CN103108930B - 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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- CN103108930B CN103108930B CN201180044682.0A CN201180044682A CN103108930B CN 103108930 B CN103108930 B CN 103108930B CN 201180044682 A CN201180044682 A CN 201180044682A CN 103108930 B CN103108930 B CN 103108930B
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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
- 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
-
- 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
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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
- 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
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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
- 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
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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
- B32B2250/02—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
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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
- B32B2255/20—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
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 light solidified transparent pressure-sensitive adhesive sheet is solidified with composition and obtain is fixing with transparent pressure-sensitive adhesive sheet composition for the nesa coating of the laminating of nesa coating, nesa coating is fixed with transparent pressure-sensitive adhesive sheet and fixed with transparent pressure-sensitive adhesive sheet and be characterised in that the fixing duplexer that sticks on the conductive layer surface of nesa coating with transparent pressure-sensitive adhesive sheet of nesa coating with the curing nesa coating obtaining of composition.
Background technology
In recent years in the field such as portable phone, game machine, start to load touch panel.Touch panel is for being used optics with transparent pressure-sensitive adhesive sheet, top layer to be had to its transparency protected and the duplexer that forms of the display unit class optical component laminating such as liquid-crystal display 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 pressure when touch panel mainly contains 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 contacting 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 containing in tackiness agent, produces the problem that conducting function reduces.Therefore, for nesa coating is fixing, with adhesive sheet, require high preventing metal corrosion.
As the adhesive sheet with preventing metal corrosion, the adhesive sheet (for example patent documentation 1) that contains preventing metal corrosion agent has been proposed.In addition, propose the nitrogen atom composition that contains specified quantitative by the sour composition with respect to binder layer, 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 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 containing in binder layer.
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 if the curing transparent pressure-sensitive adhesive sheet obtaining is provided directly fits and 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 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 inventor etc. be take foregoing problems that touch panel exists with light solidified transparent pressure-sensitive adhesive sheet and are 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, based on this discovery, completes the present invention; What described light solidified transparent pressure-sensitive adhesive sheet had a high molecular with composition compounding contains (methyl) acryl (chemical formula :-COCH=CH
2,-COC (CH
3)=CH
2) polyolefin compound, there is hydroxyl (chemical formula: (methyl) acrylate, photopolymerization monomer and Photoepolymerizationinitiater initiater-OH), the carboxylic monomer containing in photopolymerization monomer is below specified amount.
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 photopolymerization monomer 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 and (D) Photoepolymerizationinitiater initiater, and the total amount (C) with the photopolymerization monomer beyond (methyl) acrylate with respect to (C) containing carboxylic monomer with hydroxyl containing in the photopolymerization monomer beyond (methyl) acrylate of hydroxyl is below 0.1 quality %.
(2) according to the light solidified transparent pressure-sensitive adhesive sheet composition (1) described; it is characterized in that; with respect to the total amount of composition for light solidified transparent pressure-sensitive adhesive sheet, contain (A) weight-average molecular weight and be photopolymerization monomer 20～88 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 and (D) Photoepolymerizationinitiater initiater 0.2～5 quality %.
(3) according to the light solidified transparent pressure-sensitive adhesive sheet composition above-mentioned (1) or (2) Suo Shu, it is characterized in that, the photopolymerization monomer (C) having beyond (methyl) acrylate of hydroxyl does not comprise containing carboxylic monomer.
(4) according to the light solidified transparent pressure-sensitive adhesive sheet composition described in any one in above-mentioned (1)～(3), it is characterized in that (B) had to (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 light solidified transparent pressure-sensitive adhesive sheet composition described in any one in above-mentioned (1)～(4), it is characterized in that, the photopolymerization monomer (C) having beyond (methyl) acrylate of hydroxyl is simple function (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester.
(6) according to the light solidified transparent pressure-sensitive adhesive sheet composition described in any one 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 polyolefin polyhydric alcohol compound, have and in (methyl) acrylate of hydroxyl and a part, have the compounds with (methyl) acryl that the compound reaction of two above isocyanate group obtains.
