (c) containing hydroxyl obtained divided by the equivalent of (methyl) acryl existed in above-mentioned urethane (methyl) acrylate resin (A).
As above-mentioned urethane (methyl) acrylate resin (A), from having excellent clinging power and confining force concurrently, and the viewpoint can giving good coating operability is set out, preferred use has the resin of the weight-average molecular weight of 1000 ~ 50000, more preferably use the resin with the weight-average molecular weight of 10000 ~ 25000, the scope of 12000 ~ 25000 is particularly preferred.In addition, the weight-average molecular weight of above-mentioned urethane (methyl) acrylate resin (A) is the value using gel permeation chromatography (GPC) to be converted by vinylbenzene and obtain.
As above-mentioned polyvalent alcohol (a), have no particular limits, can use polyester polyol, polyether glycol, polycarbonate polyol, polyacrylic polyvalent alcohol etc., these polyvalent alcohols can be used alone or two or more merges use.Wherein, from having excellent clinging power and confining force concurrently, and the viewpoint that can improve the weather resistance of tackiness agent tunicle, particularly hydrolytic resistance is set out, and preferably uses polyether glycol.
As the polyether glycol that can use in above-mentioned polyvalent alcohol (a), can enumerate such as by the one kind or two or more of the oxyalkylenes such as ethylene oxide, propylene oxide, oxybutylene with have more than 2 active hydrogens compound addition polymerization resultant, the polytetramethylene glycol that tetrahydrofuran ring opening polymerization is obtained, make the modification polytetramethylene glycol of tetrahydrofuran (THF) and the copolymerization of alkyl substituted tetrahydro furans, make the modification polytetramethylene glycol of neopentyl glycol and tetrahydrofuran (THF) copolymerization.
As the above-mentioned compound with more than 2 active hydrogens, such as ethylene glycol can be used, glycol ether, triglycol, Tetraglycol 99, 1,2-PD, 1,3-PD, dipropylene glycol, tripropylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butanediol, 1,5-PD, 1,5-hexylene glycol, 1,6-hexylene glycol, 2,5-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane, 1,12-dodecanediol, 2-methyl isophthalic acid, ammediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1,3-hexylene glycol, 2-methyl isophthalic acid, 8-ethohexadiol, glycerine, Glycerol dimer, TriMethylolPropane(TMP), two (trishydroxymethyl) propane, three (trishydroxymethyl) propane, 1,2,6-hexanetriol, trolamine, tri-isopropanolamine, tetramethylolmethane, Dipentaerythritol, Sorbitol Powder, sucrose, quadrol, N-ethyl diethylenetriamine, 1，2-diaminopropane, 1,3-diaminopropanes, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-Diaminobutane, diethylenetriamine, phosphoric acid, phosphate ester acid etc.
In addition, except these compounds, the polyether glycol with alicyclic structure can also be used.
Wherein, from the viewpoint of good adhesion physical property can be given, more preferably use aliphatic poly ethoxylated polyhydric alcohol, particularly preferably use the polytetramethylene glycol obtained by tetrahydrofuran ring opening polymerization.
Other chain extension agent containing active hydrogen can be combinationally used together with the above-mentioned polyester polyol, polyether glycol, polycarbonate polyol, polyacrylic polyvalent alcohol etc. as above-mentioned polyvalent alcohol (a).
The chain extension agent of active hydrogen is contained as above-mentioned other, can be used alone or two or more merge use such as, ethylene glycol, 1, 2-propylene glycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, 3-methyl isophthalic acid, 5-pentanediol, 1, 6-hexylene glycol, 3, 3 '-dihydroxymethyl heptane, 1, 4-cyclohexanedimethanol, neopentyl glycol, 3, two (hydroxymethyl) heptane of 3-, glycol ether, dipropylene glycol, glycerine, TriMethylolPropane(TMP), Sorbitol Powder, the polyvalent alcohols such as hydroquinore dihydroxyethylether, quadrol, propylene diamine, 1, 6-hexanediamine, trimethylhexamethylenediamine, isophorone diamine, 4, 4 '-dicyclohexyl methyl hydride diamines, diamino-cyclohexane, methyl diamino-cyclohexane, the polyamines etc. such as norbornylene diamines (norbornene diamine).
As above-mentioned polyvalent alcohol (a), from the viewpoint of giving good cohesive force and flexibility to adhering agent layer, preferred use has the polyvalent alcohol of the weight-average molecular weight of the scope of 500 ~ 2000, more preferably uses the polyvalent alcohol with the weight-average molecular weight of the scope of 500 ~ 1500.In addition, the weight-average molecular weight of above-mentioned polyvalent alcohol (a) is the value using gel permeation chromatography (GPC) to be converted by vinylbenzene and obtain.
As above-mentioned polyisocyanates (b), to can be used alone or two or more merging uses such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, the aromatic diisocyanates such as naphthalene diisocyanate, hexamethylene diisocyanate, lysinediisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, 4, 4 '-dicyclohexyl methane diisocyanate, cyanato methyl hexanaphthene, tetramethylxylylene diisocyanate etc. contain the vulcabond etc. of aliphatics or aliphatics ring structures.Wherein, from having excellent clinging power and confining force concurrently, and the viewpoint improving heat-resisting xanthochromia is considered, preferred use contains the vulcabond of aliphatics ring structures, more preferably HMDI, isophorone diisocyanate, cyclohexyl diisocyanate, cyanato methyl hexanaphthene is used.
As above-mentioned (methyl) acrylic compounds (c) containing hydroxyl; use to import (methyl) acryl in above-mentioned urethane (methyl) acrylate resin (A), use containing can with the compound of the hydroxyl of isocyanic ester radical reaction.
As above-mentioned (methyl) acrylic compounds containing hydroxyl, can use such as, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) alkyl acrylate containing hydroxyl such as the own ester of vinylformic acid 6-hydroxyl, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, multifunctional (methyl) acrylate containing hydroxyl such as Dipentaerythritol five (methyl) acrylate, polyethylene glycol monoacrylate, polypropylene glycol mono acrylic ester etc.Wherein, the easiness, the solidified nature that obtain from the viewpoint of raw material and can give good adhesion physical property, more preferably use vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 4-hydroxy butyl ester.
