CN103360999B - Sticker and adhesive sheet - Google Patents
Sticker and adhesive sheet Download PDFInfo
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- CN103360999B CN103360999B CN201310111386.9A CN201310111386A CN103360999B CN 103360999 B CN103360999 B CN 103360999B CN 201310111386 A CN201310111386 A CN 201310111386A CN 103360999 B CN103360999 B CN 103360999B
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- Prior art keywords
- methyl
- sticker
- agent layer
- adhering agent
- acrylate polymer
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Abstract
A kind of concavo-convex tracing ability and the sticker of excellent heat resistance and adhesive sheet, it is characterized in that: using adhering agent layer gel fraction time newly formed as G1, at 23 DEG C after adhering agent layer is formed, when carrying out the gel fraction after keeping in 7 days in the environment of 50%RH as G2, the gel fraction rate of change calculated from following formula is within 3%, elongation at break during tension test is 100-250%, and fracture strength is 0.2-0.6N/mm2.The gel fraction rate of change (%)=| (G2-G1)/G2| × 100.
Description
Technical field
The present invention relates to sticker (material that adherence composition hardens) and adhesive sheet.
Background technology
In recent years, the excellent sticker as the concavo-convex tracing ability of of character of sticker is expected to.
Such as, in liquid crystal panel, in order to make polarizer and polarizer at the glass substrate etc. of liquid crystal cells
On then, adhesion agent composition the adhering agent layer formed is used.In recent years, slim along with liquid crystal panel
The progress changed, will carry out mechanical lapping to liquid crystal cells, make to thinning.Such mechanical lapping can make liquid crystal
The surface of unit becomes coarse, but, for guaranteeing the liquid crystal cells of rough surface and the close of adhering agent layer
The property, it is desirable to the raising concavo-convex tracing ability to the adhering agent layer on the surface of roughening.
It addition, be set to the surface bubble-free etc. of the transparent conducting film of the transparency conducting layer of pattern-like
Be mixed into by adhering agent layer lamination, or on hard coated thin film surface, be provided with the printing of the section difference of patterning
Layer, on a surface, bubble-freely by adhering agent layer lamination, or by the framework of suitable portable telephone
The section difference adhering agent layer of the light shield layer of part is buried etc., it is desirable to uses midway various, obtains concavo-convex
The sticker that tracing ability is excellent.
In order to make the concavo-convex tracing ability of adhering agent layer improve, such as, as patent document 1 and 2
, plasticizer and Liquid Paraffin are added in acrylic acid series sticker, so that the adhering agent layer appropriateness obtained
Soft.
Look-ahead technique document
Patent document
[patent document 1] Japanese Unexamined Patent Publication 5-45517 publication
[patent document 2] Japanese Unexamined Patent Publication 9-137143 publication
But, the sticker that the interpolation of plasticizer and Liquid Paraffin obtains, have cohesive force insufficient,
The foaming of adhesion step-down, the problem that heat resistance is low under high temperature.It addition, plasticizer and flowing over time
Paraffin oozes out from adhering agent layer, makes then durability step-down, and to-be-adhered object is contaminated, various
Problem is worried.
The present invention, it is simply that in view of such actual state, improves a kind of concavo-convex tracing ability and resistance to
Hot excellent sticker and adhesive sheet.
Summary of the invention
The purpose of the present invention can be reached by following technical scheme:
1. a sticker, it is characterised in that: using adhering agent layer gel fraction time newly formed as G
1, adhering agent layer formed after at 23 DEG C, carry out in the environment of 50%RH 7 days keeping after gel
When point rate is as G2, the gel fraction rate of change calculated from following formula within 3%,
The gel fraction rate of change (%)=| (G2-G1)/G2| × 100
Elongation at break during tension test is 100-250%, and fracture strength is 0.2
-0.6N/mm2。
According to the sticker of above-mentioned 1, thus obtain physical property completely can not prediction, concavo-convex tracing ability and
The effect of excellent heat resistance.
Sticker described in the most above-mentioned 1, it is characterised in that: described sticker is for making to divide containing weight average
Son amount is (methyl) acrylate polymer (A) and the weight averaged molecular of 600,000-200 ten thousand
Amount is 30,000-10 ten thousand, and reactivity (methyl) acrylate that side chain has polymerism double bond gathers
The adherence composition of compound (B) hardens under the irradiation of active energy beam and forms.
Sticker described in the most above-mentioned 2, it is characterised in that: reactive (methyl) acrylate polymer (
B) the polymerism double bond on side chain is contained in (methyl) acryloyl being imported side chain by isocyanates
In base.
Sticker described in the most above-mentioned 2, it is characterised in that: to (methyl) acrylate polymer (A
) 100 mass parts, the amount of described reactivity (methyl) acrylate polymer (B) is 5-30
Mass parts.
Sticker described in the most above-mentioned 2, it is characterised in that: described adherence composition, contains further
Photoepolymerizationinitiater initiater (C).
Sticker described in the most above-mentioned 5, it is characterised in that: to described reactivity (methyl) acrylate
Polymer (B) 100 mass parts, the amount of described Photoepolymerizationinitiater initiater (C) is 5-30 mass parts
。
Sticker described in the most above-mentioned 2, it is characterised in that: the exposure of described active energy beam is 5
0-1000mJ/cm2。
Sticker described in the most above-mentioned 1, it is characterised in that: described sticker is active energy beam hardening
The sticker of type.
Sticker described in the most above-mentioned 1, it is characterised in that: when adhering agent layer is newly formed with described 7 days
Gel fraction after Bao Guan is 30-60%.
Sticker described in the most above-mentioned 1, it is characterised in that: described haze value is below 1.0%.
11. 1 kinds of adhesive sheets, have base material and adhering agent layer, it is characterised in that: described adhering agent layer by
Sticker described in any one of above-mentioned 1-10 is formed.
Adhesive sheet described in 12. above-mentioned 11, it is characterised in that: described base material is optics.
13. 1 kinds of adhesive sheets, it is characterised in that: include the stripping film of 2 pieces and clamped by described stripping film,
The adhering agent layer that thus release surface with described 2 pieces of stripping films connects, it is characterised in that: described adhering agent layer
It is made up of the sticker described in any one of above-mentioned 1-10.
The effect of invention
The sticker of the present invention, by making adhering agent layer divide upon gel when being formed and after keeping in 7 days
The rate rate of change within the limits prescribed while, by make elongation at break and fracture strength regulation
Scope, thus obtain physical property completely can not prediction, concavo-convex tracing ability and the effect of excellent heat resistance.?
To concavo-convex tracing ability and the adhesive sheet of excellent heat resistance.
Accompanying drawing explanation
The sectional view of the adhesive sheet of the embodiment of the 1st of Fig. 1 present invention.
The sectional view of the adhesive sheet of the embodiment of the 2nd of Fig. 2 present invention.
Fig. 3 illustrates the plane of the concavo-convex tracing ability test of adhering agent layer.
The concavo-convex tracing ability of adhering agent layer is tested the schematic section illustrated by Fig. 4.
Detailed description of the invention
Hereinafter, embodiments of the present invention are illustrated.
(physical property of sticker)
The sticker of present embodiment is,
Gel fraction when using adhering agent layer upon formation, as G1, from adhering agent layer formation, arrives
23 DEG C, in the environment of 50%RH in 7 days keeping after gel fraction as G2, with following
Formula
The gel fraction rate of change (%)=| (G2-G1)/G2| × 100
Within the gel fraction rate of change calculated is 3%, the elongation at break of tension test is 100-25
0%, and fracture strength is 0.2-0.6N/mm2.Meet the sticker of this physical property,
Concavo-convex tracing ability and excellent heat resistance.Its reason is the most indefinite, but the above-mentioned gel fraction rate of change
, elongation at break and fracture strength are relevant with the both sides of concavo-convex tracing ability and heat resistance.
Here, so-called adhering agent layer is upon when being formed, formed for adhering agent layer, until the most another when using
Initial period in the state of outer artificial disposal.Such as, the sticker of active energy beam constrictive type
Occasion, refer to active energy beam just irradiate after the meaning.It addition, in practical measurement, due to from sample
Being fabricated into various mensuration when starting to need the corresponding time, so-called adhering agent layer, upon when being formed, never refers to
Carry out the state of above-mentioned artificial disposal again to the time approximately passing through degree on the half.
The assay method of above-mentioned gel fraction, test example described as follows is such.Gel fraction as above-mentioned
Within the rate of change is 3%, refer to from adhering agent layer upon formed time to sticker be hardened to the completeest
?.That is, stabilize upon all physical property to sticker when being formed from adhering agent layer.But, this embodiment party
The sticker of formula is, it is not necessary to the most necessary maturation, thus, has the adhesion formed by this sticker
Dispatching from the factory and putting into next operation of the parts of oxidant layer just can promptly be carried out, and this is at intermediate materials
Stock's burden and the face of production efficiency be very favorable.
