CN103108930A - Light-curing composition for use in transparent pressure-sensitive adhesive sheet - Google Patents
Light-curing composition for use in transparent pressure-sensitive adhesive sheet Download PDFInfo
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- CN103108930A CN103108930A CN2011800446820A CN201180044682A CN103108930A CN 103108930 A CN103108930 A CN 103108930A CN 2011800446820 A CN2011800446820 A CN 2011800446820A CN 201180044682 A CN201180044682 A CN 201180044682A CN 103108930 A CN103108930 A CN 103108930A
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- Prior art keywords
- methyl
- adhesive sheet
- sensitive adhesive
- transparent pressure
- acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
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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
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
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- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
Abstract
The purpose of the present invention is to provide: a light-curing composition for use in a transparent pressure-sensitive adhesive sheet that is highly transparent and well suited to punching, has a strongly cohesive pressure-sensitive adhesive-agent layer, and does not corrode a conductive layer of a transparent conductive film even if bonded directly to the surface of said conductive layer; and a pressure-sensitive adhesive sheet. The present invention is a light-curing composition for use in a transparent pressure-sensitive adhesive sheet, said composition comprising: (A) a (meth)acryl-group-containing polyolefin compound that has a weight-average molecular weight of 10,000-300,000; (B) a (meth)acrylic acid ester that has a hydroxyl group; (C) photopolymerizable monomers other than (meth)acrylic acid esters having hydroxyl groups; and (D) a photopolymerization initiator. Said light-curing composition for use in a transparent pressure-sensitive adhesive sheet is characterized in that carboxyl-group-containing monomers constitute no more than 0.1% of the mass of the (C) photopolymerizable monomers.
Description
Technical field
The present invention relates to light solidified transparent pressure-sensitive adhesive sheet composition, be characterised in that the light solidified transparent pressure-sensitive adhesive sheet that the light solidified transparent pressure-sensitive adhesive sheet is solidified with composition and obtain is used for the nesa coating of applying of nesa coating fixing with the transparent pressure-sensitive adhesive sheet composition, fixing to solidify with composition the nesa coating that obtains with transparent pressure-sensitive adhesive sheet fixing with transparent pressure-sensitive adhesive sheet and be characterised in that nesa coating fixes the duplexer that sticks on the conductive layer surface of nesa coating with transparent pressure-sensitive adhesive sheet with nesa coating.
Background technology
In recent years begin to load touch panel in the field such as portable phone, game machine.Touch panel is for using optics with transparent pressure-sensitive adhesive sheet, the top layer to be had its transparency protected and the display unit class optical component such as the liquid-crystal display duplexer of fitting and forming of transparent substrate, glass and protection of the nesa coatings such as ITO (tin indium oxide).
The electrostatic detection that is derived from human body when the touch panel of the resistive film mode that the pressure when touch panel mainly contains the utilization input detects and utilization input is inputted the touch panel of the capacitance-type (capacitive type) at position.In the touch panel of capacitance-type, the conductive layer surface of nesa coating is fixed in the mode that contacts with the adhesive layer surface of adhesive sheet.Therefore, the conductive layer surface of nesa coating contacts with binder layer, has thus the oxidizing reaction that metal occurs due to the sour composition that contains in tackiness agent, produces the problem that conducting function reduces.Therefore, fixing with the demanding preventing metal corrosion of adhesive sheet for nesa coating.
As the adhesive sheet with preventing metal corrosion, proposed to contain the adhesive sheet (for example patent documentation 1) of preventing metal corrosion agent.In addition, propose to contain by the sour composition with respect to binder layer the nitrogen atom composition of specified quantitative, thereby reduced the corrosive adhesive sheet (for example patent documentation 2) for nesa coating.
But there is preventing metal corrosion agent variable color and make the problems such as optical characteristics reduction in endurance test in the adhesive sheet that contains the preventing metal corrosion agent.In addition, for the adhesive sheet of the nitrogen atom composition that contains specified quantitative, there is the problem of the resistance value rising that can not fully suppress ITO due to the sour composition that contains in binder layer.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-45315 communique
Patent documentation 2: TOHKEMY 2010-144002 communique
Summary of the invention
The problem that invention will solve
The problem to be solved in the present invention is, even provide the transparent pressure-sensitive adhesive sheet that curing obtains also can not corrode conductive layer, the light solidified transparent pressure-sensitive adhesive sheet composition of the force of cohesion of binder layer, the transparency and stamping-out excellent in workability to direct applying of the conductive layer surface of nesa coating.Further, the problem to be solved in the present invention is, and then this transparent pressure-sensitive adhesive sheet is provided.
For the scheme of dealing with problems
The foregoing problems that the inventor etc. exist with the light solidified transparent pressure-sensitive adhesive sheet take touch panel is in depth studied as background, found that a kind of light solidified transparent pressure-sensitive adhesive sheet composition, the preventing metal corrosion of the transparency, binding property and the nesa coating of the light solidified transparent pressure-sensitive adhesive sheet that this light solidified transparent pressure-sensitive adhesive sheet is solidified with composition and obtain is good, completes the present invention based on this discovery; Described light solidified transparent pressure-sensitive adhesive sheet contains (methyl) acryl (chemical formula :-COCH=CH with what the composition compounding had a high molecular
2,-COC (CH
3)=CH
2) polyolefin compound, (chemical formula :-OH) (methyl) acrylate, photopolymerization monomer and Photoepolymerizationinitiater initiater, the carboxylic monomer that contains in photopolymerization monomer is below specified amount to have hydroxyl.
The present invention is as shown in following (1)～(11).
(1) a kind of light solidified transparent pressure-sensitive adhesive sheet composition, it is characterized in that, it contains (A) weight-average molecular weight is 10,000～300,000 the polyolefin compound that contains (methyl) acryl, (B) has (methyl) acrylate of hydroxyl, (C) have photopolymerization monomer and (D) Photoepolymerizationinitiater initiater beyond (methyl) acrylate of hydroxyl, (C) having the carboxylic monomer that contains that contains in (methyl) acrylate photopolymerization monomer in addition of hydroxyl is below 0.1 quality % with respect to the total amount that (C) has (methyl) acrylate photopolymerization monomer in addition of hydroxyl.