(7) according to the light solidified transparent pressure-sensitive adhesive sheet composition described in any one 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 transparent pressure-sensitive adhesive sheet composition, it is characterized in that, the light solidified transparent pressure-sensitive adhesive sheet described in any one in above-mentioned (1)～(7) is solidified with composition and the light solidified transparent pressure-sensitive adhesive sheet that obtains for the laminating of nesa coating.
(9) nesa coating is fixing is characterized in that with a transparent pressure-sensitive adhesive sheet, and above-mentioned by making (8) described nesa coating is fixed and solidified to obtain with composition with transparent pressure-sensitive adhesive sheet.
(10) according to the nesa coating above-mentioned (9) Suo Shu is fixing, with transparent pressure-sensitive adhesive sheet, it is characterized in that, gel fraction is 80～100%.
(11) duplexer, is characterized in that, by the nesa coating above-mentioned (9) or (10) Suo Shu is fixing, with the conductive layer surface that transparent pressure-sensitive adhesive sheet sticks on nesa coating, forms.
the effect of invention
Light solidified transparent pressure-sensitive adhesive sheet of the present invention with composition owing to containing the polyolefin compound that contains (methyl) acryl of high molecular in composition; make it solidify flexibility, the resistance to excellent moisture permeability of the adhesive sheet obtaining; further owing to only containing micro-carboxyl 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
The present invention is described in detail below.
[light solidified transparent pressure-sensitive adhesive sheet composition]
Light solidified transparent pressure-sensitive adhesive sheet of the present invention contains photopolymerization monomer 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 and (D) Photoepolymerizationinitiater initiater with composition.
(polyolefin compound that (A) contains (methyl) acryl)
As the polyolefin compound that contains (methyl) acryl, if there is 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.From the viewpoint of photostabilization, the transparency (amorphism), operability (liquid state), consider, be preferably hydrogenated butadiene polymer, hydrogenated polyisoprene skeleton.It should be noted that, (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; can exemplify use (methyl) vinylformic acid and molecular end etc. be there is to the polyolefine esterification of reactive hydroxyl; or first the isocyanate compound in a part with two above isocyanate group is added to polyolefinic hydroxyl; make isocyanate group and (methyl) acrylate reactions with hydroxyl, carry out thus the method for (methyl) propylene acidylate.
Wherein, polyolefin polyhydric alcohol compound is reacted with the isocyanate compound in a part with two above isocyanate group; then carry out with (methyl) acrylate with hydroxyl that urethane reacts and the polyolefin compound that contains (methyl) acryl that obtains is high preferred from the viewpoint of the force of cohesion of resulting adhesive sheet.
Polyolefin polyhydric alcohol compound has more than two hydroxyl in a part, preferably has 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.
Compound as having 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, from the viewpoint of photostabilization, the reactive easiness of controlling, consider, be preferably isophorone diisocyanate.In these a part, have the compound of two above isocyanate group can be separately with or two or more combination use.As the consumptions in a part with the isocyanate compound of two above isocyanate group, with respect to 100 mass parts polyolefin polyhydric alcohol, be preferably 8～35 mass parts, more preferably 10～30 mass parts, more preferably 11～25 mass parts.If there is the consumption of the isocyanate compound of two above isocyanate group in a part, be less than 8 mass parts; 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 (methyl) acrylate with hydroxyl with isocyanic ester radical reaction, can list (methyl) vinylformic acid hydroxyalkyl acrylate that the carbonatoms such as alkyl is 2～7 etc., as their concrete example, can exemplify (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 1, 3-butanediol ester, (methyl) vinylformic acid 1, 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, from reactive viewpoint, consider, be preferably vinylformic acid 2-hydroxy methacrylate and 2-hydroxyethyl methacrylate.As the consumption with (methyl) acrylate of hydroxyl, with respect to 100 mass parts polyolefin polyhydric alcohol, be preferably 3～18 mass parts, more preferably 4～15 mass parts, more preferably 5～13 mass parts.If there is the consumption of (methyl) acrylate of hydroxyl, be less than 3 mass parts; likely there is the olefin(e) compound without (methyl) acryl; the strength decreased of adhesive sheet; if there is 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.
