CN104250537B - Adhesive composition, bonding agent and adhesive sheet - Google Patents
Adhesive composition, bonding agent and adhesive sheet Download PDFInfo
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- CN104250537B CN104250537B CN201410284016.XA CN201410284016A CN104250537B CN 104250537 B CN104250537 B CN 104250537B CN 201410284016 A CN201410284016 A CN 201410284016A CN 104250537 B CN104250537 B CN 104250537B
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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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Present invention offer is a kind of will not to bring harmful effect, while the adhesive composition of excellent in te pins of durability, bonding agent and adhesive sheet to the bonded object of nesa coating etc..In order to solve above-mentioned problem, a kind of adhesive composition is provided, it contains (methyl) acrylate polymer (A), isocyanates crosslinking agent (B) and the silane coupler (C) with sulfydryl, the weight average molecular weight of (methyl) acrylate polymer (A) is 1,400,000~2,500,000, contains the monomer with hydroxyl, the monomer with ester ring type structure and the monomer with carboxyl as the monomeric unit for forming polymer；(methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, containing 1 mass %~5 mass % there is the monomer of hydroxyl, containing 0.1 mass %~0.8 mass % there is the monomer of carboxyl.
Description
Technical field
The present invention is on a kind of adhesive composition, bonding agent (material for being crosslinked adhesive composition) and bonding
Piece, especially in regard to a kind of adhesive composition, bonding agent and the adhesive sheet of the optical component for being suitable as polarized light piece etc..
Background technology
In recent years in electronic equipment of various, it is to use the contact panel for being also used as display device and input equipment more.Touch surface
The species of plate mainly has resistance-type, condenser type, optical profile type and ultrasonic type.Electric resistance touch-control panel have artifical resistance formula and
Matrix resistive, capacitance type touch-control panel have surface type and projection type.
The contact panel of the mobile electronic equipments such as the smart mobile phone that attracts attention recently, tablet personal computer terminal use more
The capacitive contact panel of projection type.As the projection type capacitance type touch-control panel of the mobile electronic equipment, for example, grinding
Study carefully and propose from bottom to top stratified liquid crystal display device (LCD), bond layer, nesa coating (tin-doped indium oxide in order：
ITO), the contact panel of the protective layer such as glass substrate, nesa coating (ITO) and strengthened glass.
As the optical component of above-mentioned composition liquid crystal display device, typically using liquid crystal cells.Liquid crystal cells are usually will
The oriented layer of two panels transparent electrode substrate formed with oriented layer is used as inner side, by distance piece (ス ペ ー サ), to form rule
Surely the mode being spaced is configured, by its peripheral sealing, the unit of clamping liquid crystal material between two panels transparent electrode substrate.It is logical
Often, the outside of the two panels transparent electrode substrate in liquid crystal cells, is bonded polarized light piece by bonding agent respectively.
Here, as described above, by the polarized light piece of liquid crystal display device by bond layer at nesa coating (ITO)
In the composition of upper fitting, bonding agent directly contacts with ITO.Therefore, because comprising largely as sour composition carboxyl bonding agent,
ITO can be produced to be corroded or the problem of ITO resistance value changes.
As the bonding agent of optics, for example, as it is known that there is the bonding agent that patent document 1 describes.The bonding agent contains by 50
The mass % of alkyl ester monomer that the carbon number of mass % (methyl) acrylic acid of quality %~90 is 4~12,3 mass %~10
The hydroxyalkyl ester monomer of mass % (methyl) acrylic acid of the ester ring type alkyl ester monomer of (methyl) acrylic acid, 0.1 mass %~1.0
And the alkyl ester monomer (amounting to 100 mass %) that the carbon number of mass % (methyl) acrylic acid of 3 mass %~10 is 1~3
Composition copolymer (contain hydroxyl in copolymer, but be free of carboxyl, weight average molecular weight be 700,000~120 ten thousand), crosslinking agent it is (relative
In 100 mass parts copolymers, for the mass parts of 0.02 mass parts~1) and crosslinking coagent (relative to 100 mass parts copolymers, be
The mass parts of 0.5 mass parts~5.0).The bonding agent is not susceptible to above-mentioned ask due to not containing the carboxyl as sour composition
Topic.
Prior art literature
Patent document
Patent document 1：Japanese Patent Publication 2012-001647 publications
The content of the invention
(1) the technical problem to be solved in the present invention
On the other hand, with the slimming of mobile electronic equipment in recent years, the polarized light piece as composition component is also begun to
Slimming.Specifically, it is inclined using keeping reducing as the thickness of the protective film of the polyvinyl alcohol of polarizer in both sides
Shake mating plate.The polarized light piece, due to preventing the ability of polarizer thermal contraction by protective film, therefore thermal contraction has than original
To become big tendency.In addition, the material as the protective film, is also easily arranged using cyclic olefin polymer (COP) etc.
Optically functional film of gas etc. replaces Triafol T.Therefore, to the bonding agent for these, it is desirable to have than now more
High reliability (durability).
But in the case of using the bonding agent of patent document 1 in polarized light piece as described above, durability is not filled
Point, under the high temperature conditions or under wet heat condition, it may occur that float or peel off.
The present invention be in view of such present situation and complete, and it is an object of the present invention to provide a kind of will not be to the quilt of nesa coating etc.
Sticky object brings harmful effect, meanwhile, adhesive composition, bonding agent and the adhesive sheet of excellent in te pins of durability.