Adhering agent layer is upon the gel fraction after gel fraction G1 when being formed and keeping in above-mentioned 7 days
G2 is, is preferred with 30-60% respectively, is particularly preferred with 32-56%, enters one
Step is preferred with 35-50%.If gel fraction is 30% not enough less than the cohesive force of, sticker
, durability (heat resistance) under high temperature has the occasion of step-down.It addition, if gel fraction is more than 60%
, the concavo-convex tracing ability of sticker has the occasion of step-down.
Above-mentioned tension test is, the width 10mm formed by lamination etc., length 20mm, and
The sticker sheet (without the single adhering agent layer of base material etc.) of thickness 500 μm with tension test with
The speed tensile that 200mm/ divides is carried out.The above-mentioned tension test of the sticker of present embodiment
Elongation at break is characterized with 100-250%.Elongation at break such as 100% less than, concavo-convex
Tracing ability has the occasion of step-down, as more than 250%, has the occasion of heat resistance step-down.From such sight
Point, above-mentioned elongation at break, preferably 110-240%, particularly preferably 115-23
0%, more preferably 130-200%.
It addition, the fracture strength of above-mentioned tension test is with 0.2-0.6N/mm2It is characterized.
If fracture strength is 0.2N/mm2Less than, there is the possibility of heat resistance step-down, as more than 0.6
N/mm2, concavo-convex tracing ability has the occasion of step-down.From such viewpoint, above-mentioned fracture strength, excellent
Elect 0.2-0.5N/mm as2。
The haze value (value measured by JISK7105) of the sticker of present embodiment is,
Less than 1.0% is preferably, is particularly preferred with less than 0.7%, further with 0.5% with
Lower is preferred.If haze value is less than 1.0%, the transparency is the highest, it is considered to fitting of optical applications etc.
With, for suitably.
(adherence composition)
The sticker of present embodiment, is preferred with the sticker of active energy beam constrictive type.It addition,
The sticker of so-called active energy beam constrictive type, uses as sticker after irradiating for active energy beam
Sticker.
There is the sticker of above-mentioned physical property, will be preferably 600,000-20 containing weight average molecular weight
(methyl) acrylate polymer (A) of 00000 (below, has the field only claiming " polymer (A) "
Close.) and, weight average molecular weight is 30,000-10 ten thousand, and side chain has the reaction of polymerism double bond
Property (methyl) acrylate polymer (B) (following, to have the occasion only claiming " polymer (B) ")
Adherence composition (hereinafter referred to as " adherence composition P "), carry out with the irradiation of active energy beam
Harden and obtain.It addition, in this specification, so-called (methyl) acrylate, refer to acrylate and first
Two sides of base acrylate.Other similar term is too.It addition, " polymer " also includes " altogether
Polymers " concept.
In the past, the polymer of low-molecular-weight uses as plasticizer, obtains from above-mentioned adherence composition P
To sticker in, the polymer (B) of multiple low-molecular-weights, the irradiation of active energy-ray, side chain
The cracking of polymerism double bond, be mutually bonded formation three-dimensional mesh structure.The polymer of multiple HMWs
(A), being inserted in three-dimensional mesh structure and restrained, the polymer (A) of HMW is each other
Form crosslinked configuration as intending (although restrained, but the structure of whether covalent bond) (presumption) (these
Structure is all is referred to as " structure X " below.Due to such structure X, this sticker, it is believed to
Play excellent concavo-convex tracing ability and heat resistance.Hereinafter, above-mentioned adherence composition P is illustrated
。
(methyl) acrylate polymer (A), for (the first that carbon number is 1-20 of preferred alkyl
Base) alkyl acrylate, (methyl) acrylate containing alkoxyalkyl used as required, root
According to need use the monomer (containing functional group monomer) with functional group and use as required other
The copolymer of monomer.Carbon number containing alkyl be 1-20 (methyl) alkyl acrylate and
Contain (methyl) acrylate with alkoxyalkyl, available desired to sticker imparting
Adhesion strength, containing functional group monomer be, this functional group the polarity having, be believed to make polymerization
Thing (A) effectively inserts in the three-dimensional mesh structure of polymer (B).
As (methyl) alkyl acrylate that carbon number is 1-20 of alkyl, (methyl can be enumerated
) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl)
N-butyl, (methyl) acrylic acid n-amyl group ester, (methyl) acrylic acid n-hexyl ester
, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) propylene
Acid isooctyl acrylate, (methyl) acrylic acid n-certain herbaceous plants with big flowers base ester, (methyl) acrylic acid n-dodecyl base ester,
(methyl) myristyl base ester, (methyl) acrylic acid palmityl ester, (methyl) stearyl acrylate
Base ester etc..They can be used alone, it is also possible to two or more is applied in combination.
As (methyl) acrylate containing alkoxyalkyl, (methyl) acrylic acid first can be enumerated
Epoxide methyl ester, (methyl) methoxyethyl ethyl ester, (methyl) methoxypropyl base ester,
(methyl) methoxyethyl butyl ester, (methyl) ethioxy methyl ester, (methyl) propylene
Acid ethoxyethyl group ester, (methyl) ethioxy propyl diester, (methyl) ethioxy butyl
Ester etc..They can be used alone, it is also possible to two or more is applied in combination.It addition, alkoxyalkyl
Carbon number be that less than 20 degree are preferred.
As containing functional group monomer, it may be preferred to enumerating intramolecular has the monomer (hydroxyl monomer) of hydroxyl
, intramolecular has the monomer (containing carboxylic monomer) of carboxyl, and intramolecular has the monomer of amino (containing ammonia
Base monomer) etc..
As hydroxyl monomer, (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) can be enumerated
Acrylic acid 2-hydroxy-propyl ester, (methyl) acrylic acid 3-hydroxy-propyl ester, (methyl) acrylic acid 2
-hydroxybutyl ester, (methyl) acrylic acid 3-hydroxybutyl ester, (methyl) acrylic acid 4-hydroxyl fourth
(methyl) hydroxyalkyl acrylates etc. of base ester etc..They can be used alone, it is also possible to 2 kinds with
On be applied in combination.
As containing carboxylic monomer, acrylic acid can be enumerated, methacrylic acid, crotonic acid, maleic acid,
Itaconic acid, twists the ethene unsaturated carboxylic acid of health acid etc..They can be used alone, it is also possible to 2 kinds with
On be applied in combination.It addition, adherence composition P contains the occasion of following aziridine system crosslinking agent, by
Excellent with the reactivity of the '-aziridino of aziridine system crosslinking agent in carboxyl, so (methyl) acrylate
Polymer (A) at least contains carboxyl group-containing monomer preferably as component unit.
As emulsion stability, can enumerate, (methyl) acrylic-amino ethyl ester, (methyl) propylene
Acid n-Butylaminoethyl ester etc..They can be used alone, it is also possible to two or more is applied in combination.
As other monomer above-mentioned, can enumerate and there is having of (methyl) cyclohexyl acrylate etc.
(methyl) acrylate of aliphatic ring, (methyl) phenyl acrylate etc. there is aromatic ring
(methyl) acrylate, acrylic acid amides, (methyl) third of the non-crosslinked of Methacrylamide etc.
Enoic, (methyl) acrylic acid N, N-dimethyl aminoethyl ester, (methyl) acrylic acid N,
(methyl) acrylate of the tertiary amine groups with non-crosslinked of N-dimethylaminopropyl ester etc., vinegar
Acid vinyl esters, styrene etc..They can be used alone, it is also possible to two or more is applied in combination.
(methyl) acrylate polymer (A) is, as the unit of this polymer of composition, alkyl
Carbon number is (methyl) alkyl acrylate of 1-20 and containing the ester (methyl) of alkoxyalkyl
Acrylate altogether, being preferred, especially with 70-95 containing 70-99 mass %
Quality % is preferably, further being preferred containing 80-95 mass %.(methyl) alkyl acrylate
Base ester and containing alkoxyalkyl the amount of total of (methyl) acrylate in above-mentioned scope
In, suitable adhesion strength can be obtained as sticker.It addition, such as above-mentioned (methyl) acrylic acid alkyl
Ester and containing alkoxyalkyl the amount of total of (methyl) acrylate be 70 mass %
Less than, the possibility that cohesively is too low.It addition, (methyl) acrylate polymer (A) is, only
By (methyl) alkyl acrylate that the carbon number of alkyl is 1-20 and containing alkoxyalkyl (
Methyl) acrylate is constituted can also.