As the manufacture method of above-mentioned urethane (methyl) acrylate resin (A), such as following method can be enumerated: in reaction system, add above-mentioned polyvalent alcohol (a) and above-mentioned containing after (methyl) acrylic compounds (c) of hydroxyl under solvent-free, supply above-mentioned polyisocyanates (b), mix, make it react, thus manufacture the method for urethane (methyl) acrylate resin (A); Under solvent-free, make above-mentioned polyvalent alcohol (a) and the reaction of above-mentioned polyisocyanates (b) obtain the polyurethane prepolymer that molecular end has isocyanate group, then above-mentioned (methyl) acrylic compounds (c) containing hydroxyl is supplied, mix, make it react, thus manufacture the method etc. of urethane (methyl) acrylate resin (A).Above-mentioned reaction is all preferred carries out roughly 30 minutes ~ 24 hours under the condition of 20 ~ 120 DEG C.
The manufacture of above-mentioned urethane (methyl) acrylate resin (A) can be carried out under the existence of organic solvent, water-medium.In addition, organic solvent, water-medium can be replaced, manufacture under (methyl) described later acrylic monomer (B) exists.Wherein, when manufacturing duplexer, never need to remove organic solvent, water-medium, manufacturing process aspect can be simplified consider, preferably carry out under solvent-free, or the viscosity from the viewpoint of inhibited reaction system, preferably carries out under (methyl) acrylic monomer (B) exists.
Above-mentioned polyvalent alcohol (a) and the reaction of above-mentioned polyisocyanates (b) with above-mentioned (methyl) acrylic compounds (c) containing hydroxyl, the total amount of the hydroxyl that the hydroxyl had above-mentioned polyvalent alcohol (a) and above-mentioned (methyl) acrylic compounds (c) containing hydroxyl have, carry out in the scope of the equivalents ratio [total amount of isocyanate group/hydroxyl]=0.75 ~ 1.00 of the isocyanate group had with polyisocyanates (b), this is preferred in the molecular weight of urethane (methyl) acrylate resin (A) controlling gained, more preferably carry out in the scope of 0.79 ~ 0.95.In addition, although can react when above-mentioned equivalents ratio is greater than 1, in this situation, in order to make the terminal isocyanate group inactivation of urethane (methyl) acrylate resin (A), preferably the alcohol such as methyl alcohol are used.In this situation, the total amount of the hydroxyl that the hydroxyl preferably above-mentioned polyvalent alcohol (a) had and above-mentioned (methyl) acrylic compounds (c) containing hydroxyl have and the hydroxyl that alcohol has, to be adjusted in above-mentioned scope with above-mentioned polyisocyanate-based equivalents ratio [total amount of isocyanate group/hydroxyl].
In addition, as the alcohol in order to the terminal isocyanate group inactivation of above-mentioned urethane (methyl) acrylate resin (A) can be made to use, can use such as, 1 functional alcohol, 1 such as methyl alcohol, ethanol, propyl alcohol, butanols, 2-propylene glycol, 1,3 butylene glycol etc. comprise 2 functional alcohol etc. of primary hydroxyl and secondary hydroxyl.
In addition, when manufacturing urethane (methyl) acrylate resin (A), stopper, polyurethane-reinforcement catalyzer etc. can be used as required.
As above-mentioned stopper, can use such as, 3,5-di-t-butyl-4-hydroxytoluene, quinhydrones, toluhydroquinone, Hydroquinone monomethylether (p methoxy phenol), p-tert-butyl catechol, methoxyphenol, 2,6-di-tertiary butyl methyl phenol, thiodiphenylamine, tetramethyl-thiuram disulfide, pentanoic, dinitrobenzene etc.
As above-mentioned polyurethane-reinforcement catalyzer, can use such as, the organometallic compounds such as metal-salt, dibutyl tin laurate etc. such as the nitrogenous compounds such as triethylamine, Triethylene Diamine, N-methylmorpholine, potassium acetate, Zinic stearas, stannous octoate.
Next, (methyl) acrylic monomer (B) used in the present invention is described.
Above-mentioned (methyl) acrylic monomer contain second-order transition temperature more than 50 DEG C can be formed homopolymer containing (methyl) acrylic monomer (b-1) of nitrogen and (methyl) acrylic monomer (b-2) that can form homopolymer of second-order transition temperature less than-20 DEG C.
As (methyl) acrylic monomer (b-1) containing nitrogen that can form homopolymer of above-mentioned second-order transition temperature more than 50 DEG C, from the viewpoint of improving excellent clinging power and confining force further, (methyl) acrylic monomer containing nitrogen that can form homopolymer of preferred glass transition temperature 55 ~ 160 DEG C, more preferably (methyl) acrylic monomer (b-1) containing nitrogen that can form homopolymer of second-order transition temperature 140 ~ 160 DEG C.
As (methyl) acrylic monomer containing nitrogen operable in above-mentioned (b-1), such as (methyl) acrylamide can be enumerated, dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-dimethyl propyl (methyl) acrylamide methviium ammonium chloride, (methyl) acryloyl morpholine, sec.-propyl (methyl) acrylamide, N-(methyl) acryloyl-oxyethyl hexahydrophthalic phthalimide, hydroxyethyl (methyl) acrylamide etc., these monomers can be used alone or two or more merges use.
Wherein, from the viewpoint of improving solidified nature; preferred use contains the acrylic monomer of nitrogen; excellent clinging power and confining force is had concurrently from the viewpoint of improving further; more preferably use acryloyl morpholine, DMAA, dimethylaminopropylacryl acid amides, N-acryloyl-oxyethyl hexahydrophthalic phthalimide, particularly preferably use acryloyl morpholine.
As (methyl) acrylic monomer (b-2) that can form homopolymer of above-mentioned second-order transition temperature less than-20 DEG C, excellent clinging power and confining force is had concurrently, more preferably (methyl) acrylic monomer that can form homopolymer of second-order transition temperature-25 ~-80 DEG C from the viewpoint of improving further.