(2) light solidified transparent pressure-sensitive adhesive sheet composition described according to (1); it is characterized in that; with the total amount of composition, contain (A) weight-average molecular weight and be photopolymerization monomer 20～88 quality % and (D) Photoepolymerizationinitiater initiater 0.2～5 quality % beyond 10,000～300,000 the polyolefin compound that contains (methyl) acryl 10～50 quality %, (methyl) acrylate 1～30 quality % that (B) has hydroxyl, (methyl) acrylate that (C) has hydroxyl with respect to the light solidified transparent pressure-sensitive adhesive sheet.
(3) according to above-mentioned (1) or (2) described light solidified transparent pressure-sensitive adhesive sheet composition, it is characterized in that, (methyl) acrylate photopolymerization monomer in addition that (C) has hydroxyl does not comprise and contains carboxylic monomer.
(4) according to the described light solidified transparent pressure-sensitive adhesive sheet of any one composition in above-mentioned (1)～(3), it is characterized in that (B) had (methyl) acrylate of hydroxyl and (C) have the photopolymerization monomer polymerization beyond (methyl) acrylate of hydroxyl and the theoretical second-order transition temperature of the polymkeric substance that obtains is 0 ℃～50 ℃.
(5) according to the described light solidified transparent pressure-sensitive adhesive sheet of any one composition in above-mentioned (1)～(4), it is characterized in that, (methyl) acrylate photopolymerization monomer in addition that (C) has hydroxyl is simple function (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester.
(6) according to the described light solidified transparent pressure-sensitive adhesive sheet of any one composition in above-mentioned (1)～(5); it is characterized in that, (A) weight-average molecular weight is that 10,000～300,000 the polyolefin compound that contains (methyl) acryl is to make the polyolefin polyhydric alcohol compound, have the compound with (methyl) acryl that the compound reaction that has two above isocyanate group in (methyl) acrylate of hydroxyl and a part obtains.
(7) according to the described light solidified transparent pressure-sensitive adhesive sheet of any one composition in above-mentioned (1)～(6), it is characterized in that, acid number is below 0.5mgKOH/g.
(8) a kind of nesa coating is fixing with the transparent pressure-sensitive adhesive sheet composition, it is characterized in that, the light solidified transparent pressure-sensitive adhesive sheet that the middle described light solidified transparent pressure-sensitive adhesive sheet of any one in above-mentioned (1)～(7) is obtained with composition curing is used for the applying of nesa coating.
(9) a kind of nesa coating is fixing uses transparent pressure-sensitive adhesive sheet, it is characterized in that, above-mentioned by making (8) described nesa coating is fixing to be solidified to obtain with composition with transparent pressure-sensitive adhesive sheet.
(10) fixingly according to above-mentioned (9) described nesa coating use transparent pressure-sensitive adhesive sheet, it is characterized in that, gel fraction is 80～100%.
(11) a kind of duplexer, is characterized in that, forms by the fixing conductive layer surface that sticks on nesa coating with transparent pressure-sensitive adhesive sheet of above-mentioned (9) or (10) described nesa coating.
The effect of invention
Light solidified transparent pressure-sensitive adhesive sheet of the present invention with composition due to the polyolefin compound that contains (methyl) acryl that contains high molecular in composition; make flexibility, the anti-excellent moisture permeability of the adhesive sheet that its curing obtains; further due to the carboxyl that only contains trace in composition; can suppress the corrosion of the conductive layer surface of the nesa coating that the sour composition by resulting transparent pressure-sensitive adhesive sheet causes; owing to containing (methyl) acrylate with hydroxyl in composition, the force of cohesion of resulting adhesive sheet and excellent to the adaptation of base material.
Embodiment
Below the present invention is described in detail.
[light solidified transparent pressure-sensitive adhesive sheet composition]
Light solidified transparent pressure-sensitive adhesive sheet of the present invention contains photopolymerization monomer and (D) Photoepolymerizationinitiater initiater beyond (A) weight-average molecular weight is 10,000～300,000 the polyolefin compound that contains (methyl) acryl, (B) has hydroxyl (methyl) acrylate, (methyl) acrylate that (C) has hydroxyl with composition.
((A) contains the polyolefin compound of (methyl) acryl)
As the polyolefin compound that contains (methyl) acryl, if having polyolefin backbone and then imported the polyolefin compound of (methyl) acryl, can use.As polyolefin backbone, can list the skeletons such as polyethylene, polypropylene, ethylene-propylene copolymer, divinyl, isoprene, hydrogenated butadiene polymer, hydrogenated polyisoprene, cycloolefin.Consider from the viewpoint of photostabilization, the transparency (amorphism), operability (liquid state), be preferably hydrogenated butadiene polymer, hydrogenated polyisoprene skeleton.Need to prove, (methyl) acryl refers to CH
2=CH-CO-or CH
2=C (CH
3)-CO-.
The introduction method that (methyl) acryl is imported in polyolefine is not particularly limited; but illustration go out to use (methyl) vinylformic acid molecular end etc. to be had the polyolefine esterification of reactive hydroxyl; perhaps at first the isocyanate compound that has two above isocyanate group in a part is added to polyolefinic hydroxyl; make isocyanate group and have (methyl) acrylate reactions of hydroxyl, carrying out thus the method for (methyl) propylene acidylate.
Wherein, make the isocyanate compound reaction that has two above isocyanate group in polyolefin polyhydric alcohol compound and a part; the polyolefin compound that contains (methyl) acryl that then carries out the urethane reaction with (methyl) acrylate with hydroxyl and obtain, preferred from the force of cohesion high aspect consideration of resulting adhesive sheet.