Here, (methyl) alkyl acrylate that the carbon number of alkyl is 1-20 and containing alkoxyl
The occasion of (methyl) acrylate of alkyl, the carbon number of the alkyl in both be 1-20 (
Methyl) amount occupied of alkyl acrylate, it is preferred more than 50 mass %, 70 mass %
It is more than particularly preferred, more than 80 mass % is further preferred.It addition, as the two
The higher limit of use level, the carbon number of alkyl be (methyl) alkyl acrylate of 1-20 be 100
Quality % can also.
(methyl) acrylate polymer (A) is, as the component unit of this polymer, above-mentioned contains
Functional group monomer, with 1-30 mass % containing promising preferably, particularly contain with 2-20 mass %
For preferably, further with 3-10 mass % containing promising preferably.Contain in above-mentioned scope containing functional group monomer
Sometimes, and the intermiscibility raising of following polymer (B), above-mentioned structure X efficiency can be made well
Formed (presumption), its result, obtain that there is low haze value, and the sticker of excellent heat resistance.
Adherence composition P is the occasion containing following aziridine system crosslinking agent, (methyl) acrylic acid
Ester polymer (A), as the unit of this polymer of composition, containing carboxyl group-containing monomer, with containing 1.
0-10.0 mass % is preferably, particularly with 3.0-5.0 mass % containing promising preferably.
Thus, polymer (A), between aziridine system, cross-linking agents structure can be formed well.
The polymerization state of (methyl) acrylate polymer (A) is, randomcopolymer can also, embedding
Section copolymer can also.
The weight average molecular weight of (methyl) acrylate polymer (A) is 600,000-200 ten thousand
, preferably 700,000-180 ten thousand, it is particularly preferably 800,000-150 ten thousand.That is, (methyl
) acrylate polymer (A) is heavy polymer composition.It addition, the weight in this specification
Mean molecule quantity is, for the polystyrene conversion value being measured by gel permeation chromatography (GPC) method
。
In being above-mentioned scope such as the weight average molecular weight of (methyl) acrylate polymer (A), poly-
Compound (A) has the big molecular weight compared, and can form above-mentioned structure X (presumption) well.
Here, if the weight average molecular weight of (methyl) acrylate polymer (A) is not 600,000 not
Full, the gel fraction of the sticker obtained is low, has the possibility of poor heat resistance.It addition, (methyl) third
The weight average molecular weight of olefine acid ester polymer (A) is such as more than 2,000,000, with reactive (methyl)
The intermiscibility of acrylate polymer (B) etc. is deteriorated, and has the possibility of the concavo-convex tracing ability step-down of sticker
Property.
It addition, in adherence composition P, (methyl) acrylate polymer (A) is, Yi Zhongdan
Solely use also can, 2 kinds of uses that combine also may be used.
Reactivity (methyl) acrylate polymer (B) on side chain with polymerism double bond is, excellent
Gated make as component unit containing containing functional group's monomer (methyl) acrylic polymeric (x)
Thing (b1) with have the substituent (y) that (x) reacts with functional group containing polymerism double bond chemical combination
Thing (b2) reacts and obtains.
(methyl) acrylic acid series polymeric compounds (b1) is preferably, containing functional group's (x) monomer and,
The carbon number of the alkyl used as required is (methyl) alkyl acrylate of 1-20, and according to need
The copolymer of other monomer to be used.
The above-mentioned (x) monomer containing functional group is, intramolecular have polymerism double bond and, hydroxyl, carboxylic
Base, amino, substituted-amino, the monomer of the functional group of epoxy radicals etc., preferably hydroxyl unsaturation chemical combination
Thing and/or the unsaturated compound Han carboxyl.
Such concrete example containing functional group's (x) monomer, can enumerate 2-hydroxyethylacrylate
Ester, 2-HEMA, 2-acrylate, 2-hydroxypropyl first
Hydroxyl (methyl) acrylate of base acrylate etc. and, acrylic acid, methacrylic acid, clothing health
The carboxylated compound of acid etc., these can individually or two or more use that combines.
As (methyl) alkyl acrylate that carbon number is 1-20 and other the monomer of alkyl,
The thing as (methyl) acrylate polymer (A) can be used.
(methyl) acrylic acid series polymeric compounds (b1), as constituting this this monomer unit, containing above-mentioned
Functional group's (x) monomer is usual 3-100 mass %, preferably 5-40 mass %, particularly
The amount of preferably 10-30 mass %, the carbon number of abovementioned alkyl is (methyl) acrylic acid of 1-20
The component unit that Arrcostab comes usually contains 0-97 mass %, preferably 60-95 mass %,
It is particularly preferably the amount of 70-90 mass %.
It addition, (methyl) acrylate polymer (A) constitute monomer containing functional group monomer and
The (x) monomer containing functional group constituting monomer of (methyl) acrylic acid series polymeric compounds (b1) is, can
To enumerate, carboxyl group-containing monomer and hydroxyl monomer, make their kind not be all preferably respectively.This is
The reason only polymer (A) worked due to crosslinking agent (D) and silane coupling agent (E).
On the other hand, the substituent (y) that (b2) containing polymerism double bond compound has is, according to
The functional group containing functional group's unit (x) that (methyl) acrylic acid series polymeric compounds (b1) has (
X) kind, suitably selects.Can enumerate, functional group is (x) hydroxyl, amino or replacement
The occasion of amino, alternatively base (y), be preferred with NCO or epoxy radicals, functional group (x
) it is the occasion of carboxyl, alternatively base (y) preferably '-aziridino, epoxy radicals or oxazolyl, sense
Base is (x) the occasion of epoxy radicals, alternatively base (y), is excellent with amino, carboxyl or '-aziridino
Choosing.Such substituent (y) is, every 1 molecule of (b2) containing polymerism double bond compound one.
Additionally containing in polymerism double bond compound (b2), polymerism double bond (carbon-to-carbon double bond) is
, every 1 molecule is usually 1-5, preferably 1-2.As such containing polymerism double bond
Compound (b2), can enumerate (methyl) acryloyloxyethyl isocyanate, methyl isopropyl thiazolinyl α
, α-dimethylbenzyl isocyanates, (methyl) propenoyl isocyanate, allyl iso cyanurate；
Diisocyanate cpd or polyisocyanate compounds and hydroxyethyl (methyl) acrylate are carried out instead
(methyl) the acryloyl group monoisocyanate compound that should obtain；Diisocyanate cpd or poly-isocyanide
Ester compound and polyol compound and (methyl) dihydroxypropyl ethyl ester react the (methyl obtained
) acryloyl group monoisocyanate compound；Diglycidyl (methyl) acrylate；(methyl) third
Olefin(e) acid；2-(1-aziridine) ethyl (methyl) acrylate, 2-vinyl 2-oxazoline,
2-isopropenyl 2-oxazoline etc..
As containing polymerism double bond compound (b2), among above-mentioned, alternatively base (y), tool
There is NCO, as containing polymerism double bond base, there is the base of ethene double bond, particularly have
The compound of (methyl) acryloyl group is preferably, specifically, and (methyl) acrylyl oxy-ethyl isocyanide
Acid esters, particularly methylacryoyloxyethyl isocyanates are preferred.
As in reactive (methyl) acrylate polymer (B) containing polymerism double bond compound (
The amount of substituent (y) b2) is, to above-mentioned (methyl) acrylic acid series polymeric compounds (b1
) the amount (x) of the functional group containing functional group's (x) monomer, rub with 0.05-0.8
Your equivalent is preferably, and particularly 0.1-0.6 molar equivalent is preferably, further with 0.1-
0.4 molar equivalent is preferred.
(methyl) acrylic acid series polymeric compounds (b1) and anti-containing polymerism double bond compound (b2)
Should be, usually normal pressure, under reactive atmosphere does not encloses gas, in the heating of room temperature or 40-70 DEG C, vinegar
In the organic solvent of acid ethyl ester etc., within 12-48 hour, degree is carried out.During reaction, catalyst and poly-
Conjunction forbids that agent etc. can suitably use.Can enumerate, functional group is (x) the acrylic copolymer of hydroxyl
Thing (b1) and substituent (y) are that (b2) containing polymerism double bond compound of NCO enters
The occasion of row reaction, the preferably catalyst of the organotin system of dibutyl tin lauryl etc. is used.It addition, root
According to functional group (x) with the combination of substituent (y), can be to the temperature of reaction, pressure, solvent,
Time, the presence or absence of catalyst, the kind of catalyst suitably selects.Thus, (methyl) acrylic acid series gathers
Present in compound (b1), functional group (x) and contains taking in polymerism double bond compound (b2)
Dai Ji (y) reacts, reactivity (methyl) acrylate that in side chain, polymerism double bond is imported into
Polymer (B) is obtained.Functional group in this reaction (x) with the reactivity of substituent (y),
Usual more than 70%, preferably more than 80%, unreacted functional group is (x) in reactive (first
Base) remaining can also in acrylate polymer (B).