As operable (methyl) acrylic monomer in above-mentioned (b-2), such as ethyl propenoate can be enumerated, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-pentyl ester, isoamyl acrylate, the just own ester of vinylformic acid, the positive heptyl ester of vinylformic acid, vinylformic acid isocyanate, n-octyl, Isooctyl acrylate monomer, vinylformic acid ester in the ninth of the ten Heavenly Stems, the positive Lauryl Ester of methacrylic acid, Tridecyl methacrylate base ester, the different myristyl ester of vinylformic acid, 2-EHA, vinylformic acid 2-methylbutyl butenoate, vinylformic acid 3-methylbutyl butenoate, vinylformic acid 2-methyl pentyl ester, vinylformic acid 2-methoxy acrylate, vinylformic acid 3-methoxyl group propyl ester, vinylformic acid 3-methoxybutyl, vinylformic acid 2-ethoxy ethyl ester, vinylformic acid 2-oxyethyl group propyl ester, vinylformic acid 2-Ethoxybutyl etc., these monomers can be used alone or two or more merges use.
Wherein, from the viewpoint of can solidified nature be improved, preferably use acrylic monomer, have excellent clinging power and confining force concurrently from the viewpoint of improving further, more preferably use n-butyl acrylate, 2-EHA.
By making the mass ratio of above-mentioned (b-1) and above-mentioned (b-2) in above-mentioned (methyl) acrylic monomer for (b-1)/(b-2)=20/80 ~ 60/40, can obtain and have excellent clinging power and the tackiness agent of confining force concurrently.Wherein, from the viewpoint of improving excellent clinging power and confining force further, above-mentioned (b-1) is more preferably (b-1)/(b-2)=30/70 ~ 50/50 with the mass ratio of above-mentioned (b-2).If above-mentioned (b-1) is less than 20 with the mass ratio of above-mentioned (b-1) in the mass ratio of above-mentioned (b-2), then clinging power is bad especially, in addition, if be greater than 60, then have due to high cohesive force that hardness increases, can not get the problem of tackiness agent.
In addition, as above-mentioned (methyl) acrylic monomer used in the present invention, in the scope not destroying effect of the present invention, except above-mentioned (b-1) and (b-2), can merge and use other vinyl monomer.
As other vinyl monomer above-mentioned, (methyl) vinylformic acid can be enumerated, dimethyl aminoethyl (methyl) acrylate, N hydroxymethyl acrylamide, NVP, vinyl cyanide, N-vinyl formamide, methylene-succinic acid (acid anhydride), toxilic acid (acid anhydride), fumaric acid, β-crotonic acid, carboxy ethyl (methyl) acrylate, carboxy pentyl (methyl) acrylate, (methyl) methyl acrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, (methyl) tert-butyl acrylate, n-amylmethacrylate, isopentyl methacrylate, methacrylic acid peopentyl ester, the just own ester of methacrylic acid, the positive heptyl ester of methacrylic acid, methacrylic acid isocyanate, n octyl methacrylate, Isooctyl methacrylate, nonyl methacrylate, (methyl) cyclohexyl acrylate, 2-Ethylhexyl Methacrylate, (methyl) isobornyl acrylate, (methyl) dodecylacrylate, phenyl methacrylate, glycidyl methacrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid trifluoromethyl methyl esters, (methyl) vinylformic acid 2-trifluoromethyl ethyl ester, (methyl) vinylformic acid 2-perfluoro-ethyl ethyl ester, (methyl) vinylformic acid 2-perfluoro-ethyl-2-perfluoro butyl ethyl ester, (methyl) vinylformic acid 2-perfluor ethyl ester, (methyl) perfluoroethyl methyl esters, (methyl) vinylformic acid two perfluoro-methyl methyl esters, (methyl) vinylformic acid 2-perfluoro-methyl-2-perfluoro-ethyl ethyl ester, (methyl) vinylformic acid 2-perfluoro hexyl ethyl ester, (methyl) vinylformic acid 2-perfluoro decyl ethyl ester, (methyl) acrylic monomers such as (methyl) vinylformic acid 2-perfluor hexadecyl ethyl ester, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) acrylic monomer containing hydroxyl such as tetramethylolmethane three (methyl) acrylate, vinylbenzene, p-methylstyrene, ethyl styrene, propylstyrene, isopropyl styrene, the styrenic monomers such as p-tert-butylstyrene, vinyl-acetic ester, propionate, the vinyl monomers such as new vinyl acetate acid.
From the viewpoint of having excellent clinging power and confining force concurrently, the usage quantity of above-mentioned (methyl) acrylic monomer (B) preferably uses relative to above-mentioned urethane (methyl) acrylate resin (A) 100 mass parts in the scope of 30 ~ 200 mass parts, more preferably use in the scope of 40 ~ 150 mass parts, use in the scope particularly preferably in 50 ~ 100 mass parts.
Next, the Photoepolymerizationinitiater initiater used in the present invention (C) is described.
Above-mentioned Photoepolymerizationinitiater initiater (C) produces free radical by rayed, heating etc., causes the radical polymerization of above-mentioned urethane (methyl) acrylate resin (A), above-mentioned (methyl) acrylic monomer (B).
As above-mentioned Photoepolymerizationinitiater initiater, can use such as, the acetophenones 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-(methylthio group) phenyl]-2-morpholino-1-acetone, 2,2-dimethoxy-2-phenyl acetophenone; The bitter almond oil camphor classes such as the different ethyl ether of bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 '-methyldiphenyl thioether, 3, the benzophenones such as 3 '-dimethyl-4-methoxy benzophenone; The thioxanthene ketone such as thioxanthone, CTX, 2,4-bis-clopenthixal ketones, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, isopropyl thioxanthone, 2,4-diisopropylthioxanthone; 4,4 '-dimethylamino thioxanthone, 4, the Anthraquinones such as 4 '-diethylamino benzophenone, α-acyl group oxime ester, benzil, methylbenzoyl formate (" Vicure 55 "), 2-ethyl-anthraquinone; The acylphosphine oxide class such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (" Lucirin TPO "), two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide (" IRGACURE819 "); 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone [" BTTB " of Nippon Yushi (Co., Ltd.)], acrylated benzophenone etc.
As above-mentioned Photoepolymerizationinitiater initiater, from having excellent clinging power and confining force concurrently, and can prevent adhering agent layer through time variable color, can improve and consider with the consistency of specific (methyl) acrylic monomer, the viewpoint of solidified nature that use in the present invention, preferred use 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.Wherein, 1 kind in the above-mentioned 2-hydroxy-2-methyl of preferred use-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone or combinationally use 2 kinds and 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4,6-trimethylbenzoyl) in-phenyl phosphine oxide a kind or combinationally use 2 kinds.