The polyolefin polyhydric alcohol compound has two above hydroxyls in a part, preferably have 2～4 hydroxyls.In addition, the weight-average molecular weight of polyolefin polyhydric alcohol compound is preferably 5000～30000, and more preferably 10000～15000.If the weight-average molecular weight of polyolefin polyhydric alcohol compound lower than 5000, exists the molecular weight of the polyolefin compound of (methyl) acryl of resulting containing can not raise, can not get the tendency of sufficient adhesive sheet intensity.In addition, if higher than 30000, there is the too high and reluctant tendency of molecular weight of the polyolefin compound of (methyl) acryl of resulting containing in the weight-average molecular weight of polyolefin polyhydric alcohol compound.
As the compound that has two above isocyanate group in a part, can list such as tolylene diisocyanate, eylylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethyl-eylylene diisocyanate, isophorone diisocyanate and their diisocyanate cpds such as hydride.Wherein, consider from the viewpoint of photostabilization, the reactive easiness of controlling, be preferably isophorone diisocyanate.Have in these a part the compound of two above isocyanate group can be separately with or two or more combination use.As the consumption of the isocyanate compound that has two above isocyanate group in a part, be preferably 8～35 mass parts with respect to 100 mass parts polyolefin polyhydric alcohol, more preferably 10～30 mass parts, more preferably 11～25 mass parts.Be less than 8 mass parts if having the consumption of the isocyanate compound of two above isocyanate group in a part; due to resulting containing (methyl) acryl too high being difficult to of the molecular weight of polyolefin compound process; if the consumption of isocyanate compound more than 35 mass parts, exist due to resulting containing (methyl) acryl the molecular weight of polyolefin compound too low and can not fully obtain the tendency of adhesive sheet intensity.
as with (methyl) acrylate with hydroxyl of isocyanic ester radical reaction, the carbonatoms that can list such as alkyl is (methyl) vinylformic acid hydroxyalkyl acrylate of 2～7 etc., as their concrete example, can (methyl) vinylformic acid 2-hydroxy methacrylate be shown example, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 1, the 3-butanediol ester, (methyl) vinylformic acid 1, the 4-butanediol ester, (methyl) vinylformic acid 1, 6-hexylene glycol ester, (methyl) vinylformic acid 3-methyl pentanediol ester etc., can be separately with or two or more combination use.Wherein, consider from reactive viewpoint, be preferably vinylformic acid 2-hydroxy methacrylate and 2-hydroxyethyl methacrylate.As the consumption of (methyl) acrylate with hydroxyl, be preferably 3～18 mass parts with respect to 100 mass parts polyolefin polyhydric alcohol, more preferably 4～15 mass parts, more preferably 5～13 mass parts.Be less than 3 mass parts if having the consumption of (methyl) acrylate of hydroxyl; might there be the olefin(e) compound with (methyl) acryl; the strength decreased of adhesive sheet; if have the consumption of (methyl) acrylate of hydroxyl more than 18 mass parts, exist due to the amount that imports to (methyl) acryl in alkene too much and the tendency of adhesive sheet hardening.
Contain the importing number of (methyl) acryl of the polyolefin compound of (methyl) acryl as (A) of the present invention, more than one, (methyl) acryl gets final product if having in a part, has 1～2 in preferred a part.
(A) the molecular weight preferable weight-average molecular weight that contains the polyolefin compound of (methyl) acryl is 10,000～300,000, more preferably 20,000～200,000, more preferably 30,000～100,000.Weight-average molecular weight was less than 10,000 o'clock, and due to the force of cohesion reduction of resulting adhesive sheet, the intensity of adhesive sheet might be insufficient, so not preferred.In addition, molecular weight was greater than 300,000 o'clock, and because the light solidified transparent pressure-sensitive adhesive sheet was processed with too high being difficult to of the viscosity of composition, so the remarkable variation of operability is not preferred.Need to prove, the weight-average molecular weight in the present invention is for using gel permeation chromatography (the Shodex GPC-101 processed of Showa Denko K. K), and normal temperature is measured under the following conditions, the value of utilizing the polystyrene standard typical curve to try to achieve.
Chromatographic column: clear and electrician LF-804 processed
Column temperature: 40 ℃
Sample: 0.2 quality % tetrahydrofuran solution of multipolymer
Flow: 1ml/ minute
Elutriant: tetrahydrofuran (THF)
Detector: RI
Contain the content of polyolefin compound in light solidified transparent pressure-sensitive adhesive sheet use composition of (methyl) acryl as (A), be preferably 10～50 quality % in composition, more preferably 15～45 quality %, more preferably 20～40 quality %.When being less than 10 quality %, resulting adhesive sheet becomes fragile, so not preferred.During more than 50 quality %, the bounding force of resulting adhesive sheet might reduce, so not preferred.
((B) has hydroxyl (methyl) acrylate)
preferably do not have carboxyl at this alleged (methyl) acrylate with hydroxyl, the carbonatoms that can list such as alkyl is (methyl) vinylformic acid hydroxyalkyl acrylate of 2～7 etc., as their concrete example, can (methyl) vinylformic acid 2-hydroxy methacrylate be shown example, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 1, the 3-butanediol ester, (methyl) vinylformic acid 1, the 4-butanediol ester, (methyl) vinylformic acid 1, 6-hexylene glycol ester, (methyl) vinylformic acid 3-methyl pentanediol ester etc., can be separately with or two or more combination use.Wherein, consider from the viewpoint of the bounding force of resulting adhesive sheet, be preferably vinylformic acid 2-hydroxy methacrylate.For the content of (methyl) acrylate that (B) has hydroxyl, preferably contain 1～30 quality % at the light solidified transparent pressure-sensitive adhesive sheet in composition, more preferably 5～25 quality %, more preferably 10～20 quality %.During less than 1 quality %, resulting adhesive sheet is insufficient to the adaptation of base material, so not preferred.In addition, during more than 30 quality %, so the water tolerance variation of adhesive sheet is not preferred.