The importing number of (methyl) acryl of the polyolefin compound that contains (methyl) acryl as (A) of the present invention, if having above (methyl) acryl in a part, preferably has 1～2 in 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 is less than at 10,000 o'clock, and due to the force of cohesion reduction of resulting adhesive sheet, the intensity of adhesive sheet is likely insufficient, so not preferred.In addition, molecular weight is greater than at 300,000 o'clock, and because light solidified transparent pressure-sensitive adhesive sheet was processed with too high being difficult to of viscosity of composition, the remarkable variation of operability, so not preferred.It should be noted that, the weight-average molecular weight in the present invention is for being used 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 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
The polyolefin compound that contains (methyl) acryl as (A), at the content in composition for light solidified transparent pressure-sensitive adhesive sheet, is preferably 10～50 quality %, more preferably 15～45 quality %, more preferably 20～40 quality % in composition.While 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 likely reduces, so not preferred.
((B) has hydroxyl (methyl) acrylate)
At this alleged (methyl) acrylate with hydroxyl, preferably do not there is carboxyl, can list (methyl) vinylformic acid hydroxyalkyl acrylate that the carbonatoms such as alkyl is 2～7 etc., as their concrete example, can exemplify (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 1, 3-butanediol ester, (methyl) vinylformic acid 1, 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, from the viewpoint of the bounding force of resulting adhesive sheet, consider, be preferably vinylformic acid 2-hydroxy methacrylate.For the content of (methyl) acrylate that there is hydroxyl for (B), preferably at light solidified transparent pressure-sensitive adhesive sheet with containing 1～30 quality % in composition, more preferably 5～25 quality %, more preferably 10～20 quality %.While being 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 %, the water tolerance variation of adhesive sheet, so not preferred.
((C) has the photopolymerization monomer beyond hydroxyl (methyl) acrylate)
(C) photopolymerization monomer (being sometimes referred to as below " photopolymerization monomer (C) ") having beyond (methyl) acrylate of hydroxyl is photopolymerization monomer, refer to the photopolymerization monomer having beyond (methyl) acrylate of hydroxyl, be preferably and do not contain carboxyl (chemical formula: monomer-COOH).As this monomer, be not particularly limited, can by 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, be for example 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, 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-bis-(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 acryloxy 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, diethyl acrylamide, the acrylamide derivatives such as (methyl) acryloyl morpholine, (methyl) acrylate that (methyl) glycidyl acrylate etc. contains epoxy group(ing) etc.Photopolymerization monomer as (C) of the present invention; from the Combination of polyolefin compound with containing (methyl) acryl, the binding property of adhesive sheet, intensity, photostabilization, stable on heating viewpoint consider, be preferably simple function (methyl) alkyl acrylate or (methyl) vinylformic acid cyclic alkyl ester.At this alleged simple function or polyfunctional functional group, refer to (methyl) acryl.(C) content of photopolymerization monomer preferably at light solidified transparent pressure-sensitive adhesive sheet with containing 20～88 quality % in composition, 20～70 quality % more preferably.40～69 quality % more preferably.While being 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 containing in the photopolymerization monomer of (C), methacrylic acid etc., containing for carboxylic monomer, with respect to the total amount of the photopolymerization monomer of (C), be below 0.1 quality %, more preferably below 0.05 quality %.(C) photopolymerization monomer does not further preferably comprise containing carboxylic monomer.If 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 containing carboxylic monomer.
The theoretical second-order transition temperature that there is the polymkeric substance that (methyl) acrylate of hydroxyl and photopolymerization monomer (C) form by (B) of the present invention from the intensity of adhesive sheet, the consideration of the viewpoint of bonding force, 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 the Tg of homopolymer (homopolymer) and the massfraction of this monomer (copolymerization ratio) based on forming each monomer of raw material monomer be calculated by the formula (1) of following FOX.
[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
nfor the massfraction (=(compounding amount/monomer total mass of each monomer)) 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 recording as in " Nian Ji Intraoperative Ha Application De Block ッ Network " (< < adhering technique handbook > >) of the Nikkan Kogyo Shimbun of Co., Ltd. of known data or the < < Polymer Handbook > > (< < polymer handbook > >) of Wiley-Interscience.Tg for the homopolymer of the monomer of not recording in above-mentioned known data, adopts the value of being tried to achieve by following method.That is, the monomer that becomes object is carried out to solution polymerization and obtain homopolymer solution, make this homopolymer solution curtain coating on release liner dry, make 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 ℃/min carries out means of differential scanning calorimetry mensuration, adopts 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.