In addition, at the above-mentioned 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone of use, 1 kind in 1-hydroxycyclohexylphenylketone or combinationally use 2 kinds, and 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, two (2, 4, 6-trimethylbenzoyl) in-phenyl phosphine oxide a kind or when combinationally using 2 kinds, from the viewpoint of improving further and the consistency of specific (methyl) acrylic monomer that uses in the present invention and solidified nature, more preferably 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone is used with the mass ratio of 20/80 ~ 80/20, 1 kind in 1-hydroxycyclohexylphenylketone or combinationally use 2 kinds, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, two (2, 4, 6-trimethylbenzoyl) in-phenyl phosphine oxide a kind or combinationally use 2 kinds, particularly preferably use with the ratio of 45/55 ~ 65/35.
The usage quantity of above-mentioned Photoepolymerizationinitiater initiater (C) preferably uses relative to above-mentioned urethane (methyl) acrylate resin (A) 100 mass parts in the scope of 0.1 ~ 20 mass parts, more preferably uses in the scope of 0.5 ~ 15 mass parts.
In addition, the tackiness agent comprising ultraviolet hardening tackiness agent resin combination of the present invention uses in optics, from the viewpoint of light fastness stability can be improved, in preferred ultraviolet hardening adhesion agent composition of the present invention, resistance to photostabilizer (D) can also be contained.
Above-mentioned resistance to photostabilizer (D) refers to the material catching the free radical produced due to light deterioration, can use such as, radical scavenger and the UV light absorber etc. such as benzophenone series, benzoic ether based compound such as mercaptan system, thioether system, hindered amine based compound, these resistance to photostabilizers can be used alone or two or more merges use.Wherein, have excellent clinging power and confining force concurrently from maintaining, and can improve further and considers with the consistency of specific (methyl) acrylic monomer that uses in the present invention and the viewpoint of light fastness stability, preferably use hindered amine based compound.
As above-mentioned hindered amine based compound, can enumerate such as, hexanaphthene and peroxidation N-butyl 2, 2, 6, 6-tetramethyl--4-piperylhydrazine-2, 4, 6-trichlorine 1, 3, the resultant of reaction of 5-triazine and 2-monoethanolamine resultant of reaction (trade(brand)name: Tinuvin (registered trademark) 152 (BASF Japan (strain) makes)), 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 resultant of reaction etc. of 1-dimethyl ethyl hydroperoxide and octane 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 base system hindered amine compounds such as 5-diketone (trade(brand)name: Hostavin (registered trademark) 3058 (Clariant Japan (strain) system)), 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, 1-dimethyl ethyl)-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 (trade(brand)name: Tinuvin (registered trademark) 622LD (BASF Japan (strain) system)) of 6-tetramethyl--1-piperidine ethanol, propanedioic acid [{ 4-p-methoxy-phenyl } methylene radical]-bis-(1, 2, 2, 6, 6-pentamethyl--4-piperidyl) the N-alkyl system hindered amine compound etc. of ester (trade(brand)name: Hostavin (registered trademark) PR-31 (Clariant Japan (strain) system)).Wherein, excellent clinging power and confining force is had concurrently from maintaining, and can improve further and consider with the consistency of specific (methyl) acrylic monomer that uses in the present invention and the viewpoint of light fastness stability, particularly preferably use the hindered amine compound with amino ether.
From the viewpoint of the heat-resisting xanthochromia can giving tackiness agent tunicle, the usage quantity of above-mentioned resistance to photostabilizer (D) preferably uses relative to above-mentioned urethane (methyl) acrylate resin (A) 100 mass parts in the scope of 0.01 ~ 10 mass parts, more preferably uses in the scope of 0.1 ~ 5 mass parts.
In addition, the tackiness agent comprising ultraviolet hardening tackiness agent resin combination of the present invention uses in optics, from the viewpoint of improving heat-resisting xanthochromia, also containing antioxidant (E) in preferred ultraviolet hardening adhesion agent composition of the present invention.
Above-mentioned antioxidant (E), can enumerate the phosphorus system, chalcogenide compound (secondary antioxidant) etc. that catch the superoxide that the hindered phenol based compound (secondary antioxidant) of free radical, the Sum decomposition that produce due to thermal degradation when produce due to thermal degradation when, these antioxidants can be used alone or merge use.
As above-mentioned hindered phenol based compound, can enumerate such as, triglycol-bis--[3-(the 3-tertiary butyl-5-methyl-4 hydroxy phenyl) propionic ester] (trade(brand)name: IRGANOX (registered trademark) 245 (BASF Japan (strain) system)), tetramethylolmethane four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester (trade(brand)name: IRGANOX (registered trademark) 1010 (BASF Japan (strain) system)), octadecyl [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester (trade(brand)name: IRGANOX (registered trademark) 1076 (BASF Japan (strain) system)), two [the 3-(3 of thiodiethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester] (trade(brand)name: IRGANOX (registered trademark) 1035 (BASF Japan (strain) system), phenylpropionic acid-3, 5-two (1, 1-dimethyl ethyl)-4-hydroxyl-C7-C9 pendant alkyl group ester (trade(brand)name: IRGANOX (registered trademark) 1135 (BASF Japan (strain) system)), 4, two (dodecylthiomethyl) ortho-cresol (trade(brand)name: the IRGANOX (registered trademark) 1726 (BASF Japan (strain) system) of 6-, N-phenylaniline and 2, 4, the resultant of reaction (trade(brand)name: IRGANOX (registered trademark) 5057 (BASF Japan (strain) system)) of 4-2,4,4-Trimethyl-1-pentene, 2 tertiary butyl-6-(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-, 1-dimethyl ethyl] 2, 4, 8, 10-tetra- spiral shell (55) undecane (trade(brand)name: Sumilizer (registered trademark) GA-80 (Sumitomo Chemical (strain) system)), 2,6-di-tert-butyl-4-methy phenol (trade(brand)name: Nocrac200 (the emerging chemical industry of imperial palace (strain) system)), 2,2 '-methylene-bis (4-methyl-6 tert.-butyl phenol) (trade(brand)name: NocracNS-6 (the emerging chemical industry of imperial palace (strain) system)), 2,5 di tert amlyl hydroquinone (trade(brand)name: NocracDAH (the emerging chemical industry of imperial palace (strain) system) etc.