((C) has the photopolymerization monomer beyond hydroxyl (methyl) acrylate)
(C) have photopolymerization monomer beyond (methyl) acrylate of hydroxyl (below be sometimes referred to as " photopolymerization monomer (C) ") and be photopolymerization monomer, refer to the photopolymerization monomer beyond (methyl) acrylate with hydroxyl, be preferably and do not contain carboxyl (chemical formula :-COOH) monomer.Be not particularly limited as this monomer, can with have the simple function of vinyl, (methyl) acryl etc. or multi-functional photopolymerization monomer separately with or two or more combination use.as the photopolymerization monomer of (C) of the present invention, for example be preferably (methyl) acrylic compound with (methyl) acryl, for example can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) isodecyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) stearyl acrylate ester, (methyl) lauryl acrylate, (methyl) alkyl acrylates such as (methyl) tridecyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid norbornene ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid norborneol alkyl ester, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid double cyclopentenyl 2-ethoxyethyl acetate, (methyl) vinylformic acid dicyclo pentyl ester, (methyl) vinylformic acid dicyclo amyl group 2-ethoxyethyl acetate, (methyl) vinylformic acid cyclic alkyl esters such as tristane dihydroxymethyl two (methyl) acrylate etc.can list (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid butoxyethyl, (methyl) vinylformic acid 2-methoxy ethoxy ethyl ester, (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid 2-ethoxy ethoxy ethyl ester, methoxyl group glycol ether (methyl) acrylate, ethoxydiglycol (methyl) acrylate, alkoxyl group (gathering) aklylene glycol (methyl) acrylate such as methoxyl group dipropylene glycol (methyl) acrylate, (methyl) vinylformic acid fluorinated alkyl esters such as (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid N, the N-dimethylamino ethyl ester, (methyl) vinylformic acid N, (methyl) propenoic acid dialkyl aminoalkyl esters such as N-diethylamino ethyl ester, polyoxyethylene glycol two (methyl) acrylate, glycol ether two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triglycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, hydroxy new pentane acid ester neopentyl glycol two (methyl) acrylate, two (hydroxyethyl)-5 of 1,3-, 5-T10 two (methyl) acrylate, α, the two glycol ether phthalic esters of ω-two (methyl) acryl, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, two propylene acyloxy ethyl phosphonic acid esters, Dipentaerythritol trihydroxy-(methyl) acrylate, trimethylolpropane tris (methyl) acrylate, multi-functional (methyl) acrylate such as tetramethylolmethane four (methyl) acrylate, acrylamide and DMAA, the diethyl acrylamide, the acrylamide derivatives such as (methyl) acryloyl morpholine, (methyl) glycidyl acrylate etc. contain (methyl) acrylate of epoxy group(ing) etc.Photopolymerization monomer as (C) of the present invention; from considering with Combination, the binding property of adhesive sheet, intensity, photostabilization, the stable on heating viewpoint of the polyolefin compound that contains (methyl) acryl, be preferably simple function (methyl) alkyl acrylate or (methyl) vinylformic acid cyclic alkyl ester.Refer to (methyl) acryl at this alleged simple function or polyfunctional functional group.The content of photopolymerization monomer (C) preferably contains 20～88 quality % at the light solidified transparent pressure-sensitive adhesive sheet in composition, more preferably 20～70 quality %.40～69 quality % more preferably.During less than 20 quality %, resulting adhesive sheet is insufficient to the adaptation of base material, so not preferred.In addition, the force of cohesion due to adhesive sheet during more than 88 quality % reduces, and bounding force reduces, so not preferred.
In the present invention, for the vinylformic acid that contains in the photopolymerization monomer of (C), methacrylic acid etc. contain carboxylic monomer, be below 0.1 quality % with respect to the total amount of the photopolymerization monomer of (C), more preferably below 0.05 quality %.(C) photopolymerization monomer does not further preferably comprise and contains carboxylic monomer.Surpass with respect to the total amount of the photopolymerization monomer of (C) corrosion that 0.1 quality % is difficult to suppress the conductive layer surface of nesa coating if contain carboxylic monomer.
Has the theoretical second-order transition temperature of the polymkeric substance that (methyl) acrylate of hydroxyl and (C) photopolymerization monomer form from the intensity of adhesive sheet, the viewpoint consideration of bonding force by (B) of the present invention, be preferably 0～50 ℃, more preferably 5～45 ℃, more preferably 10～40 ℃.During lower than 0 ℃, resulting adhesive sheet is because the impact of the polyolefin compound that contains (methyl) acryl becomes too soft, so the reduction of the bonding force of adhesive sheet, so not preferred.In addition, during higher than 50 ℃, resulting adhesive sheet is really up to the mark, can not get sufficient binding property, so not preferred.At this, theoretical second-order transition temperature (Tg) can be calculated by the formula (1) of following FOX based on the Tg of the homopolymer (homopolymer) of each monomer that consists of raw material monomer and the massfraction (copolymerization ratio) of this monomer.
[mathematical expression 1]
1/Tg=W
1/T
1+W
2/T
2+…W
n/T
n(1)
W in formula (1)
1, W
2W
nBe the massfraction (=(the compounding amount of each monomer/monomer total mass)) of each monomer, T
1, T
2T
nSecond-order transition temperature (absolute temperature) for the homopolymer of each monomer.As the Tg of homopolymer, adopt the value of record in " Polymer Handbook " (" polymer handbook ") of " Nian Ji Intraoperative Ha Application De Block ッ Network " as the Nikkan Kogyo Shimbun of Co., Ltd. of known data (" adhering technique handbook) or Wiley-Interscience.For the Tg of homopolymer of the monomer of record not in above-mentioned known data, adopt the value of being tried to achieve by following method.That is, the monomer that will become object carries out solution polymerization and obtains homopolymer solution, makes this homopolymer solution curtain coating on release liner dry, makes test sample.For this test sample, using differential scanning calorimeter (DSC) to make temperature be changed to 280 ℃ from-80 ℃ with the heat-up rate of 10 ℃/minute carries out means of differential scanning calorimetry and measures, adopt the heat absorption starting temperature of glass transition as the Tg of this homopolymer.