As carbonyl, it is Photoepolymerizationinitiater initiater, can list for example benzophenone, dibenzoyl, bitter almond oil camphor, ω-bromoacetophenone, monochloroacetone, methyl phenyl ketone, 2, 2-diethoxy acetophenone, 2, 2-dimethoxy-2-phenyl methyl phenyl ketone, to dimethylamino benzoylformaldoxime, to dimethylamino Propiophenone, 2-chlorobenzophenone, 4, 4 '-dichloro benzophenone, 4, 4 '-bis-diethylamino benzophenone, Michler's keton, benzoin methylether, bitter almond oil camphor ethyl isobutyl ether, benzoin n-butylether, benzil dimethyl ketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, benzoyl methyl-formiate, 2, 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.As quinone, be Photoepolymerizationinitiater initiater, can list such as benzoquinones, anthraquinone etc.As azo, be Photoepolymerizationinitiater initiater, can list for example azobis isobutyronitrile, 2,2 '-di-isopropyl diazene (2,2 '-azobispropane), hydrazine etc.As thioxanthone, be Photoepolymerizationinitiater initiater, 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 by 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.
From the intensity of light solidified and resulting adhesive sheet, the viewpoint of fusible balance consider, (D) content of Photoepolymerizationinitiater initiater preferably at light solidified transparent pressure-sensitive adhesive sheet with in composition being 0.2～5 quality %, more preferably 0.5～3 quality %, more preferably 0.8～2 quality %.If (D) content of Photoepolymerizationinitiater initiater is less than 0.2 quality % and has the inadequate tendency of photocuring, if surpass the tendency that 5 quality % exist the binding property reduction of resulting adhesive sheet, so not preferred.
For light solidified transparent pressure-sensitive adhesive sheet of the present invention with for composition, preferably the total amount with composition with respect to light solidified transparent pressure-sensitive adhesive sheet, contains 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 the total amount with composition with respect to light solidified transparent pressure-sensitive adhesive sheet, contains 15～45 quality % (A) compositions, 5～25 quality % (B) compositions, 20～70 quality % (C) compositions and 0.2～5 quality % (D) composition.And further the preferred total amount of using composition with respect to light solidified transparent pressure-sensitive adhesive sheet, contains 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, with in composition, in order to improve the bonding force of resulting adhesive sheet, can also can not reduce in transparent scope and add tackifying resin as required.Example as tackifying resin, can list the rosin series resins such as carboxylate of rosin, rosin, the terpenes such as diterpene polymkeric substance, α-pinene-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.From sunproof viewpoint, consider, preferably by the few carboxylate of staybelite of unsaturated double-bond, the carboxylate of 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 with respect to composition 100 mass parts for light solidified transparent pressure-sensitive adhesive sheet (with respect to (A) composition, (B) composition, (C) composition and (D) total amount 100 mass parts of composition), add 1～10 mass parts.
In addition, light solidified transparent pressure-sensitive adhesive sheet of the present invention, with in composition, as required, can also contain known various additive in not damaging transparent scope.As additive, can list the such static inhibitor of the photostabilizers such as softening agent, surface lubricant, flow agent, tenderizer, antioxidant, protective agent, photostabilizer, UV light absorber, stopper, benzotriazole system, phosphoric acid ester system and other fire retardant, tensio-active agent etc.
In addition, the viscosity while 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 used organic solvent, 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 be used 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.It should be noted that, the acid number of composition is for measuring the value obtaining according to JISK0070.For example measure as described below.
With the precision balance about 2g of precision weighing left and right sample in 100ml Erlenmeyer flask, add wherein the mixed solvent 10ml of ethanol/diethyl ether=1/1 (weight ratio) to dissolve.Further in this container, add 1～3 phenolphthalein ethanolic soln as indicator, fully stir until sample is even.It is carried out to titration with 0.1N potassium hydroxide-ethanol solution, when the incarnadine of indicator continues 30 seconds as the terminal 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 transparent pressure-sensitive adhesive sheet composition)
Nesa coating of the present invention is fixing with adhesive sheet composition, fixing with adhesive sheet composition with the nesa coating of composition for comprising above-mentioned light solidified transparent pressure-sensitive adhesive sheet.