Reactive (methyl) acrylate polymer (B) ((methyl) acrylic acid series polymeric compounds (b1
)) polymerization state, can be randomcopolymer, it is also possible to for block copolymer.
The weight average molecular weight of reactive (methyl) acrylate polymer (B) is 10,000-10
Ten thousand, preferably 30,000-8 ten thousand, it is particularly preferably 40,000-6 ten thousand.That is, reactivity (methyl) third
Olefine acid ester polymer (B), compares with (methyl) acrylate polymer (A), for low-molecular-weight
Component of polymer.
If the weight average molecular weight of reactive (methyl) acrylate polymer (B) is in above-mentioned scope
In, the distinctive three-dimensional mesh structure of sticker of present embodiment is formed, to excellent concavo-convex tracing ability
And heat resistance has contribution.That is, the weight such as reactive (methyl) acrylate polymer (B) is put down
Average molecular weight be 10,000 less than, good three-dimensional mesh structure cannot obtain, and just has heat resistance to be deteriorated
Occasion.On the other hand, such as the weight averaged molecular of reactive (methyl) acrylate polymer (B)
Amount, more than 100,000, with the intermiscibility step-down of (methyl) acrylate polymer (A) etc., has mist degree
Value rises occasion.It addition, the polymer in the three-dimensional mesh tectosome of polymer (B) formation further
(A) restrained condition is insufficient, its result, and the sticker obtained has the occasion of poor heat resistance.
It addition, in adherence composition P, reactive (methyl) acrylate polymer (B), one
Also can kind be used alone, 2 kinds of uses that combine also may be used.
To (methyl) acrylate polymer (A) 100 mass parts, reactive (methyl) acrylic acid
The use level of ester polymer (B) is to be preferred with 5-30 mass parts, particularly with 7-25 matter
Amount part be preferred, is preferred with 10-20 mass parts further.
From obtain with aforementioned proportion containing (methyl) acrylate polymer (A) and reactivity (
Methyl) sticker that obtains of the adherence composition P of acrylate polymer (B), can be well
Obtain above-mentioned structure X (presumption).
Here, as the active energy beam that adherence composition P is irradiated, use the occasion of ultraviolet,
Adherence composition P, preferably further contains Photoepolymerizationinitiater initiater (C).So draw containing photopolymerization
Sending out agent (C), reactive (methyl) acrylate polymer (B) can be hardened well by efficiency,
Aziridine propionate and light exposure additionally can be made to reduce.
As such Photoepolymerizationinitiater initiater (C), specifically, benzophenone, benzene second can be enumerated
Ketone, benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl
Base ether, benzoin benzoic acid, benzoin benzoic acid methyl, benzoin dimethyl ketal, 2,4
-diethyl thioxanthone, 1-hydroxycyclohexylphenylketone, benzyldiphenyl sulfide, the tetramethyl autumn is blue
Nurse mole, azobis isobutyronitrile, benzyl, dibenzyl, diacetyl, β-chloroanthraquinone, (2,
4,6-trimethyl benzyl diphenyl) phosphine oxide, 2-[4-morpholinodithio N, N-diethyl-dithio
Carbamate etc..
The amount of Photoepolymerizationinitiater initiater (C), to reactive (methyl) acrylate polymer (B) 1
00 mass parts, for 1-50 mass parts, particularly 5-30 mass parts is in the range of preferably.
Adherence composition P, above-mentioned polymer (A), polymer (B) and Photoepolymerizationinitiater initiater
(C) beyond, as required, it is also possible to containing crosslinking agent (D) and silane coupling agent (E),
It addition, acrylic acid series sticker, it is possible to use normally used various additives, adhesion can be enumerated and invest
Agent, charged preventor, antioxidant, ultra-violet absorber, light stabilizer, softening agent, filler
Deng.
As crosslinking agent (D), as long as not hindering the effect of the present invention, it is possible to use desired by other
Ground glue crosslinking agent, has carboxyl at (methyl) acrylate polymer (A) as reactive functional group
Occasion, the use of aziridine system crosslinking agent carrying out well with this carboxyl reacting is preferred.So use
Aziridine system crosslinking agent makes (methyl) acrylate polymer (A) cross-link, the sticker obtained resistance to
Property, particularly humidity resistance can improve for a long time.
It is to enumerate as aziridine system crosslinking agent, diphenyl methane 4, double (the 1-nitrogen third of 4'-
Pyridine formamide), trimethylolpropane tris β-aziridine propionate, tetramethylol methane three β-aziridine
Propionic ester, toluene 2,4-is double (1-aziridine formamide), Persistol, double different adjacent benzene
Dimethyl 1-(2-methylaziridine), three 1-(2-methylaziridines) phosphine, trihydroxy methyl
Propane three β-(2-methylaziridine) propionic ester etc..
The amount of the crosslinking agent (D) in adherence composition P is, gathers (methyl) acrylate
The amount of the reactive functional group (can enumerate, carboxyl) of compound (A), the friendship of this crosslinking agent (D)
The amount of connection property base (can enumerate, '-aziridino), is preferred with 0.001-0.1 molar equivalent
, it is particularly preferred with 0.003-0.02 molar equivalent.
Adherence composition P is, as containing silane coupling agent (E), the sticker obtained to glass
The adherence of substrate can be improved.Can enumerate, as (methyl) acrylate polymer (A
) reactive functional group is the occasion of carboxyl, the organic reaction base of silane coupling agent (E) etc. and (first
Base) carboxyl reaction of acrylate polymer (A), the alcoxyl of the silane coupling agent (E) of the opposing party
Base silicyls etc. act on the to-be-adhered object face of glass substrate etc..Thus, exist at such as polarizer
The occasion of the upper laminating such as liquid-crystalline glasses, the adherence between sticker and liquid-crystalline glasses can be the best.
It addition, the reactive functional group of polymer (A) is beyond carboxyl in occasion, selection has and this reaction
Property functional group's effect the silane coupling agent (E) of organic reaction base suitable.
It is that intramolecular has having of an at least alkoxysilyl as silane coupling agent (E)
Organic silicon compound, good with the intermiscibility of sticker composition, and have photopermeability, the most substantially transparent
Thing suitable.The use level of such silane coupling agent (E) is, to (methyl) acrylic ester polymerization
Thing (A) 100 mass parts, is preferred with 0.01-1.0 mass parts, particularly with 0.0
5-0.5 mass parts is preferred.
The concrete example of silane coupling agent (E), can enumerate vinyltrimethoxy silane, vinyl three
Ethoxysilane, (methyl) acryloxypropyl trimethoxy silane etc. containing polymerism unsaturated group
Silicon compound；3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxycyclohexyl
) silicon compound with epoxy structure of ethyl trimethoxy silane etc.；3-aminopropyl trimethoxy
Silane, N-(2-amino-ethyl)-3-TSL 8330, N-(2-ammonia
Base ethyl)-3-amino propyl methyl dimethoxysilane etc. containing aminosilicon compounds；3-chlorine third
Base trimethoxy silane；3-isocyanates propyl-triethoxysilicane etc..They can be used alone, also
Can be with 2 kinds of uses that combine.
(manufacture method of adherence composition)
Adherence composition P is, by (methyl) acrylate polymer (A) and, reactive (first
Base) acrylate polymer (B) manufactures respectively, while they being mixed, as required
, can be in the arbitrary stage by Photoepolymerizationinitiater initiater (C), crosslinking agent (D), silane coupling agent (E
) etc. add manufacture.
(methyl) acrylate polymer (A) is, can be by common radical polymerization system
Make.The polymerization of (methyl) acrylate polymer (A), can use polymerization initiator as required
, can carry out with solution polymerization process etc..As polymerization solvent, acetic acid ethyl ester, acetic acid n can be enumerated
-butyl ester, i-butyl base ester, toluene, acetone, hexane, methyl ethyl ketone etc., more than 2 kinds
Can be used together.
As polymerization initiator, Azo can be enumerated, organic peroxide etc., 2 kinds with
Going up and use can also.As Azo, 2 can be enumerated, 2'-azobis isobutyronitrile, 2,2'
-azo is double (2-methylbutyronitrile), and 1,1'-azo is double (hexamethylene 1-nitrile), and 2,2'-azos are double
(2,4-methyl pentane nitrile), double (2, the 4-dimethyl 4-methoxyl-valeronitrile of 2,2'-azos
), dimethyl 2,2'-azo is double (2 Methylpropionic acid ester), double (the 4-cyano group penta of 4,4'-azos
Acid), 2,2'-azos are double (2-hydroxymethyl propionitrile), double ［ the 2-(2-miaow of 2,2'-azos
Oxazoline 2-yl) propane ］ etc..