((D) Photoepolymerizationinitiater initiater)
As (D) Photoepolymerizationinitiater initiater in the present invention, can list such as carbonyl is that Photoepolymerizationinitiater initiater, sulfide-based Photoepolymerizationinitiater initiater, quinone are that Photoepolymerizationinitiater initiater, azo are that Photoepolymerizationinitiater initiater, SULPHURYL CHLORIDE are that Photoepolymerizationinitiater initiater, thioxanthone are Photoepolymerizationinitiater initiater, peroxidation system Photoepolymerizationinitiater initiater etc.
be Photoepolymerizationinitiater initiater as carbonyl, can list for example benzophenone, dibenzoyl, bitter almond oil camphor, ω-bromoacetophenone, monochloroacetone, methyl phenyl ketone, 2, the 2-diethoxy acetophenone, 2, 2-dimethoxy-2-phenyl methyl phenyl ketone, to the dimethylamino benzoylformaldoxime, to the dimethylamino Propiophenone, the 2-chlorobenzophenone, 4, 4 '-dichloro benzophenone, 4, 4 '-two diethylamino benzophenone, Michler's keton, benzoin methylether, the bitter almond oil camphor ethyl isobutyl ether, benzoin n-butylether, the benzil dimethyl ketal, the 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, the benzoyl methyl-formiate, 2, the 2-diethoxy acetophenone, 4-N, N '-dimethyl acetophenone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone etc.
As sulfide-based Photoepolymerizationinitiater initiater, can list such as Diphenyl disulfide ether, benzyldithio toluene, tetraethylthiuram disulfide, tetramethyl-one ammonium sulfide etc.Be Photoepolymerizationinitiater initiater as quinone, can list such as benzoquinones, anthraquinone etc.Be Photoepolymerizationinitiater initiater as azo, can list for example azobis isobutyronitrile, 2,2 '-di-isopropyl diazene (2,2 '-azobispropane), hydrazine etc.Be Photoepolymerizationinitiater initiater as thioxanthone, can list such as thioxanthone, CTX, 2-methyl thioxanthone etc.As peroxidation system Photoepolymerizationinitiater initiater, can list such as benzoyl peroxide, di-t-butyl peroxide etc.In these Photoepolymerizationinitiater initiaters, from considering with the deliquescent viewpoint composition at resulting light solidified transparent pressure-sensitive adhesive sheet, be preferably 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone.These Photoepolymerizationinitiater initiaters can be separately with or two or more combination use.
Consider from the viewpoint of the intensity of light solidified and resulting adhesive sheet, fusible balance, (D) content of Photoepolymerizationinitiater initiater is preferably 0.2～5 quality % at the light solidified transparent pressure-sensitive adhesive sheet in composition, more preferably 0.5～3 quality %, more preferably 0.8～2 quality %.If (D) there is the inadequate tendency of photocuring in the content of Photoepolymerizationinitiater initiater less than 0.2 quality %, if surpass the tendency that there is the binding property reduction of resulting adhesive sheet in 5 quality %, so not preferred.
For light solidified transparent pressure-sensitive adhesive sheet of the present invention for composition, preferably with respect to the total amount of light solidified transparent pressure-sensitive adhesive sheet with composition, contain 10～50 quality % (A) compositions, 1～30 quality % (B) composition, 20～88 quality % (C) compositions and 0.2～5 quality % (D) composition.And, more preferably with respect to the total amount of light solidified transparent pressure-sensitive adhesive sheet with composition, contain 15～45 quality % (A) compositions, 5～25 quality % (B) compositions, 20～70 quality % (C) compositions and 0.2～5 quality % (D) composition.And, further preferably with respect to the total amount of light solidified transparent pressure-sensitive adhesive sheet with composition, contain 20～40 quality % (A) compositions, 10～20 quality % (B) compositions, 40～69 quality % (C) compositions and 0.5～3 quality % (D) composition.
Light solidified transparent pressure-sensitive adhesive sheet of the present invention in order to improve the bonding force of resulting adhesive sheet, can also add tackifying resin with in composition as required in the scope that can not reduce the transparency.Example as tackifying resin, can list the rosin series resins such as carboxylate of rosin, rosin, diterpene polymkeric substance, α-pinene-terpenes such as phenol multipolymer are resin, the petroleum resin such as fat family (C5 system), fragrant family (C9 system), and phenylethylene resin series, phenolic aldehyde are resin, xylene resin etc.Consider from sunproof viewpoint, preferably the carboxylate of the carboxylate of the staybelite that unsaturated double-bond is few, nilox resin, aliphatics through-stone oleo-resinous, aromatic series through-stone oleo-resinous, high Tg vinylformic acid (ester) resin etc. add in adhesive sheet.As the addition of tackifying resin, preferably add 1～10 mass parts with respect to the light solidified transparent pressure-sensitive adhesive sheet with composition 100 mass parts (with respect to (A) composition, (B) composition, (C) composition and (D) total amount 100 mass parts of composition).
In addition, light solidified transparent pressure-sensitive adhesive sheet of the present invention as required, can also contain known various additive with in composition in the scope of not damaging the transparency.As additive, can list the such static inhibitor of photostabilizer, phosphoric acid ester system and other fire retardant, the tensio-active agent such as softening agent, surface lubricant, flow agent, tenderizer, antioxidant, protective agent, photostabilizer, UV light absorber, stopper, benzotriazole system etc.
In addition, the viscosity when being coated with in order to adjust, light solidified transparent pressure-sensitive adhesive sheet of the present invention can also with an organic solvent form solution with composition.As the organic solvent that uses, can list such as methylethylketone, acetone, ethyl acetate, tetrahydrofuran (THF), diox, pimelinketone, normal hexane, toluene, dimethylbenzene, n-propyl alcohol, Virahol etc.These organic solvents can use separately or two or more mixing.