As using the fixing nesa coating of using composition with adhesive sheet of nesa coating of the present invention, if at least the top layer of one side 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 applicable to using the tin indium oxide of the transparency, excellent electric conductivity.In nesa coating, as the base material of evaporation, coated with conductive material, be not particularly limited, can list glass, resin film etc.
(nesa coating is fixing with transparent pressure-sensitive adhesive sheet)
Nesa coating of the present invention is fixing is to make above-mentioned nesa coating fixing fixing with transparent pressure-sensitive adhesive sheet with the curing nesa coating forming of composition with 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 duplexer that, the fixing stickup of the conductive layer surface with transparent pressure-sensitive adhesive sheet and nesa coating of nesa coating forms can be used as touch panel suitably.In addition, nesa coating of the present invention is fixing can be for having the adhesive sheet of base material or not having the double-sided adhesive sheet that base material is only formed by binder layer with transparent pressure-sensitive adhesive sheet.In addition, binder layer can only be formed by simple layer or stacked multilayer forms.Wherein, from guaranteeing the viewpoint consideration of the transparency, product having shape-following-up properties, be preferably the double-sided adhesive sheet that does not there is base material and only formed by binder layer.
Nesa coating of the present invention is fixing can be obtained as follows with transparent pressure-sensitive adhesive sheet: on demoulding PET film, be coated with nesa coating fixing with transparent pressure-sensitive adhesive sheet composition, be coated with composition used to the irradiation ultraviolet radiations 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.Nesa coating is fixing is preferably 5～500 μ m with the thickness of adhesive sheet, 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 laminating that 5 μ m are difficult to carry out adhesive sheet the tendency that 500 μ m are difficult to control thickness.
The gel fraction of being tried to achieve by following formula (3) that nesa coating of the present invention is fixing while preferably flooding 24 hours under room temperature in toluene with adhesive sheet is 80～100%, more preferably 90～100%.Lower than 80% time, there is stamping-out to add easily to produce man-hour the tendency of the wire drawing etc. that is derived from processing end face in the gel fraction of adhesive sheet.
[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 to more specific description by the following examples, but the present invention is not subject to any restriction of these examples.
The polyolefin compound that < contains (methyl) acryl (A-1) >
To thering is thermometer, agitator, dropping funnel, in four neck flasks of the cooling tube of subsidiary drying tube, add 101.2g isophorone diisocyanate and 844.3g C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system, goods name: GI-3000, weight-average molecular weight 14000), at 60 ℃, react, at residual isocyanate base, it is the time point below 1%, add 53.9g vinylformic acid 2-hydroxy methacrylate, be warming up to 70 ℃ of reactions 2 hours, by IR, measure and confirm after isocyanate group disappearance, finish reaction, the polyolefin compound that is contained (methyl) acryl (A-1) (weight-average molecular weight is 50000).
The polyolefin compound that < contains (methyl) acryl (A-2) >
To having in the four neck flasks of cooling tube of thermometer, agitator, dropping funnel, subsidiary drying tube, 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), react at 60 ℃.At residual isocyanate base, it is the time point below 1%; add 81.7g vinylformic acid 2-hydroxy methacrylate; be warming up to 70 ℃ of reactions 2 hours; by IR, measure and confirm after isocyanate group disappearance; finish reaction, the polyolefin compound that is contained (methyl) acryl (A-2) (weight-average molecular weight is 55000).
The polyolefin compound that < contains (methyl) acryl (A-3) >
To thering is thermometer, agitator, dropping funnel, in four neck flasks of the cooling tube of subsidiary drying tube, add 246.1g isophorone diisocyanate and 618.5g C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system, goods name: GI-1000, weight-average molecular weight 3000), at 60 ℃, react, at residual isocyanate base, it is the time point below 1%, add 135.0g vinylformic acid 2-hydroxy methacrylate, be warming up to 70 ℃ of reactions 2 hours, by IR, measure and confirm after isocyanate group disappearance, finish reaction, the polyolefin compound that is contained (methyl) acryl (A-3) (weight-average molecular weight is 5000).