As above-mentioned phosphorus series compound, can enumerate such as, triphenylphosphine, two [two (1,1-the dimethyl ethyl)-6-aminomethyl phenyl of 2,4-] ethide phosphite ester, triphenyl phosphite, trisnonylphenyl phosphite, three (2,4-dibutylphenyl) 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, tridecyl phosphite, octyl diphenyl phosphorous acid ester, two (decyl) single phenyl phosphites, two (tridecyl) pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, two (2,4-dibutylphenyl) pentaerythritol diphosphites, two (2,6-dibutyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4,6-tributyl phenyl) pentaerythritol diphosphites, two (2,4-dicumylphenyl) pentaerythritol diphosphites, four (tridecyl) isopropylidene xenol diphosphites, two (2-butyl-5-methylphenol) diphosphites of four (tridecyl)-4,4 '-positive butylidene, six (tridecyl)-1,1,3-tri-(2-methyl-4-hydroxyl-5-butyl phenyl) butane GW-540, four (2,4-dibutylphenyl) biphenylen, 9,10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2,2 '-methylene-bis (4,6-butyl phenyl)-2-ethylhexyl phosphorous acid ester, 2,2 '-methylene-bis (4,6-butyl phenyl)-octadecyl phosphorous acid ester, 2,2 '-ethylenebis (4,6-dibutylphenyl) fluorophosphites, three (2-((2,4,8,10-tetrabutyl dibenzo (d, f) (1,3,2) two phosphorus suberane-6-base) oxygen base) ethyl) phosphorous acid ester etc. of amine, 2-ethyl-2-butyl propylene glycol and 2,4,6-tributyl phenol.
As above-mentioned chalcogenide compound, can enumerate such as, two (dodecyls)-3, 3 '-thiopropionate, dilauryl-3, 3 '-thiodipropionate, dilauryl dithionite, two (tridecyls)-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, sulfuration two [2-methyl-4-(the positive alkylthio propionyloxy of 3-)-5 tert-butyl-phenyls], β-lauryl thiopropionate, 2-mercaptobenzimidazole, 2-sulfydryl-5-tolimidazole, two (octadecyls)-3, 3 '-thiodipropionate etc.
Wherein, excellent clinging power and confining force is had concurrently from maintaining, and improve further and consider with the consistency of specific (methyl) acrylic monomer that uses in the present invention and the viewpoint of heat-resisting xanthochromia, preferred use phosphorus series compound, particularly preferably use triphenylphosphine, two [2, two (1,1-the dimethyl ethyl)-6-aminomethyl phenyl of 4-] ethide phosphite ester, tetramethylolmethane four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester.
From the viewpoint of giving good heat-resisting xanthochromia to tackiness agent tunicle, the usage quantity of above-mentioned antioxidant (E) preferably uses relative to above-mentioned urethane (methyl) acrylate resin (A) 100 mass parts in the scope of 0.01 ~ 10 mass parts, more preferably uses in the scope of 0.1 ~ 5 mass parts.
In addition, the tackiness agent of ultraviolet hardening tackiness agent resin combination of the present invention is comprised at optics, when using in the manufacture of particularly liquid crystal touch screen, from the indium tin oxide prevented as transparent conductive material (hereinafter referred to as ITO.) metallic corrosion (rust-preventing characteristic) viewpoint consider, preferably in ultraviolet hardening adhesion agent composition of the present invention also containing rust-preventive agent (F).
As above-mentioned rust-preventive agent (F), can use such as, three azole compounds, organic carboxyl acid amine salt, nitrous acid amine salt, phosphate amine salt, amine carbonate, hetero ring type amine etc., these rust-preventive agent can be used alone or merge use.Excellent clinging power and confining force is had concurrently from maintaining, and the consistency of specific (methyl) acrylic monomer improved further when not destroying light fastness stability, heat-resisting xanthochromia and use in the present invention and the viewpoint of rust-preventing characteristic are considered, preferably use three azole compounds.
As above-mentioned three azole compounds, can use such as, 1-(two (2-ethylhexyl) amino methyl) benzotriazole, Methylbenzotriazole, dimethylbiphenyl triazole, ethyl benzotriazole, ethyl-methyl benzotriazole, diethyl benzotriazole, unsubstituting phenenyl triazole, 5-methyl isophthalic acid H-benzotriazole, N, N-two (2-ethylhexyl)-(4 or 5)-methyl isophthalic acid H-benzotriazole-1-methylamine, the triazole compounds etc. shown in following general formula (1).
[changing 1]
(in formula, R1 and R2 represents 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.)
As the triazole compounds shown in above-mentioned general formula (1), can be applicable to using two (2-ethylhexyl)-[(1,2, the 4-triazol-1-yl) methyl] amine of N, N-etc.
As above-mentioned three azole compounds, the commercially available products such as " IRGAMET (trade mark registration) 30 ", " IRGAMET (trade mark registration) 38S " (more than, BASF Japan (strain) make) can be used.
From the viewpoint of giving good rust-preventing characteristic when not making adhesion physical property reduce, the usage quantity of above-mentioned rust-preventive agent (F) preferably uses relative to above-mentioned urethane (methyl) acrylate resin (A) 100 mass parts in the scope of 0.001 ~ 5 mass parts, more preferably uses in the scope of 0.01 ~ 2 mass parts.
Next, ultraviolet hardening tackiness agent resin combination of the present invention is described.
Ultraviolet hardening tackiness agent resin combination of the present invention can be manufactured by following method: such as, after independent manufacture urethane (methyl) acrylate resin (A), (methyl) acrylic monomer (B), Photoepolymerizationinitiater initiater (C) and resistance to photostabilizer (D) as required, antioxidant (E), rust-preventive agent (F) are carried out the method mixed; Or, under the existence of part or all of (methyl) acrylic monomer (B), manufacture urethane (methyl) acrylate resin (A), then polymerization starter (C) and resistance to photostabilizer (D) as required, antioxidant (E), rust-preventive agent (F) are carried out the method such as mixing.
The ultraviolet hardening tackiness agent resin combination obtained by aforesaid method has no particular limits, good from the viewpoint of the operation of tackiness agent solution when good coating and coating, viscosity is preferably 500 ~ 20000mPas, is more preferably 1000 ~ 10000mPas.In addition, above-mentioned viscosity table is shown in 25 DEG C of employing Brookfield viscometers and measures the value obtained.