Light solidified transparent pressure-sensitive adhesive sheet of the present invention is preferably 0～0.5mgKOH/g with the acid number of composition, more preferably 0～0.1mgKOH/g, more preferably 0～0.05mgKOH/g.If acid number is difficult to suppress the corrosion of the conductive layer surface of nesa coating higher than 0.5mgKOH/g.Need to prove, the acid number of composition is for measuring the value that obtains according to JISK0070.For example measure as described below.
With precision balance about 2g left and right sample of precision weighing in the 100ml Erlenmeyer flask, add wherein the mixed solvent 10ml of ethanol/diethyl ether=1/1 (weight ratio) to dissolve.Further add 1～3 phenolphthalein ethanolic soln as indicator in this container, fully stir until sample is even.It is carried out titration with 0.1N potassium hydroxide-ethanol solution, when the incarnadine of indicator continues 30 seconds as the terminal point of neutralization.To use value that following calculating formula (2) obtains as the acid number of composition by this result.
[mathematical expression 2]
Acid number (mgKOH/g)=[B * f * 5.611]/S (2)
The consumption (ml) of B:0.1N potassium hydroxide-ethanol solution
The factor of f:0.1N potassium hydroxide-ethanol solution
S: the amount of taking of sample (g)
(nesa coating is fixing with the transparent pressure-sensitive adhesive sheet composition)
Nesa coating of the present invention is fixing with the adhesive sheet composition, and is fixing with the adhesive sheet composition with the nesa coating of composition for comprising above-mentioned light solidified transparent pressure-sensitive adhesive sheet.
Fixing with the nesa coating of adhesive sheet with composition as using nesa coating of the present invention, get final product if top layer at least simultaneously has the nesa coating of conductive layer, can list the nesa coating that conducting material is set by evaporation, coating on the top layer of transparent substrate.Evaporation, the conducting material that is coated on the conductive layer of nesa coating are not particularly limited, particularly, can list tin indium oxide, Indium sesquioxide, stannic oxide, zinc oxide, Cadmium oxide, gallium oxide, titanium oxide etc.Wherein, be fit to use the tin indium oxide of the transparency, excellent electric conductivity.In nesa coating, be not particularly limited as the base material of evaporation, coated with conductive material, can list glass, resin film etc.
(the fixing transparent pressure-sensitive adhesive sheet of using of nesa coating)
Nesa coating of the present invention is fixing is the fixing nesa coating that forms with composition curing with transparent pressure-sensitive adhesive sheet of above-mentioned nesa coating to be fixed use transparent pressure-sensitive adhesive sheet with transparent pressure-sensitive adhesive sheet, can paste suitably with the conductive layer surface of nesa coating and be difficult for producing the corrosion of conductive layer.Therefore, the fixing duplexer that forms with the conductive layer surface stickup of transparent pressure-sensitive adhesive sheet and nesa coating of nesa coating can be used as touch panel suitably.In addition, nesa coating of the present invention is fixing can or not have the double-sided adhesive sheet that base material is only formed by binder layer for adhesive sheet with base material with transparent pressure-sensitive adhesive sheet.In addition, binder layer can only be formed by simple layer or stacked multilayer forms.Wherein, consider from the viewpoint of guaranteeing the transparency, product having shape-following-up properties, be preferably the double-sided adhesive sheet that does not have base material and only formed by binder layer.
Nesa coating of the present invention is fixing can followingly be obtained with transparent pressure-sensitive adhesive sheet: the coating nesa coating is fixing with the transparent pressure-sensitive adhesive sheet composition on demoulding PET film, the composition that is coated with used the irradiation ultraviolet radiation such as UV irradiation equipment and make its photocuring, can obtain thus nesa coating of the present invention and fixedly use transparent pressure-sensitive adhesive sheet.The fixing thickness with adhesive sheet of nesa coating is preferably 5～500 μ m, more preferably 10～300 μ m.If be thicker than if exist the fixing thickness with adhesive sheet of nesa coating to be thinner than the applying that 5 μ m are difficult to carry out adhesive sheet the tendency that 500 μ m are difficult to control thickness.
Nesa coating of the present invention fixing with adhesive sheet preferably in toluene under room temperature the gel fraction of by following formula (3) being tried to achieve of dipping in the time of 24 hours be 80～100%, more preferably 90～100%.There is stamping-out to add easily to produce the tendency of the wire drawing that is derived from the processing end face etc. in the gel fraction of adhesive sheet lower than 80% the time man-hour.
[mathematical expression 3]
Gel fraction (%)=[(toluene of adhesive sheet floods rear, the dried quality of toluene)/(quality before the toluene dipping of adhesive sheet)] * 100 (3)
Embodiment
With comparative example, the present invention is carried out more specific description by the following examples, but the present invention is not subjected to any restriction of these examples.
＜contain the polyolefin compound (A-1) of (methyl) acryl 〉
to having thermometer, agitator, dropping funnel, add 101.2g isophorone diisocyanate and 844.3g C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system in four neck flasks of the cooling tube of subsidiary drying tube, goods name: GI-3000, weight-average molecular weight 14000), react under 60 ℃, be time point below 1% at the residual isocyanate base, add 53.9g vinylformic acid 2-hydroxy methacrylate, be warming up to 70 ℃ of reactions 2 hours, after measuring the disappearance of confirmation isocyanate group by IR, finish reaction, the polyolefin compound (A-1) (weight-average molecular weight is 50000) that is contained (methyl) acryl.
＜contain the polyolefin compound (A-2) of (methyl) acryl 〉
Add 152.9g isophorone diisocyanate and 764.5g C-terminal hydrogenated polyisoprene (Idemitsu Kosen Co., Ltd.'s system, goods name: Epol, weight-average molecular weight 12000) in four neck flasks of the cooling tube with thermometer, agitator, dropping funnel, subsidiary drying tube, react under 60 ℃.Be time point below 1% at the residual isocyanate base; add 81.7g vinylformic acid 2-hydroxy methacrylate; be warming up to 70 ℃ of reactions 2 hours; after measuring the disappearance of confirmation isocyanate group by IR; finish reaction, contained the polyolefin compound (A-2) (weight-average molecular weight is 55000) of (methyl) acryl.