The polyolefin compound that < contains (methyl) acryl (A-4) >
To having in the four neck flasks of cooling tube of thermometer, agitator, dropping funnel, subsidiary drying tube, 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), at 60 ℃, react, at residual isocyanate base, it is the time point below 1%, add 21.3g vinylformic acid 2-hydroxy methacrylate, being warming up to 70 ℃ reacts, but result polymer quantizes, reaction is gelation midway.
(embodiment 1～6, comparative example 1～4)
With the compounding respectively of the composition shown in table 1, under room temperature, use dispersion machine to mix, 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 irradiation distance 12cm, lamp translational speed 20m/ minute, the about 500mJ/cm of irradiation dose
2condition under irradiation ultraviolet radiation above-mentioned light solidified transparent pressure-sensitive adhesive sheet is solidified with composition, the thickness that obtains being clipped by demoulding PET film is about the adhesive sheet of 200 μ m.It should be noted that; therefore due to the polyolefin compound that contains (methyl) acryl (A-4) gelation, contain the 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 by used (B) with the polymkeric substance that (methyl) acrylate of hydroxyl and photopolymerization monomer (C) form 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 is used 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 by adhesive sheet obtained above, be cut the size of 50mm * 50mm, peel off the demoulding PET film that 25 μ m are thick, 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 fitted adhesive sheet
1).By be fitted with adhesive sheet evaporation the PET film of tin indium oxide under 60 ℃, 90%RH condition, place 500 hours, under 23 ℃, 50%RH condition, place after 1 hour, 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]
Resistance value rate of rise (the %)=((R of indium tin oxides film
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: resistance value rate of rise is less than 5%
△: resistance value rate of rise is more than 5% and is less than 10%
*: resistance value rate of rise is more than 10%
(bounding force of adhesive sheet is measured)
To be cut by adhesive sheet obtained above the size of 25 * 100mm, peel off after the demoulding PET film that in the demoulding PET film that is present in adhesive sheet two sides, 100 μ m are thick, by making the rubber rollers (width: about 50mm) reciprocal 1 time adhesive face (mensuration face) is pasted on test board, make test sample of 2kg.As test board, use sheet glass.For resulting test sample, under 23 ℃, the environment of humidity 50%, place 24 hours, according to JIS Z0237, with 300mm/ minute peeling rate, carry out the tension test of 180 degree directions, measure adhesive sheet to the bounding force of sheet glass (N/25mm).Resulting measured value is as bounding force.Result is as shown in table 1.
(total light transmittance mensuration)
To by adhesive sheet obtained above, be cut the size of 30mm * 30mm, peel off the thick demoulding PET film of 25 μ m in the demoulding PET film that is present in adhesive sheet two sides, be fitted on sheet glass, using gained duplexer as test sample.For test sample, use Murakami K. K.'s dye technology institute system " HR-100 type ", measure total light transmittance (%).Result is as shown in table 1.
(gel fraction)
Adhesive sheet is cut to the size of 20mm * 40mm, make test sample.At 23 ℃, this test sample was flooded after 24 hours in toluene, from toluene, take out test sample.Then test sample is dried to 1 hour at 130 ℃.Then measure the weight of dried test sample, by above-mentioned formula (3), calculate gel fraction.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 obtaining in embodiment is compared with comparative example with composition, resistance value rate of rise, total light transmittance, bounding force excellence.
utilizability in 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 being fixedly used for of the nesa coating particularly using in the touch panel for capacitance-type says useful.