As organic peroxide, benzoyl peroxide, t-butyl benzylhydroperoxide, peroxide can be enumerated
Change hydrogen isopropyl dimethylbenzene isopropylperoxy dicarbonate, two n-peroxydicarbonate, two (2-
Ethoxyethyl group) peroxydicarbonate, t-butyl peroxy neodecanoic acid, t-butyl peroxy pivalic acid, (3
, 5,5-trimethyl acetyls) and peroxide, two propionyl peroxide, diacetyl peroxide etc..
It addition, in above-mentioned polymerization process, can be right by adding the chain-transferring agent of 2 mercapto ethanol etc.
The weight average molecular weight of the polymer obtained is adjusted.
On the other hand, reactive (methyl) acrylate polymer (B), as above-mentioned, can make (
Methyl) acrylic acid series polymeric compounds (b1) and containing polymerism double bond compound (b2) reaction manufacture
.(methyl) acrylic acid series polymeric compounds (b1), with above-mentioned (methyl) acrylate polymer (A)
Manufacture method manufacture equally.
(methyl) acrylate polymer (A) and reactive (methyl) acrylate polymer (
B) after obtaining, being mixed by the solution of polymer (A) and (B), dilution solvent adds.Thereafter
, as required, by Photoepolymerizationinitiater initiater (C), crosslinking agent (D), silane coupling agent (E) etc. adds
Adding, be sufficiently mixed, the adherence composition (coating solution) of solvent dilution is obtained.
Adherence composition is diluted to the retarder thinner of coating solution, hexane, heptane, ring can be enumerated
The aliphatic hydrocarbon of hexane etc.；Toluene, the aromatic hydrocarbon of dimethylbenzene etc.；Dichloromethane, vinyl chloride etc. be
Halogenated hydrocarbons；Methyl alcohol, ethanol, propyl alcohol, butanol, the alcohol of 1-methoxyl group 2-propyl alcohol etc.；Acetone, first
Base ethyl ketone, 2 pentanone, isophorone, the ketone of cyclohexanone etc.；Acetic acid ethyl ester, acetic acid butyl ester
Deng ester；The cellosolve series solvent etc. of ethyl cellosolve etc..
So concentration viscosity of the coating solution of modulation, as long as being coated with possible scope, does not has
Particularly limit, can according to circumstances can suitably select.Such as can be by the concentration of adherence composition
It is diluted to 10-40 mass %.During it addition, obtain coating solution, the interpolation of retarder thinner etc. is not
Necessary condition, as long as adherence composition is the viscosity etc. that coating is possible, can also without retarder thinner
.This occasion, adherence composition can be intactly as coating solution.
(formation of sticker)
The sticker of present embodiment, preferably by by adherence composition P on required object
Coating is dried, makes adherence composition P harden with the irradiation of active energy beam, obtains.
Adherence composition P is dried, air-dry can also, but usually heat (preferably,
Heated-air drying) carry out.Carry out the occasion heated, heating-up temperature, with 50-150 DEG C be
Preferably, it is particularly preferred with 70-120 DEG C.It addition, the heat time, with 10 seconds-10
It is divided into preferably, was particularly divided into preferably with 50 seconds-2.It addition, (methyl) acrylate polymer
(A) having reactive functional group, adherence composition P contains the occasion of crosslinking agent (D), passes through
Above-mentioned heating (methyl) acrylate polymer (A) is crosslinked.
As active energy beam, generally, ultraviolet, electric wire etc. is used.Active energy beam
Exposure, different according to the kind of energy line, such as, in the occasion of ultraviolet, light quantity is with 50-10
00mJ/cm2For preferably, particularly with 100-500mJ/cm2For preferably.Separately
Outward, in the occasion of electric wire, it is preferred with 10-1000krad degree.
By the irradiation of above-mentioned active energy beam, multiple reactivity (methyl) acrylate polymer (
B), the cracking of the polymerism double bond of side chain, it is mutually bonded, three-dimensional mesh structure is formed, multiple (methyl
) acrylate polymer (A) inserts described three-dimensional mesh structure, above-mentioned structure X is formed (presumption)
.Now, owing to the hardening of adherence composition P is carried out rapidly, maturation there is no need, the adhesion obtained
All physical property of agent will be stabilized from initial stage.This sticker, owing to it constructs X, can play excellent
Concavo-convex tracing ability and heat resistance.
The sticker of present embodiment, using as used for optical part be preferred, can enumerate, polarizer (
Polarizing film) and the optics of polarizer (phase-contrast film) etc. between then, or polarization
Between sheet (polarizing film) and polarizer (phase-contrast film) and glass substrate then.
The sticker of present embodiment, owing to concavo-convex tracing ability is excellent, even if surface is coarse liquid crystal list
Unit's occasion then, it is also possible to depressed part is buried, and liquid crystal cells adherence, it is hereby achieved that excellent
Optical characteristics.It addition, the sticker of present embodiment, excellent heat resistance.That is, present embodiment is viscous
Agent and can have again heat resistance with existing concavo-convex tracing ability.
(adhesive sheet)
As shown in Figure 1, the adhesive sheet 1A of the embodiment of the 1st, by from lower number, stripping film
12, the adhering agent layer 11 of the release surface lamination of stripping film 12, at the base material of adhering agent layer 11 lamination
13 are constituted.
It addition, as shown in Figure 2, the adhesive sheet 1B of the embodiment of the 2nd is, the stripping of 2 pieces
From sheet 12a, 12b and, this stripping film 12a, 12b of 2 pieces clamp, thus with this
The adhering agent layer 11 that the release surface of the stripping film 12a, 12b of 2 pieces connects is constituted.It addition,
The release surface of the so-called stripping film in this specification, for there being the face of fissility in stripping film, implements stripping
Even if process face and do not implement lift-off processing, but but there is the either of which in the face of fissility
Permissible.
Any one adhesive sheet 1A, in 1B, adhering agent layer 11 is all above-mentioned adherence combination
The sticker of thing hardening is constituted.
The thickness of adhering agent layer 11 is, can fit according to the application target of adhesive sheet 1A, 1B
Preferably determining, usually 5-100 μm, the scope of preferably 10-60 μm, such as light
The occasion that the adhering agent layer of department of the Chinese Academy of Sciences's part use, particularly polarizer uses, with 10-50 μm, special
It not to be preferred with 10-30 μm.
As base material 13, have no particular limits, the common thing used as the substrate sheets of adhesive sheet
Can use.Can enumerate, outside desired optics, artificial silk, acrylic acid, polyester
Deng with the weaving cloth of fiber or non-woven fabrics；Upper matter paper, Ge Laxin paper, containing impregnated paper, it is coated with the paper of paper etc.
Class；Aluminium, the metal forming of copper etc.；Synthetic paper；Polyurethane foaming body, the foaming body of foam polyethylene etc.
；Polyethylene terephthalate, polybutylene terephthalate (PBT), polyethylene glycol naphthalate etc.
Polyester film, polyurethane film, polyethylene film, polypropylene film, the fibre of triacetyl cellulose etc.
Dimension element film, polyvinyl chloride base film, polyvinylidene chloride film, polyvinyl alcohol film, ethene vinegar
Acid ethylenic copolymer film, polystyrene film, polycarbonate film, acrylic resin films, fall
Bornylene based resin film, the plastic sheeting of cyclic olefin resins film etc.；These laminated body of more than two kinds
Deng also may be used.Plastic sheeting is, an axle extends or the extension of two axles can.
As optics, polarizer (polarizing film), polarisation, polarizer (phase can be enumerated
Potential difference film), angle of visibility mends reward film, and briliancy improves film, and contrast improves film, polymerizable mesogenic
Thing film, diffusion film, semi-penetration film etc..
The thickness of base material 13, different according to its kind, such as in the occasion of optics, usual 1
0 μm-500 μm, preferably 50 μm-300 μm.
As stripping film 12,12a, 12b, can enumerate, polyethylene film, polypropylene is thin
Film, polybutene film, polybutadiene membrane, poly-methyl pentene film, polyvinyl chloride base film, chloroethene
Alkenyl copolymers film, pet film, poly-ethylnaphthalene dicarboxylic acid esters film, poly-right
Phthalic acid fourth glycol ester film, polyurethane film, ethylene-vinyl acetate base film, from polyimide precursor resin
Film, ethene (methyl) acrylic copolymer film, ethene (methyl) acrylate copolymer
Film, polystyrene film, polycarbonate film, imide membrane, fluorine resin film etc..It addition,
Their crosslinked film can also use.Further, their laminate film can also.