＜contain the polyolefin compound (A-3) of (methyl) acryl 〉
to having thermometer, agitator, dropping funnel, add 246.1g isophorone diisocyanate and 618.5g C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system in four neck flasks of the cooling tube of subsidiary drying tube, goods name: GI-1000, weight-average molecular weight 3000), react under 60 ℃, be time point below 1% at the residual isocyanate base, add 135.0g vinylformic acid 2-hydroxy methacrylate, be warming up to 70 ℃ of reactions 2 hours, after measuring the disappearance of confirmation isocyanate group by IR, finish reaction, the polyolefin compound (A-3) (weight-average molecular weight is 5000) that is contained (methyl) acryl.
＜contain the polyolefin compound (A-4) of (methyl) acryl 〉
Add 61.2g isophorone diisocyanate and 917.1g C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system, goods name: GI-3000, weight-average molecular weight 14000) in four neck flasks of the cooling tube with thermometer, agitator, dropping funnel, subsidiary drying tube, react under 60 ℃, be time point below 1% at the residual isocyanate base, add 21.3g vinylformic acid 2-hydroxy methacrylate, being warming up to 70 ℃ reacts, but polymer quantizes as a result, and reaction is gelation midway.
(embodiment 1～6, comparative example 1～4)
With the compounding respectively of the composition shown in table 1, use dispersion machine to mix under room temperature, prepare thus uniform light solidified transparent pressure-sensitive adhesive sheet composition.Use apparatus for coating that prepared light solidified transparent pressure-sensitive adhesive sheet is coated on demoulding PET film (100mm * 100mm * 100 μ m) with 200 μ m thickness with composition, after upper surface covers with the thick demoulding PET film of 25 μ m, use UV irradiation equipment (Nippon Storage Battery Co., Ltd's system, UV irradiating unit 4kw * 1, output: 160W/cm, metal halide lamp), at the about 500mJ/cm of irradiation distance 12cm, lamp translational speed 20m/ minute, irradiation dose
2Condition under irradiation ultraviolet radiation above-mentioned light solidified transparent pressure-sensitive adhesive sheet is solidified with composition, obtain being about by the thickness that demoulding PET film clips the adhesive sheet of 200 μ m.Need to prove; therefore due to the polyolefin compound that contains (methyl) acryl (A-4) gelation, contain light solidified transparent pressure-sensitive adhesive sheet that weight-average molecular weight surpasses 300,000 the polyolefin compound that contains (methyl) acryl and can not prepare with the comparative example of composition.
(reckoning of theoretical second-order transition temperature)
For embodiment and comparative example, the theoretical second-order transition temperature that is had the polymkeric substance that (methyl) acrylate of hydroxyl and (C) photopolymerization monomer form by (B) that use is calculated by above-mentioned formula (1).Result is as shown in table 1.
(acid number)
The light solidified transparent pressure-sensitive adhesive sheet of embodiment and comparative example uses aforesaid method through type (2) to calculate with the acid number of composition.Result is as shown in table 1.
(resistance value of indium tin oxides film is measured)
To be downcut the size of 50mm * 50mm by adhesive sheet obtained above, peel off the thick demoulding PET film of 25 μ m, fit in 100mm * 100mm evaporation the indium tin oxides film surface of PET film of tin indium oxide.Use resistance value determinator Mitsubishi chemical Co., Ltd's system " Loresta-GP " to measure initial resistance value (R to the two ends of the adhesive sheet of fitting
1).Be fitted with adhesive sheet evaporation the PET film of tin indium oxide placed 500 hours under 60 ℃, 90%RH condition, place 1 hour under 23 ℃, 50%RH condition after, measure the resistance value (R with initial same area
2).The resistance value rate of rise of indium tin oxides film is calculated by following formula (4).
[mathematical expression 4]
The resistance value rate of rise (%) of indium tin oxides film=((R
2-R
1)/R
1) * 100 (4)
The evaluation of resistance value rate of rise is undertaken by following benchmark.Result is as shown in table 1.
Zero: the resistance value rate of rise is less than 5%
△: the resistance value rate of rise is more than 5% and less than 10%
*: the resistance value rate of rise is more than 10%
(bounding force of adhesive sheet is measured)
To be downcut by adhesive sheet obtained above the size of 25 * 100mm, after peeling off the demoulding PET film that in the demoulding PET film that is present in the adhesive sheet two sides, 100 μ m are thick, rubber rollers by making 2kg (width: approximately 50mm) pastes adhesive face (mensuration face) on test board for reciprocal 1 time, makes test sample.Use sheet glass as test board.For resulting test sample, placed 24 hours under 23 ℃, the environment of humidity 50%, carry out the tension tests of 180 degree directions according to JIS Z0237 with 300mm/ minute peeling rate, measure adhesive sheet to the bounding force (N/25mm) of sheet glass.Resulting measured value is as bounding force.Result is as shown in table 1.
(total light transmittance mensuration)
To be downcut the size of 30mm * 30mm by adhesive sheet obtained above, peel off the thick demoulding PET film of 25 μ m in the demoulding PET film that is present in the adhesive sheet two sides, be fitted on sheet glass, with the gained duplexer as test sample.Use Murakami K. K.'s dye technology institute system " HR-100 type " for test sample, measure total light transmittance (%).Result is as shown in table 1.
(gel fraction)
Adhesive sheet is downcut the size of 20mm * 40mm, make test sample.After under 23 ℃, this test sample being flooded 24 hours in toluene, take out test sample from toluene.Then with test sample under 130 ℃ dry 1 hour.Then measure the weight of dried test sample, calculate gel fraction by above-mentioned formula (3).Result is as shown in table 1.