In addition, ultraviolet hardening tackiness agent resin combination of the present invention, except mentioned component, can also contain other additive.
As other additive above-mentioned, can use such as, thixotropy conferring agents, sensitizing agent, stopper, solidifying agent, curing catalyst, flow agent, tackifier, wax, thermo-stabilizer, white dyes, whipping agent, thermoplastic resin, thermosetting resin, organic solvent, conductivity-imparting agent, static inhibitor, water vapour permeability improving agent, water repllents, hollow foam, compound containing crystal water, fire retardant, water-retaining agent, moisture adsorbent, reodorant, suds-stabilizing agent, defoamer, mould inhibitor, sanitas, algaecide, anti-hard caking agent, hydrolysis preventing agent, organic and inorganic water-soluble compound etc.
As above-mentioned sensitizing agent, can use such as, biphenyl, Isosorbide-5-Nitrae-dimethylnaphthalene, 9-Fluorenone, fluorenes, phenanthrene, benzo [9,10] phenanthrene, anthracene, 9,10-diphenylanthrancene, 9,10-dimethoxy anthracene, 9,10-diethoxy anthracenes, 9,10-dipropoxy anthracenes, 9,10-dibutoxy anthracene, benzophenone, 4,4 '-dimethoxy-benzophenone, methyl phenyl ketone, 4-methoxyacetophenone, phenyl aldehyde etc.
As above-mentioned solidifying agent, can use by the derivative affixture such as tolylene diisocyanate, hexamethylene diisocyanate and be representative with isocyanuric acid ester body etc. polyisocyanate compound, multi-functional epoxy compound, melamine compound, metallo-chelate etc.
Ultraviolet hardening tackiness agent resin combination of the present invention can be solidified by the irradiation of ultraviolet homenergic ray.
As the method making ultraviolet hardening tackiness agent resin composition of the present invention, such as, can be cured by using the known ultraviolet illumination injection devices such as xenon lamp, xenon-mercuryvapour lamp, metal halide lamp, high pressure mercury vapour lamp, Cooper-Hewitt lamp to irradiate regulation ultraviolet.
Above-mentioned ultraviolet irradiation is preferably 50 ~ 5000mJ/cm 2scope, be more preferably 100 ~ 3000mJ/cm 2scope, be particularly preferably 300 ~ 1500mJ/cm 2scope.In addition, ultraviolet irradiation amount measures the value that obtains as benchmark to use UVCheckerUVR-N1 (GS soup shallow (strain) system) in the wavelength region may of 300 ~ 390nm.
In addition, when ultraviolet hardening tackiness agent resin combination of the present invention contains other additive above-mentioned, after above-mentioned ultraviolet irradiation, can heat at about 40 ~ 80 DEG C as required, thus promote solidification further.
The tackiness agent comprising ultraviolet hardening tackiness agent resin combination of the present invention has excellent clinging power and confining force concurrently, therefore can be suitable as the tackiness agent used in optics.Particularly, can be suitable for manufacturing liquid crystal touch screen, liquid-crystal display, plasma display, OLED display etc.
As the preferred use-pattern of tackiness agent comprising ultraviolet hardening tackiness agent resin combination of the present invention, can enumerate such as,
In liquid crystal touch screen, make plastic basis material, flexible printing base material, glass baseplate or on the substrate evaporation as the tackiness agent of the Graphene of transparent conductive material, ITO and the laminatings such as the base material that obtains,
In a liquid crystal display, by the tackiness agent that the transparent substrate be made up of glass, plastics etc. is fitted with the outermost polarization plates forming liquid crystal display,
In a liquid crystal display, what arrange between the transparency protected base material be made up of glass, plastics etc. and liquid crystal display is called as the tackiness agent used in the space of air gap,
Etc..
Comprise the tackiness agent of ultraviolet hardening tackiness agent resin combination of the present invention, in above-mentioned liquid crystal touch screen, as making plastic basis material, flexible printing base material, glass baseplate, or on the substrate evaporation as the Graphene of transparent conductive material, when the tackiness agent of ITO and the laminatings such as the base material that obtains, adopt following manner: at least using the tackiness agent comprising ultraviolet hardening tackiness agent resin combination of the present invention and stacked by being selected from plastic basis material on the two sides of layer (i) formed, flexible printing base material, glass baseplate, evaporation ITO (indium tin oxide) and layer (ii) that a kind of base material in the base material that obtains is formed on the substrate.
Here, above-mentioned layer (i) can use the tackiness agent comprising ultraviolet hardening tackiness agent resin combination of the present invention to be formed, although field that its thickness uses according to liquid crystal touch screen etc. and different, but in order to realize the slimming of liquid-crystal display, therefore be preferably the thickness of about 10 ~ 500 μm, be more preferably the thickness of 50 ~ 500 μm.
Above-mentioned layer (ii) by be selected from plastic basis material, flexible printing base material, glass baseplate and on the substrate evaporation ITO and a kind of base material in the base material obtained formed, identical or different base material can be used on the two sides of above-mentioned layer (i).
As above-mentioned plastic basis material, the base material be made up of acrylic resin etc. of general use, 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 sheet, the film forming the nesa coating of touch-screen or sheet etc. can be used.
As the method manufacturing above-mentioned duplexer, such as, the surface of a kind of base material in the base material being selected from the plastic basis material, flexible printing base material, glass baseplate or the evaporation ITO on the substrate that form above-mentioned layer (ii) can be coated with ultraviolet hardening tackiness agent resin combination of the present invention, after irradiating above-mentioned ultraviolet, other above-mentioned base material is loaded immediately on this coated face, after placement, obtain duplexer of the present invention.In addition, when above-mentioned base material is light transmission, the surface of above-mentioned base material is coated with ultraviolet hardening tackiness agent resin combination of the present invention, after this coated face loads other above-mentioned base material, irradiate above-mentioned ultraviolet from above-mentioned base material, thus duplexer of the present invention can be obtained.
In addition, when ultraviolet hardening tackiness agent resin combination of the present invention contains other additive above-mentioned, after irradiating above-mentioned ultraviolet as required, can heat at about 40 ~ 80 DEG C as required.