In the release surface (face particularly connected with adhering agent layer 11) of above-mentioned stripping film, at stripping
What reason had been carried out is preferred.The remover that lift-off processing uses, can enumerate alkyd system, polysiloxanes
System, fluorine system, unsaturated polyester (UP) system, polyolefin, the remover of wax system.It addition, stripping film, with can
It is preferred with the thing of the permeability through active energy beam.
Stripping film 12,12a, the thickness of 12b the most particularly limits, usually 20-1
50 μm degree.
The manufacture of above-mentioned adhesive sheet 1A, is in the release surface of stripping film 12, will be containing adherence group
Solution (coating solution) coating of compound P, is dried and arrives the film of adherence composition, at this film
Expose side, by base material 13 lamination.Then, irradiate through above-mentioned stripping film with active energy beam, make
Adhering agent layer 11 is formed.Now, maturation need not.It addition, about the condition of active energy beam,
As above-mentioned.
It addition, in the manufacture of above-mentioned adhesive sheet 1B, at stripping film 12a(or 12b)
Release surface on, be coated with the coating solution containing above-mentioned adherence composition, be dried to obtain adhesion
The film of property composition, in the exposed surface side of this film by stripping film 12b lamination.Then, from stripping
Active energy beam is irradiated by the either side of sheet 12a or 12b, forms adhering agent layer 11.
It addition, be irradiated active energy beam forming adhering agent layer through stripping film as above-mentioned
Outside 11, it is also possible to be that the film layer making adherence composition P on stripping film is formed, its film layer
Under the state exposed, active energy beam is irradiated, form adhering agent layer 11, thereafter, at this sticker
By base material 13 and stripping film lamination on layer 11.Further, it is also possible on base material 13, directly
Form the film layer of adherence composition P, this film layer is carried out active energy beam irradiation, form adhesion
Oxidant layer 11.
As the method that above-mentioned coating solution is coated, bar code method, scraper for coating method can be enumerated
, roller rubbing method, scraper for coating method, mould rubbing method, gravure coating method etc..
Here, in the manufacture of the liquid crystal display device such as constituted at liquid crystal cells and polarizer, as viscous
The base material 13 of sheet 1A, use polarizer, the stripping film 12 of this adhesive sheet 1A is peeled off, will dew
The adhering agent layer 11 gone out and liquid crystal cells are fitted.
It addition, the system of the liquid crystal display device such as between liquid crystal cells and polarization, polarizer configured
In making, as an example, first, by stripping film 12a(or 12b of a side of adhesive sheet 1B)
Peeling off, adhering agent layer 11 and polarizer that adhesive sheet 1B exposes are fitted, then, and will be as base
Material 13 uses the stripping film 12 of the adhesive sheet 1A of polarizer to peel off, the adhesion that adhesive sheet 1A exposes
Oxidant layer 11 and above-mentioned polarizer are fitted.Further, from the adhering agent layer 1 of above-mentioned adhesive sheet B
1 by stripping film 12b(or 12a of another-side) peel off, by the sticker exposed of adhesive sheet B
Layer 11 is fitted with liquid crystal cells.
According to above adhesive sheet 1A, 1B, due to the excellent concavo-convex tracing ability of adhering agent layer 11
Even if being the occasion then of the liquid crystal cells of roughening to surface, this adhering agent layer 11 and liquid crystal cells
Can positively adherence.
Embodiments described above is to describe ground to understand the present invention, does not has the present invention
Any restriction.But, each key element disclosed in above-mentioned embodiment, in the scope of the technology belonging to the present invention
Whole design alterations and equivalent to the part for the present invention.
Such as, the stripping film 12 of adhesive sheet 1A can omit, the stripping film 12 in adhesive sheet 1B
Any one of a, 12b can also be omitted.
Embodiment
Hereinafter, by embodiment etc., the present invention is carried out the brightest, but the scope of the present invention
Do not limited by these embodiments etc..
(embodiment 1)
1. the modulation of polymer (A1)
To equipped with mixer, thermometer, circulation cooler, dripping device and the reaction of nitrogen ingress pipe
In container, add n-butyl 76.5 mass parts, methoxyethyl ethyl ester 20
Mass parts, acrylic acid 3.0 mass parts, acrylic acid 2-hydroxyethyl ester 0.5 mass parts, acetic acid
Ethyl ester 200 mass parts, and 2,2'-azobis isobutyronitrile 0.08 mass parts, by above-mentioned
Air nitrogen in reaction vessel replaces.This nitrogen atmosphere gas is stirred below, while by reaction solution liter
Temperature, to 60 DEG C, after reaction in 16 hours, is cooled to room temperature.Here, by obtain one of solution with
Following method carries out the mensuration of molecular weight, the polymer (A1) of weight average molecular weight 800,000
Generation is identified.
2. the modulation of polymer (B1)
To equipped with mixer, thermometer, circulation cooler, the reaction of dripping device and nitrogen ingress pipe is held
In device, by n-butyl 85 mass parts, acrylic acid 2-hydroxyethyl ester (HEA)
15 mass parts, acetic acid ethyl ester 200 mass parts, 2,2'-azobis isobutyronitrile 0.16 matter
Amount part, and the addition of 2 mercapto ethanol 0.3 mass parts, the air nitrogen in above-mentioned reaction vessel
Replace.It is stirred on this nitrogen atmosphere gas limit, while reaction solution to be warming up to 70 DEG C, reaction in 6 hours
After, be cooled to room temperature, (x) have as functional group hydroxyl (methyl) acrylic acid series polymeric compounds (
B1) it is obtained.
Then, will be different as the polymerism 2-methylacryoyloxyethyl containing double bond compound (b2)
Cyanate (MOI) adds, and makes the amount of NCO of this MOI to (methyl) acrylic acid series
The HEA of polymer (b1) is 0.1 molar equivalent, as catalyst, adds dibutyltindilaurylmercaptide osmanthus
Ester, normal temperature (23 DEG C) normal pressure carries out stirring in 24 hours.Here, by obtain one of solution with
Following method carries out the mensuration of molecular weight, the life of the polymer (B1) of weight average molecular weight 50,000
One-tenth is identified.
3. the modulation of adherence composition
(solid constituent converts polymer (A1) 100 mass parts above-mentioned operation (1) obtained
Value) and, (solid constituent converts polymer (B1) 20 mass parts that above-mentioned operation (2) obtains
Value) mixing after, will be as the benzophenone of Photoepolymerizationinitiater initiater (C) and 1-hydroxy-cyclohexyl benzene
Base ketone with the mixture of the mass ratio of 1:1 (Ciba Specialty Chemicals company system,
IRGACURE500) 2.0 mass parts (occasion of polymer (B1) 100 mass parts,
Photoepolymerizationinitiater initiater (C) is the suitable amount of 10 mass parts) add, it is sufficiently stirred for, adherence group
The dilute solution of compound is obtained.
4. there is the manufacture of the polarizer of adhering agent layer
By the dilute solution of the adherence composition that above-mentioned operation (3) obtains, in poly terephthalic acid second
One face polysiloxane series stripping agent of terephthalate films has carried out the stripping film (Lin get Ke of lift-off processing
Company's system, SP-PET3811, thickness: 38 μm) lift-off processing face on, use scraper
Rubbing method enters cloth coating, and 90 DEG C carry out 1 minute heating, and the film of adherence composition is obtained.
Then, being constituted by discoid band liquid crystal layer polarizing film, polarizing film and angle of visibility expand film one
The film of the polarizer of body and above-mentioned adherence composition is fitted, the most above-mentioned adherence composition
The exposed surface of film and the surface of disc-like liquid crystal layer connect, thereafter, through stripping film at following bar
Part, irradiates with ultraviolet, makes the film of adherence composition become adhering agent layer, obtain having adhering agent layer
Polarizer.It addition, the thickness of adhering agent layer is 25 μm
＜ ultraviolet irradiates condition ＞
Fusion company electrodeless lamp uses H bulb
Illumination 600mW/cm2, light quantity 150mJ/cm2
UV illumination quantometer uses EYEGRAPHICS company system " UVPF-36 "
(embodiment 2)
Make as the 2-methylacryoyloxyethyl isocyanates containing polymerism double bond compound (b2)
(MOI) reacting with (methyl) acrylic acid series polymeric compounds (b1), now this MOI's is different
The amount of cyanic acid ester group to the HEA of (methyl) acrylic acid series polymeric compounds (b1) is 0.2 mole and works as
Amount.In addition, as the polymer (B1) of embodiment 1, the system of polymer (B2) is carried out
Make.The mensuration carrying out molecular weight by following method of solution that will obtain, weight average molecular weight 5
The generation of the polymer (B2) of ten thousand is identified.
In addition to polymer (B1) is replaced with polymer (B2), similarly to Example 1,
Carry out the modulation of adherence composition, use this adherence composition to carry out the polarizer with adhering agent layer
Manufacture.It addition, the thickness of adhering agent layer is 25 μm.