[table 1]
As shown in Table 1, the light solidified transparent pressure-sensitive adhesive sheet of the present invention that obtains in embodiment is compared with comparative example with composition, resistance value rate of rise, total light transmittance, bounding force excellence.
Utilizability on industry
Light solidified transparent pressure-sensitive adhesive sheet of the present invention is excellent owing to having the high transparency, preventing metal corrosion and binding property with composition, fixing as nesa coating is useful with adhesive sheet, and fixedly being used for of the nesa coating that particularly uses in the touch panel for capacitance-type says useful.
Claims (11)
1. light solidified transparent pressure-sensitive adhesive sheet composition, it is characterized in that, it contains (A) weight-average molecular weight is 10,000～300,000 the polyolefin compound that contains (methyl) acryl, (B) has (methyl) acrylate of hydroxyl, (C) have photopolymerization monomer and (D) Photoepolymerizationinitiater initiater beyond (methyl) acrylate of hydroxyl, (C) having the carboxylic monomer that contains that contains in (methyl) acrylate photopolymerization monomer in addition of hydroxyl is below 0.1 quality % with respect to the total amount that (C) has (methyl) acrylate photopolymerization monomer in addition of hydroxyl.
2. light solidified transparent pressure-sensitive adhesive sheet composition according to claim 1; it is characterized in that; with the total amount of composition, contain (A) weight-average molecular weight and be photopolymerization monomer 20～88 quality % and (D) Photoepolymerizationinitiater initiater 0.2～5 quality % beyond 10,000～300,000 the polyolefin compound that contains (methyl) acryl 10～50 quality %, (methyl) acrylate 1～30 quality % that (B) has hydroxyl, (methyl) acrylate that (C) has hydroxyl with respect to the light solidified transparent pressure-sensitive adhesive sheet.
3. light solidified transparent pressure-sensitive adhesive sheet composition according to claim 1 and 2, is characterized in that, (methyl) acrylate photopolymerization monomer in addition that (C) has hydroxyl does not comprise and contains carboxylic monomer.
4. the described light solidified transparent pressure-sensitive adhesive sheet of any one composition according to claim 1～3, it is characterized in that (B) had (methyl) acrylate of hydroxyl and (C) have the photopolymerization monomer polymerization beyond (methyl) acrylate of hydroxyl and the theoretical second-order transition temperature of the polymkeric substance that obtains is 0 ℃～50 ℃.
5. the described light solidified transparent pressure-sensitive adhesive sheet of any one composition according to claim 1～4, it is characterized in that, (methyl) acrylate photopolymerization monomer in addition that (C) has hydroxyl is simple function (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester.
6. the described light solidified transparent pressure-sensitive adhesive sheet of any one composition according to claim 1～5; it is characterized in that, (A) weight-average molecular weight is that 10,000～300,000 the polyolefin compound that contains (methyl) acryl is to make the polyolefin polyhydric alcohol compound, have the compound with (methyl) acryl that the compound reaction that has two above isocyanate group in (methyl) acrylate of hydroxyl and a part obtains.
7. the described light solidified transparent pressure-sensitive adhesive sheet of any one composition according to claim 1～6, is characterized in that, acid number is below 0.5mgKOH/g.
8. a nesa coating is fixing with the transparent pressure-sensitive adhesive sheet composition, it is characterized in that, the described light solidified transparent pressure-sensitive adhesive sheet of any one in claim 1～7 is solidified and the light solidified transparent pressure-sensitive adhesive sheet that obtains is used for the applying of nesa coating with composition.
9. a nesa coating is fixed and is used transparent pressure-sensitive adhesive sheet, it is characterized in that, nesa coating claimed in claim 8 is fixing to be solidified to obtain with composition with transparent pressure-sensitive adhesive sheet by making.
10. nesa coating according to claim 9 is fixing uses transparent pressure-sensitive adhesive sheet, it is characterized in that, gel fraction is 80～100%.
11. a duplexer is characterized in that, forms by the fixing conductive layer surface that sticks on nesa coating with transparent pressure-sensitive adhesive sheet of the described nesa coating of claim 9 or 10.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010209966 | 2010-09-17 | ||
| JP2010-209966 | 2010-09-17 | ||
| JP2010-256259 | 2010-11-16 | ||
| JP2010256259 | 2010-11-16 | ||
| PCT/JP2011/069288 WO2012035958A1 (en) | 2010-09-17 | 2011-08-26 | Light-curing composition for use in transparent pressure-sensitive adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103108930A true CN103108930A (en) | 2013-05-15 |
| CN103108930B CN103108930B (en) | 2014-08-20 |
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| CN201180044682.0A Active CN103108930B (en) | 2010-09-17 | 2011-08-26 | Light-curing composition for use in transparent pressure-sensitive adhesive sheet |
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| Country | Link |
|---|---|
| JP (1) | JP5854404B2 (en) |
| KR (1) | KR101494984B1 (en) |
| CN (1) | CN103108930B (en) |
| TW (1) | TWI515281B (en) |
| WO (1) | WO2012035958A1 (en) |
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| CN111484803A (en) * | 2013-10-10 | 2020-08-04 | 艾利丹尼森公司 | Adhesives and related methods |
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| US11049421B2 (en) | 2015-02-05 | 2021-06-29 | Avery Dennison Corporation | Label assemblies for adverse environments |
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| CN111556888A (en) * | 2018-01-09 | 2020-08-18 | 东亚合成株式会社 | Adhesive composition, and battery material, lithium ion battery material, heat-fusible member, and lithium ion battery packaging material using same |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103108930B (en) | 2014-08-20 |
| JP5854404B2 (en) | 2016-02-09 |
| KR20130056340A (en) | 2013-05-29 |
| KR101494984B1 (en) | 2015-02-23 |
| WO2012035958A1 (en) | 2012-03-22 |
| TWI515281B (en) | 2016-01-01 |
| TW201213482A (en) | 2012-04-01 |
| JPWO2012035958A1 (en) | 2014-02-03 |
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