[embodiment]
Below, further illustrate the present invention by embodiment, but scope of the present invention is not limited only to these embodiments.
In addition, in the present invention, unless otherwise specified, " part " is " mass parts ", and " % " is " quality % ".
[synthesis example 1]
Synthesis (A-1) > of < urethane (methyl) acrylate resin
Polytetramethylene glycol (weight-average molecular weight 1000) 465.9 mass parts, vinylformic acid 2-hydroxyl ethyl ester 9.6 mass parts, 2,6-di-tertiary butyl methyl phenol 1.7 mass parts, p methoxy phenol 0.3 mass parts is added in the reaction vessel possessing stirrer, reflux cooling pipe, nitrogen ingress pipe, thermometer.By temperature in reaction vessel to after 40 DEG C, add isophorone diisocyanate 101.5 mass parts.Then, add dioctyl two neodecanoic acid tin 0.06 mass parts, be warmed up to 80 DEG C through 1 hour.Then, keep 12 hours at 80 DEG C, after confirming that whole isocyanate group disappears, cooling, obtains polyurethane acrylate resin as (A-1).The equivalent weight of the acryl of the polyurethane acrylate resin (A-1) of gained is 7000, and weight-average molecular weight is 18000.
[embodiment 1]
The modulation > of < ultraviolet hardening tackiness agent resin combination
In the container possessing stirrer, reflux cooling pipe, thermometer, in container, temperature 80 DEG C adds urethane (methyl) acrylate resin (A-1) 100 mass parts, n-butyl acrylate 30 mass parts, acryloyl morpholine 30 mass parts that obtain in synthesis example 1, stirs.Then, cool to room temperature, under agitation adds 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone 4 mass parts, 2,4,6-trimethoxybenzoyl diphenyl phosphine oxide 3 mass parts successively, stirs.Then, with 200 order metal mesh filters, ultraviolet hardening tackiness agent resin combination is obtained.
[embodiment 2 ~ 7, comparative example 1 ~ 4]
The kind of used (b-1) composition and amount, the amount of (b-2) composition and the amount of Photoepolymerizationinitiater initiater (C) are changed as shown in table 1 ~ 3, in addition, ultraviolet hardening tackiness agent resin combination is obtained similarly to Example 1.
[making method of adhesive film]
The ultraviolet hardening tackiness agent resin combination that the surface of having carried out the polyethylene terephthalate film (demoulding PET50) of the thickness 50 μm of demoulding process on surface obtains in coating Examples and comparative example, make the postradiation thickness of UV be 175 μm, this coated face is fitted another demoulding PET50.
Next, use UV irradiating unit from the upside irradiation ultraviolet radiation of above-mentioned demoulding PET50, thus the adhesive film that making 2 demoulding PET50 are laminated into across adhering agent layer.Above-mentioned ultraviolet irradiation is 1000mJ/cm at the accumulated light through the wavelength 300 ~ 390nm after above-mentioned demoulding PET50 2condition under carry out.
[measuring method of clinging power]
Peel off and form a slice demoulding PET50 of above-mentioned adhesive film, at the polyethylene terephthalate (PET75) of this adhering agent layer coating thickness 75 μm on the surface, thus make adhesive sheet.Above-mentioned adhesive sheet is made to be cut into 25mm width, the test film that the mensuration as clinging power uses.
Another sheet demoulding PET50 is peeled off from above-mentioned test film, at SUS304 stainless steel plate, (surface finishing BA is (after cold rolling, bright heat treatment)), on polycarbonate plate, sheet glass, 23 DEG C, under the atmosphere of 50%RH with the reciprocal pressing of 2kg roller 2 times, the test film after peeling off another sheet demoulding PET50 is pasted onto on each adherend.Paste after 1 hour 23 DEG C, measure 180 degree of stripping strengths, as bonding force under the atmosphere of 50%RH.
In addition, becoming the material of caking agent for can not get tackiness agent, not carrying out the mensuration of above-mentioned 180 degree of stripping strengths.
[measuring method of confining force]
Stainless steel plate after the test film relative specular precision work adopting the method same with the test film used in the measuring method of above-mentioned clinging power to be made into is carried out stacked, its bond area is made to be 25mm × 25mm, with the reciprocal pressing of 2kg roller 2 times under 23 DEG C of 50%RH atmosphere, thus they are fitted.
Next, under 40 DEG C of atmosphere, to being pasted on the test film of above-mentioned stainless steel plate along being the loading that 0 ° of direction (shear direction) applies 1kg relative to above-mentioned stainless steel plate, measure the time till above-mentioned test film peels off from stainless steel plate, using this hold-time as confining force.In addition, when also being kept after 24 hours, using the hold-time as more than 24 hours, measure and depart from width from initial paste position, record in the lump.
In addition, becoming the material of caking agent for can not get tackiness agent, not carrying out the mensuration of above-mentioned confining force.
[table 1]
[table 2]
[table 3]
In addition, the abbreviation in his-and-hers watches 1 ~ 3 is described.
" ACMO "; Acryloyl morpholine
" BA "; N-butyl acrylate
" (C-1) "; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone
" (C-2) "; 2,4,6-trimethoxybenzoyl diphenyl phosphine oxide
" M-140 "; N-acryloyl-oxyethyl hexahydrophthalic phthalimide
" DMAA "; DMAA
" DMAPAA "; Dimethylaminopropylacryl acid amides
" DMAEA "; Dimethyl amino ethyl acrylate
" N-VP "; NVP
[embodiment 8]
The modulation > of < ultraviolet hardening tackiness agent resin combination
In the container possessing stirrer, reflux cooling pipe, thermometer, in container, at temperature 80 DEG C, add urethane (methyl) acrylate resin (A-1) 100 mass parts, n-butyl acrylate 60 mass parts, acryloyl morpholine 30 mass parts that obtain in synthesis example 1, stir.Then, cool to room temperature, under agitation add 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone 3 mass parts successively, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide 2 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) makes) 1 mass parts, triphenylphosphine 1 mass parts, (2-ethylhexyl) aminomethyl-1,2 two with 1-, 2, 4-triazole (" IRGAMET (trade mark registration) 30 ", BASF Japan (strain) makes) 0.1 mass parts, stir.Then, with 200 order metal mesh filters, ultraviolet hardening tackiness agent resin combination is obtained.