(embodiment 3, comparative example 1-3)
Except by the kind of polymer (B) and use level as shown in table 1 as in addition to change, with
Embodiment 1 is same, carries out the manufacture with the polarizer of adhering agent layer.It addition, the thickness of adhering agent layer is
25 μm.
(comparative example 4)
1. the modulation of polymer (A2)
To having mixer, thermometer, circulation cooler, the reaction of dripping device and nitrogen ingress pipe is held
In device, add n-butyl 76 mass parts, methyl acrylate 20 mass parts, propylene
Acid 4 mass parts, acetic acid ethyl ester 200 mass parts, and 2,2'-azobis isobutyronitrile 0.0
8 mass parts, the air nitrogen in above-mentioned reaction vessel replaces.Stir below at this nitrogen atmosphere gas, limit
Reaction solution is warming up to 60 DEG C, after reaction in 16 hours, is cooled to room temperature.Here, will obtain
One of solution carries out molecular weight determination, the polymer of weight average molecular weight 800,000 by following method
(A2) generation is identified.
2. the modulation of adherence composition
To polymer (A2) 100 mass parts (solid constituent obtained in above-mentioned operation (1)
Scaled value) in, add as isocyanates system crosslinking agent, add the toluene diisocynate of trimethylolpropane
Ester (TDI system) addition product (Japanese polyurethane company system, CORONATEL) 2.5 mass
Part, it is sufficiently stirred for, obtains the dilute solution of adherence composition.
3. there is the manufacture of the polarizer of adhering agent layer
Use the dilute solution of the adherence composition obtained in above-mentioned operation (2), with embodiment 1
Equally, the manufacture with the polarizer of adhering agent layer is carried out.It addition, the thickness of adhering agent layer is 25 μm
。
Here, above-mentioned weight average molecular weight (Mw) is, with gel permeation chromatography (GPC)
The weight average molecular weight of the polystyrene conversion of (GPC mensuration) it is measured by following condition.
＜ condition determination ＞
GPC determinator: Tosoh company system, HLC-8020
GPC post (following order is passed through): Tosoh company system
TSK guard column HXL-H
TSK gel GMHXL(× 2)
TSK gel G2000HXL
Mensuration solvent: oxolane
Mensuration temperature: 40 DEG C
(test example 1) (mensuration of gel fraction)
Use in the making of the polarizer that manufacture in embodiment or comparative example is had adhering agent layer is inclined
The sheet that shakes replaces with to pet film face to have carried out shelling with polysiloxane series
From the lift-off processing of agent stripping film (Lin get Ke company system, SP-PET3801, thickness:
38 μm) beyond, as embodiment or comparative example, carry out corresponding with each example have stripping film/
The making of the adhesive sheet of the composition of adhering agent layer (thickness 25 μm)/stripping film.
The adhesive sheet that will make as above-mentioned, after making at once (in half day), 80mm × 80m
The size sampling of m, only packages its adhering agent layer polyester net (net size 200), only will be viscous
The quality precision balance weighing of agent.It addition, the adhesive sheet that will make as described above, 23
DEG C, carry out keeping in 7 days, thereafter, as described above, the only matter to sticker under conditions of 50%RH
Amount carries out weighing.Using its quality as M1.
Then, the sticker encased by above-mentioned polyester net, at room temperature (23 DEG C) are at acetic acid ethyl
Ester carries out 24 hours dippings.It addition, the film ultraviolet of adherence composition is irradiated,
After adhering agent layer is formed, sampling, impregnate in acetic acid ethyl ester, the time is about half day.Thereafter
Sticker is taken out, temperature 23 DEG C, in the environment of relative humidity 50%, within 24 hours, air-dry, enter
The baking oven of one step 80 DEG C is carried out 12 hours being dried.Only accurate to the quality of dried sticker
Capacity of balance.Using quality now as M2.
From M1 and M2 obtained, with below formula
Gel fraction (%)=(M2/M1) × 100
Calculate the gel fraction G1(% of (when adhering agent layer is newly formed) when adhesive sheet makes newly formed)
, and from adhesive sheet make (adhering agent layer is formationed) extremely at 23 DEG C, in the environment of 50%RH 7
Gel fraction G2(% after it keeping).
It addition, from G1 and G2 obtained, with below formula
The gel fraction rate of change (%)=| (G2-G1)/G2| × 100
The gel fraction rate of change (%) is calculated.Result is listed in table 2.
(test example 2) (mensuration of haze value)
As measure sample, use with in the mensuration of gel fraction use adhesive sheet as adhesive sheet (
Keeping in 7 days is over).Adhering agent layer to this adhesive sheet, by haze meter (electricity Se industrial group of Japan system
, NDH2000), by JISK7105, haze value (%) is measured.Result
It is listed in table 2.
(test example 3) (tension test)
Will in embodiment or comparative example the adherence composition of modulation, in a face by with polysiloxane series
Remover has carried out stripping film (the Lin get Ke public affairs of the pet film of lift-off processing
Department system, SP-PET3811) lift-off processing face on be coated with, 100 DEG C, 1 minute heating
, the film of adherence composition is formed.This film and, of pet film
Face carried out with polysiloxane series stripping agent another stripping film of lift-off processing (Lin get Ke company system,
SP-PET3801) lift-off processing is towards laminating, in following condition, carries out ultraviolet photograph
Penetrating, make adhering agent layer be formed, adhesive sheet obtains.It addition, the thickness of adhering agent layer is 25 μm.
＜ ultraviolet irradiates condition ＞
Fusion company electrodeless lamp H bulb uses
Illumination 600mW/cm2, light quantity 150mJ/cm2
UV illumination light quantity is calculated as EYEGRAPHICS company system " UVPF-36 " use
Multiple for above-mentioned adhering agent layer layers are carried out lamination, makes the aggregate thickness of the adhering agent layer of above-mentioned adhesive sheet
It is 500 μm, and only makes the stripping film on the top layer of laminated body stay.Thereafter (only comparative example 4
, maturation is necessary, and at 23 DEG C, under the atmosphere gas of 50%RH, 2 weeks placed.), from above-mentioned adhesion
The adhesive sheet of the multiple stacking of oxidant layer cuts out the sample of 10mm width × 75mm length, by laminated body
The stripping film of skin lay-up is peeled off, and is arranged by sample, and making sample determination position is 10mm width × 2
0mm length (prolonging direction), at 23 DEG C, in the environment of 50%RH, with cupping machine (
ORIENTEC company system, Tan Xilun), divide elongation with draw speed 200mm/, fracture stretched
Long rate (%) and fracture strength (N/mm2) be measured.Result is listed in table 2.
(test example 4) (Evaluation of Heat Tolerance)
The polarizer with adhering agent layer that will obtain in embodiment or comparative example, with cutting device, (reed is wild
The super cutter of manufacturing company's system, PN1-600) adjust 233mm × 309mm size
.Stripping film is peeled off, between the adhering agent layer exposed, at poly-methyl methacrylate base ester (PMMA
) plate (mitsubishi rayon system, ACRYLITEL001 is transparent, thickness 2.0mm) patch
Attached, with 0.5MPa in the chestnut made autoclave of former making, in 50 DEG C, 20 points of pressurizations.
Thereafter, 80 DEG C be dried in the environment of put into, with 10 times of magnifying glasses after 100 hours, to float
The presence or absence risen and peel off confirms.Metewand is as described below.Result is expressed as table 2.
Zero: float, to peel off, foaming etc. is not identified.
×: floating, peel off, foaming etc. is identified.
(test example 5) (concavo-convex tracing ability test)
By the adherence composition of modulation in embodiment or comparative example, gathering benzene in thickness 100 μm
One topcoating cloth of naphthalate (PET) film, thus making dried coating thickness is 50
μm, carries out 1 minute heating (be dried and process), after obtaining the film of adherence composition by 90 DEG C
, carrying out ultraviolet irradiation in following condition, adhering agent layer is formed, and sample is made into.
＜ ultraviolet irradiates condition ＞
Fusion company electrodeless lamp uses H bulb
Illumination 600mW/cm2, light quantity 150mJ/cm2
UV illumination quantometer uses EYEGRAPHICS company system " UVPF-36 " make
With
As Fig. 3 and Fig. 4 represents, at size 125mm × 125mm, thickness 1.