Claims (9)
1. a light solidified transparent pressure-sensitive adhesive sheet composition; it is characterized in that; it contains photopolymerization monomer 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 and (D) Photoepolymerizationinitiater initiater; (C) total amount that has a photopolymerization monomer beyond (methyl) acrylate with respect to (C) containing carboxylic monomer with hydroxyl containing in the photopolymerization monomer beyond (methyl) acrylate of hydroxyl is below 0.1 quality %
(A) weight-average molecular weight is that 10,000～300,000 the polyolefin compound that contains (methyl) acryl is to make polyolefin polyhydric alcohol compound, have and in (methyl) acrylate of hydroxyl and a part, have the compounds with (methyl) acryl that the compound reaction of two above isocyanate group obtains
The acid number of described composition is 0～0.5mgKOH/g,
Acid number is according to the result of using 0.1N potassium hydroxide-ethanol solution as the neutralization titration of titrating solution, the value of using following calculating formula to calculate,
Acid number (mgKOH/g)=[B * f * 5.611]/S
The consumption of B:0.1N potassium hydroxide-ethanol solution, unit is ml,
The factor of f:0.1N potassium hydroxide-ethanol solution
S: the amount of taking of sample, unit is g.
2. light solidified transparent pressure-sensitive adhesive sheet composition according to claim 1; it is characterized in that; with respect to the total amount of composition for light solidified transparent pressure-sensitive adhesive sheet, contain (A) weight-average molecular weight and be photopolymerization monomer 20～88 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 and (D) Photoepolymerizationinitiater initiater 0.2～5 quality %.
3. light solidified transparent pressure-sensitive adhesive sheet composition according to claim 1 and 2, is characterized in that, the photopolymerization monomer (C) having beyond (methyl) acrylate of hydroxyl does not comprise containing carboxylic monomer.
4. light solidified transparent pressure-sensitive adhesive sheet composition according to claim 1 and 2, it is characterized in that (B) had to (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. light solidified transparent pressure-sensitive adhesive sheet composition according to claim 1 and 2, it is characterized in that, the photopolymerization monomer (C) having beyond (methyl) acrylate of hydroxyl is simple function (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester.
6. a nesa coating is fixing with transparent pressure-sensitive adhesive sheet composition, it is characterized in that, the light solidified transparent pressure-sensitive adhesive sheet described in any one in claim 1～5 is solidified with composition and the light solidified transparent pressure-sensitive adhesive sheet that obtains for the laminating of nesa coating.
7. nesa coating is fixing is characterized in that with a transparent pressure-sensitive adhesive sheet, and by making, nesa coating claimed in claim 6 is fixing to be solidified to obtain with composition with transparent pressure-sensitive adhesive sheet.
8. nesa coating according to claim 7 is fixing is characterized in that with transparent pressure-sensitive adhesive sheet, and gel fraction is 80～100%,
The quality of adhesive sheet when gel fraction floods 24 hours for fixing according to nesa coating with transparent pressure-sensitive adhesive sheet in toluene, the value of using following calculating formula to calculate,
Gel fraction (%)=[(toluene of adhesive sheet floods rear, the dried quality of toluene)/(quality before the toluene dipping of adhesive sheet)] * 100.
9. a duplexer, is characterized in that, by the nesa coating described in claim 7 or 8 is fixing, with the conductive layer surface that transparent pressure-sensitive adhesive sheet sticks on nesa coating, forms.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-209966 | 2010-09-17 | ||
| JP2010209966 | 2010-09-17 | ||
| JP2010256259 | 2010-11-16 | ||
| JP2010-256259 | 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 CN103108930A (en) | 2013-05-15 |
| CN103108930B true 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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| JP (1) | JP5854404B2 (en) |
| KR (1) | KR101494984B1 (en) |