[embodiment 9 ~ 11]
By the kind of used antioxidant (E) with amount is as shown in table 4 changes like that, in addition, obtain ultraviolet hardening tackiness agent resin combination similarly to Example 5.
[evaluation method of light fastness stability]
Peel off a slice demoulding PET50 forming the adhesive film obtained by aforesaid method, by this adhering agent layer surface mount on a glass, then peel off another sheet demoulding PET50, as test film.For this test film, according to JIS A 1415, to bonding plane direct irradiation ultraviolet in ultraviolet carbon arc lamp, black dish temperature 63 DEG C, UV fade meter " U48 " (Sugatest (strain) system), place 150 hours.Then, light source C, 2 °, visual field, " spectral photometric colour measuring meter " CM-5000d (KonicaMinolta (strain) system) is adopted to measure the xanthochromia degree (b* (UV)) caused by light according to JIS K 7105 this test film.
[evaluation method of heat-resisting xanthochromia]
Adopt method similar to the above to obtain test film, by this test film 85 DEG C, expose 250 hours under the condition of 85%RH.Then, light source C, 2 °, visual field, " spectral photometric colour measuring meter " CM-5000d (KonicaMinolta (strain) system) is adopted to measure the xanthochromia degree (b*) caused by heat according to JIS K 7105 this test film.
[evaluation method of rust-preventing characteristic]
Peel off and form a slice demoulding PET50 of above-mentioned adhesive film, at the polyethylene terephthalate (PET75) of this adhering agent layer coating thickness 75 μm on the surface, thus make adhesive sheet.Above-mentioned adhesive sheet is cut into the size of 40mm × 50mm, the test film that the evaluation as rust-preventing characteristic uses.
The above-mentioned test film having peeled off another sheet demoulding PET50 is fitted on Copper Foil, places 150 hours under 60 DEG C × 90%RH atmosphere.Then, visual observation copper foil surface, carries out the evaluation of rust-preventing characteristic as follows.
"○": non-corrosive.
"×": get rusty.
[table 4]
In addition, the abbreviation in his-and-hers watches 4 is described.
" Irgafos38 ": two [two (1,1-the dimethyl ethyl)-6-aminomethyl phenyl of 2,4-] ethide phosphite ester
" IrganoxPS800FD ": two (dodecyl)-3,3 '-thiopropionate
" Irganox1010 ": tetramethylolmethane four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester
[embodiment 12]
(manufacture of duplexer)
The ultraviolet hardening tackiness agent resin combination obtained in embodiment 5 is operated in the same manner as aforesaid method, obtains the adhesive film of thickness 175 μm.Then, peel off a slice demoulding PET50 film, be fitted on polycarbonate membrane.
Then, peel off another sheet demoulding PET film, laminating on a glass, obtains duplexer.

Claims (14)

1. a ultraviolet hardening tackiness agent resin combination, it is the ultraviolet hardening tackiness agent resin combination containing urethane (methyl) acrylate resin (A), (methyl) acrylic monomer (B) and Photoepolymerizationinitiater initiater (C), described urethane (methyl) acrylate resin (A) makes polyvalent alcohol (a), polyisocyanates (b) and obtains containing the reaction of hydroxyl (methyl) acrylic compounds (c)
It is characterized in that, described (methyl) acrylic monomer (B) containing second-order transition temperature more than 50 DEG C can be formed homopolymer containing (methyl) acrylic monomer (b-1) of nitrogen and (methyl) acrylic monomer (b-2) that can form homopolymer of second-order transition temperature less than-20 DEG C, the mass ratio of described (b-1) and described (b-2) is (b-1)/(b-2)=20/80 ~ 60/40.
2. ultraviolet hardening tackiness agent resin combination according to claim 1, (methyl) acrylic monomer (b-1) containing nitrogen that can form homopolymer of described second-order transition temperature more than 50 DEG C is (methyl) acrylic monomer containing nitrogen that can form homopolymer of second-order transition temperature 55 ~ 160 DEG C.
3. ultraviolet hardening tackiness agent resin combination according to claim 2, (methyl) acrylic monomer containing nitrogen that can form homopolymer of described second-order transition temperature 55 ~ 160 DEG C is selected from more than a kind in acryloyl morpholine, DMAA, dimethylaminopropylacryl acid amides and N-acryloyl-oxyethyl hexahydrophthalic phthalimide.
4. the ultraviolet hardening tackiness agent resin combination according to any one of claims 1 to 3, the described polyvalent alcohol (a) that described urethane (methyl) acrylate resin (A) uses is polyether glycol.
5. the ultraviolet hardening tackiness agent resin combination according to any one of claims 1 to 3, described Photoepolymerizationinitiater initiater (C) is selected from 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and two (2,4,6-trimethylbenzoyl) in-phenyl phosphine oxide more than a kind.
6. the ultraviolet hardening tackiness agent resin combination according to any one of claims 1 to 3, it is also containing resistance to photostabilizer (D).
7. the ultraviolet hardening tackiness agent resin combination according to any one of claims 1 to 3, it is also containing antioxidant (E).
8. the ultraviolet hardening tackiness agent resin combination according to any one of claims 1 to 3, it is also containing rust-preventive agent (F).
9. ultraviolet hardening tackiness agent resin combination according to claim 6, described resistance to photostabilizer (D) is hindered amine based compound.
10. ultraviolet hardening tackiness agent resin combination according to claim 7, described antioxidant (E) is phosphorus series compound.
11. ultraviolet hardening tackiness agent resin combinations according to claim 8, described rust-preventive agent (F) is three azole compounds.
12. 1 kinds of tackiness agents, it comprises the ultraviolet hardening tackiness agent resin combination described in any one of claim 1 ~ 11.
13. tackiness agents according to claim 12, it uses in optics.
14. 1 kinds of duplexers, it obtains as follows: at least stacked by being selected from plastic basis material, flexible printing base material, glass baseplate and evaporation indium tin oxide and layer (ii) that a kind of base material in the base material that obtains is formed on the substrate on the two sides using the tackiness agent comprising ultraviolet hardening tackiness agent resin combination described in claim 1 ~ 11 and the layer (i) formed.
CN201110439919.7A 2010-12-24 2011-12-23 Resin composition for ultraviolet ray solidifying agglutinant, agglutinant, and laminating body Active CN102533205B (en)

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