On the PMMA plate (mitsubishi rayon system, ACRYLITEL001 is transparent) of 1mm
, by size 25mm × 25mm, the PET film of thickness 25 μm or 50 μm loads,
Above-mentioned sample is attached at PMMA plate, and the sticker face making above-mentioned sample is thickness 25 μm or 5
The PET film sealing of 0 μm.Then, in Li Yuan manufacturing company autoclave, 0.5MP
A, in 50 DEG C, 20 points of pressurizations.And then, the end of the PET film of above-mentioned sealing is sent out in being closely close to
Length L(floated of raw adhering agent layer is by the PET film from thickness 25 μm or 50 μm
End, the distance to adhering agent layer and the then part of alkali-free glass plate arbitrarily measures 5 points, they is put down
Equal distance) it is measured.Metewand is following.Result is listed in table 2.
◎: the long L floated be 0.1mm less than
Zero: the long L floated be more than 0.1mm 0.5mm less than
△: the long L floated be more than 0.5mm 1.0mm less than
×: the long L floated is more than 1.0mm
[table 1]
※ is to polymer (B1) or the addition (solid constituent) of (B2) 100 mass parts Photoepolymerizationinitiater initiater (C)
[table 2]
As clear and definite in table 2, the sticker of the adhering agent layer obtained in embodiment, its gel fraction becomes
Dynamic rate, elongation at break and fracture strength, all meet the important document of the present invention, concavo-convex tracing ability and heat-resisting
Property the most excellent.
Possibility is utilized in industry
The sticker of the present invention, to optics, can enumerate then fitting of polarizer and polarizer
Preferably, it addition, the adhesive sheet of the present invention, as used for optical part the gluing of polarizer and polarizer etc.
It is also suitable for sheet.
The explanation of symbol
1A, 1B ... adhesive sheet
11 ... adhering agent layer
12,12a, 12b ... stripping film
13 ... base material
Claims (11)
1. a sticker, it is characterised in that:
Described sticker is to make containing (methyl) acrylate polymer (A) that weight average molecular weight is 600,000-200 ten thousand and weight average molecular weight to be 30,000-10 ten thousand, and the adherence composition of reactivity (methyl) acrylate polymer (B) that side chain has polymerism double bond hardens under the irradiation of active energy beam and forms；
Described reactivity (methyl) acrylate polymer (B) is for by making reacting containing monomer (methyl) acrylic acid series polymeric compounds (b1) containing functional group (x) with (b2) containing polymerism double bond compound with the substituent (y) reacted with described functional group (x) and obtaining as component unit；
As the described amount containing the described substituent (y) of polymerism double bond compound (b2) in described reactivity (methyl) acrylate polymer (B) it is, amount to the described described functional group (x) containing functional group (x) monomer of described (methyl) acrylic acid series polymeric compounds (b1), for 0.05-0.6 molar equivalent；
Using adhering agent layer gel fraction time newly formed as G1, adhering agent layer formed after at 23 DEG C, when carrying out the gel fraction after keeping in 7 days in the environment of 50%RH as G2, the gel fraction rate of change calculated from following formula within 3%,
The gel fraction rate of change (%)=| (G2-G1)/G2 | × 100
Elongation at break during tension test is 100-250%, and fracture strength is 0.2-0.6N/mm2。
2. sticker described in claim 1, it is characterised in that: the polymerism double bond on the side chain of reactive (methyl) acrylate polymer (B) is contained in (methyl) acryloyl group being imported side chain by isocyanates.
3. the sticker described in claim 1, it is characterised in that: to (methyl) acrylate polymer (A) 100 mass parts, the amount of described reactivity (methyl) acrylate polymer (B) is 5-30 mass parts.
4. the sticker described in claim 1, it is characterised in that: described adherence composition, contains Photoepolymerizationinitiater initiater (C) further.
5. the sticker described in claim 4, it is characterised in that: to described reactivity (methyl) acrylate polymer (B) 100 mass parts, the amount of described Photoepolymerizationinitiater initiater (C) is 5-30 mass parts.
6. the sticker described in claim 1, it is characterised in that: the exposure of described active energy beam is 50-1000mJ/cm2。
7. the sticker described in claim 1, it is characterised in that: when adhering agent layer is newly formed is 30-60% with the gel fraction after keeping in described 7 days.
8. the sticker described in claim 1, it is characterised in that: haze value is below 1.0%.
9. an adhesive sheet, has base material and adhering agent layer, it is characterised in that: described adhering agent layer is formed by the sticker described in any one of claim 1-8.
10. the adhesive sheet described in claim 9, it is characterised in that: described base material is optics.
11. 1 kinds of adhesive sheets, it is characterized in that: include the stripping film of 2 pieces and clamped by described stripping film, the adhering agent layer that thus release surface with described 2 pieces of stripping films connects, it is characterised in that: described adhering agent layer is made up of the sticker described in any one of claim 1-8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012082766A JP6071231B2 (en) | 2012-03-30 | 2012-03-30 | Adhesive and adhesive sheet |
| JP2012-082766 | 2012-03-30 |
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| Publication Number | Publication Date |
|---|---|
| CN103360999A CN103360999A (en) | 2013-10-23 |
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| CN201310111386.9A Active CN103360999B (en) | 2012-03-30 | 2013-04-01 | Sticker and adhesive sheet |
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|---|---|
| JP (1) | JP6071231B2 (en) |
| KR (1) | KR102071640B1 (en) |
| CN (1) | CN103360999B (en) |
| TW (1) | TWI570213B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104797672A (en) * | 2012-11-16 | 2015-07-22 | 3M创新有限公司 | Adhesive including pendant (meth) acryloyl groups, article, and method |
| KR102323947B1 (en) * | 2013-11-19 | 2021-11-09 | 닛토덴코 가부시키가이샤 | Resin sheet |
| JP6438817B2 (en) * | 2015-03-27 | 2018-12-19 | リンテック株式会社 | Adhesive composition, adhesive, adhesive sheet and optical film with adhesive layer |
| JP6754172B2 (en) * | 2015-03-28 | 2020-09-09 | 株式会社日本触媒 | Interior material |
| JP6498991B2 (en) * | 2015-03-31 | 2019-04-10 | リンテック株式会社 | Adhesive sheet and display |
| CN104861889B (en) * | 2015-06-02 | 2017-09-08 | 日东电工（上海松江）有限公司 | A kind of adhesive tape |
| JP6895228B2 (en) * | 2016-05-25 | 2021-06-30 | 王子ホールディングス株式会社 | Adhesive sheet |
| JP6902377B2 (en) * | 2017-03-30 | 2021-07-14 | アイカ工業株式会社 | Manufacturing method of 3-layer adhesive sheet |
| JP6979322B2 (en) * | 2017-10-16 | 2021-12-08 | アイカ工業株式会社 | 3-layer adhesive sheet |
| JP6947258B2 (en) * | 2018-09-05 | 2021-10-13 | 王子ホールディングス株式会社 | Adhesive sheet for bonding optical members |
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|---|---|---|---|---|
| CN102040929A (en) * | 2009-10-16 | 2011-05-04 | 琳得科株式会社 | Adhesive composition, adhesive and optical film |
| CN102051131A (en) * | 2009-10-27 | 2011-05-11 | 琳得科株式会社 | Optical adhesive composition, optical adhesive and optical film |
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| JPH0545517A (en) | 1990-12-25 | 1993-02-23 | Nippon Synthetic Chem Ind Co Ltd:The | Polarizing plate having tacky adhesive layer |
| JP3594206B2 (en) | 1995-09-14 | 2004-11-24 | 日本化薬株式会社 | Optical adhesive composition |
| JP2005344008A (en) * | 2004-06-03 | 2005-12-15 | Nitto Denko Corp | Releasable pressure-sensitive adhesive sheet |
| JP5351420B2 (en) * | 2008-01-23 | 2013-11-27 | リンテック株式会社 | Adhesive sheet and liquid crystal display device |
| JP4800363B2 (en) * | 2008-09-26 | 2011-10-26 | 日東電工株式会社 | Adhesive sheet for bonding optical members |
| JP5484104B2 (en) * | 2010-01-29 | 2014-05-07 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
| JP5743555B2 (en) * | 2010-02-02 | 2015-07-01 | リンテック株式会社 | Dicing sheet |
| JP5969162B2 (en) * | 2010-07-28 | 2016-08-17 | リンテック株式会社 | Removable adhesive sheet for coating film protection |
| JP5882107B2 (en) * | 2012-03-30 | 2016-03-09 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040929A (en) * | 2009-10-16 | 2011-05-04 | 琳得科株式会社 | Adhesive composition, adhesive and optical film |
| CN102051131A (en) * | 2009-10-27 | 2011-05-11 | 琳得科株式会社 | Optical adhesive composition, optical adhesive and optical film |
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| TWI570213B (en) | 2017-02-11 |
| JP6071231B2 (en) | 2017-02-01 |
| CN103360999A (en) | 2013-10-23 |
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| TW201339278A (en) | 2013-10-01 |
| JP2013213084A (en) | 2013-10-17 |
| KR20130111293A (en) | 2013-10-10 |
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