| CN (1) | CN103108930B (en) |
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| CN103987803B (en) * | 2011-12-13 | 2015-12-09 | 昭和电工株式会社 | The manufacture method of transparent double face adhesive sheet, transparent double face adhesive sheet |
| JP5877099B2 (en) * | 2012-03-23 | 2016-03-02 | 昭和電工株式会社 | Composition for transparent adhesive sheet |
| JP2013242724A (en) * | 2012-05-21 | 2013-12-05 | Showa Denko Kk | Photosetting composition for transparent adhesive sheet and transparent adhesive sheet |
| US20150079379A1 (en) * | 2012-06-15 | 2015-03-19 | Showa Denko K.K. | Polymerizable composition, polymer, optical adhesive sheet, image display device, and method for manufacturing image display device |
| JP6049055B2 (en) * | 2012-08-08 | 2016-12-21 | 日本化薬株式会社 | UV curable resin composition, cured product and article |
| IN2015DN03074A (en) * | 2012-10-09 | 2015-10-02 | Avery Dennison Corp | |
| JP6508869B2 (en) * | 2013-02-14 | 2019-05-08 | 日東電工株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet, optical member, and touch panel |
| JP6097132B2 (en) * | 2013-04-22 | 2017-03-15 | 昭和電工株式会社 | Photocurable composition for transparent adhesive sheet, adhesive sheet using the same, and use thereof |
| JP6226652B2 (en) * | 2013-09-09 | 2017-11-08 | 昭和電工株式会社 | Manufacturing method of image display device |
| CN109439206B (en) * | 2013-10-10 | 2021-08-27 | 艾利丹尼森公司 | Adhesives and related methods |
| CN111484803A (en) * | 2013-10-10 | 2020-08-04 | 艾利丹尼森公司 | Adhesives and related methods |
| CN110079218B (en) * | 2013-10-10 | 2022-07-15 | 艾利丹尼森公司 | Adhesives and related methods |
| KR101900529B1 (en) * | 2014-09-16 | 2018-09-20 | 주식회사 엘지화학 | Adhesive composition for touch screen panel, optical adhesive film and touch screen panel |
| MX2017010047A (en) | 2015-02-05 | 2017-12-18 | Avery Dennison Corp | Label assemblies for adverse environments. |
| JP6969235B2 (en) * | 2016-09-05 | 2021-11-24 | 荒川化学工業株式会社 | UV curable adhesive, cured product, adhesive sheet |
| KR102197326B1 (en) * | 2016-09-28 | 2020-12-31 | 동우 화인켐 주식회사 | Adhesive Composition and Adhesive Sheet Using the Same |
| WO2018118767A1 (en) | 2016-12-22 | 2018-06-28 | Avery Dennison Corporation | Convertible pressure sensitive adhesives comprising urethane (meth) acrylate oligomers |
| TWI804552B (en) | 2018-01-09 | 2023-06-11 | 日商東亞合成股份有限公司 | Adhesive composition, and material for battery, material for lithium ion battery, thermal fusible member, and packging material for lithium ion battery, each using adhesive composition |
| CN113423792B (en) * | 2019-02-11 | 2023-09-05 | 汉高股份有限及两合公司 | Photocurable (meth) acrylate resin composition for thermoplastic elastomer bonding |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1953997A (en) * | 2004-09-27 | 2007-04-25 | 日立化成工业株式会社 | Photocurable resin composition |
Family Cites Families (6)
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| JPH07138332A (en) * | 1993-11-19 | 1995-05-30 | Nippon Zeon Co Ltd | Ultraviolet-curable composition, molded item with adhesive layer formed therefrom, and method for bonding molded item |
| JP2873910B2 (en) * | 1994-05-16 | 1999-03-24 | 本田技研工業株式会社 | Sticking jig and sticking device for foil rust prevention film |
| JP2000038547A (en) * | 1998-07-24 | 2000-02-08 | Mitsubishi Rayon Co Ltd | Photocuring adhesive composition and optical member using same |
| JP5409994B2 (en) * | 2006-10-20 | 2014-02-05 | 電気化学工業株式会社 | Curable composition |
| TWI485214B (en) * | 2008-09-05 | 2015-05-21 | Kyoritsu Chemical Co Ltd | And a photohardenable resin composition for bonding an optical functional material |
| JP5277937B2 (en) * | 2008-12-17 | 2013-08-28 | Ｄｉｃ株式会社 | Double-sided adhesive sheet for fixing transparent conductive film, transparent conductive film laminate, touch panel device |
-
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Non-Patent Citations (4)
| Title |
|---|
| JP特开2000-38547A 2000.02.08 |
| JP特开2008-101151A 2008.05.01 |
| JP特开2010-144002A 2010.07.01 |
| JP特开平7-309510A 1995.11.28 |
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| KR20130056340A (en) | 2013-05-29 |
| TWI515281B (en) | 2016-01-01 |
| TW201213482A (en) | 2012-04-01 |
| KR101494984B1 (en) | 2015-02-23 |
| JPWO2012035958A1 (en) | 2014-02-03 |
| JP5854404B2 (en) | 2016-02-09 |
| CN103108930A (en) | 2013-05-15 |
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