(2) solves the technological means of technical problem
In order to reach above-mentioned purpose, first, the present invention provides a kind of adhesive composition, and it contains (methyl) acrylate
Polymer (A), isocyanates crosslinking agent (B) and the silane coupler (C) with sulfydryl, (methyl) acrylic ester polymerization
The weight average molecular weight of thing (A) is 1,400,000~2,500,000, contains the monomer with hydroxyl, tool as the monomeric unit for forming polymer
There are the monomer of ester ring type structure and the monomer with carboxyl；(methyl) acrylate polymer (A), as the composition polymerization
The monomeric unit of thing, containing 1 mass %~5 monomers described in mass % with hydroxyl, containing 0.1 mass %~0.8 mass %
The monomer (invention 1) with carboxyl.
Bonding agent obtained by foregoing invention (invention 1) described adhesive composition is crosslinked, due to (methyl) acrylic acid
Ester polymer (A) contains the monomer with hydroxyl, the monomer with ester ring type structure and with carboxyl with ormal weight respectively
Monomer is as the monomeric unit for forming the polymer, and the silane coupler (C) with sulfydryl plays excellent coupling effect
Deng, therefore excellent in te pins of durability.Further, since the amount for the carboxyl that (methyl) acrylate polymer (A) includes suppresses relatively low
Degree, therefore the unfavorable condition of the bonded object due to nesa coating caused by acid etc. can be suppressed.
In foregoing invention (invention 1), the isocyanates crosslinking agent (B), preferably trimethylolpropane are modified first time
Phenyl diisocyanate (invention 2).
(invention 1, in invention 2), isocyanates crosslinking agent (B's) contains foregoing invention described in the adhesive composition
Amount, relative to (methyl) acrylate polymer (A) described in 100 mass parts, the mass parts (invention of preferably 0.01 mass parts~1
3)。
In foregoing invention (invention 1~invention 3), the content of silane coupler (C) described in the adhesive composition, phase
For (methyl) acrylate polymer (A) described in 100 mass parts, the mass parts (invention 4) of preferably 0.01 mass parts~0.4.
In foregoing invention (invention 1~invention 4), the ester ring type structure preferably comprises cyclohexyl skeleton, dicyclopentadiene
Skeleton, adamantane framework or isoborneol skeleton (invention 5).
In foregoing invention (invention 1~invention 5), (methyl) acrylate polymer (A), as the composition polymer
Monomeric unit, preferably comprising the mass % of 0.1 mass %~20 has the monomer (invention 6) of the ester ring type structure.
Second, the present invention provides a kind of bonding agent for forming the adhesive composition (invention 1~invention 6) crosslinking
(invention 7).
In foregoing invention (invention 7), gel fraction is preferably 55%~90% (invention 8).
3rd, the present invention provides a kind of adhesive sheet, it is characterised in that it possesses base material and bond layer, the bonding agent
Layer containing the bonding agent, (9) 8) invent by invention 7, invention.
In foregoing invention (invention 9), the base material is preferably optical component (invention 10).
In foregoing invention (invention 10), the optical component is preferably polarized light piece (invention 11).
4th, the present invention provides a kind of adhesive sheet, it is characterised in that it possesses two panels stripping film and to be shelled with the two panels
The bond layer clamped from the mode that the release surface of piece connects by the stripping film, the bond layer contain the bonding agent
(invention 7, invention is 8) (invention 12).
In foregoing invention (invention 9~invention 12), to the bond layer and the layered product of nesa coating, carry out 65
DEG C, when exposing the damp and hot promotion experiment of 500 hours to the open air under 95%RH atmosphere, the nesa coating calculates according to following formula
Resistance value increment rate be preferably less than 15% (invention 13).
Resistance value increment rate (%)={ (R-R0)/R0}×100
(in formula, R0Promote the initial resistivity value before testing to be damp and hot, R is the damp and hot resistance value promoted after experiment.)
(3) invention effect
According to adhesive composition of the present invention, bonding agent and adhesive sheet, will not be glued to nesa coating etc.
Connect thing and bring harmful effect, meanwhile, excellent in te pins of durability.
Brief description of the drawings
Fig. 1 is the profile of the adhesive sheet involved by first embodiment of the present invention.
Fig. 2 is the profile of the adhesive sheet involved by second embodiment of the present invention.
Fig. 3 is the profile of the resistance value determination sample made in test example 3.
Fig. 4 is the oblique view illustrated to the test method of test example 3.
Embodiment
Hereinafter, illustrated on embodiments of the present invention.
(adhesive composition)
(hereinafter referred to as " the adhesive composition P " of adhesive composition described in present embodiment.), contain (methyl) acrylic acid
Ester polymer (A), isocyanates crosslinking agent (B) and the silane coupler (C) with sulfydryl, (methyl) acrylate gather
The weight average molecular weight of compound (A) is 1,400,000~2,500,000, contains the monomer with hydroxyl as the monomeric unit for forming polymer
(hydroxyl monomer), the monomer (structures alone containing ester ring type) with ester ring type structure and the monomer (list containing carboxyl with carboxyl
Body).In addition, (methyl) acrylate polymer (A) contains 0.1 mass % containing the mass % hydroxyl monomers of 1 mass %~5
~0.8 mass % carboxyl group-containing monomers are as the monomeric unit for forming the polymer.In addition, in this specification, described (methyl)
Acrylate refers to both of acrylate and methacrylate.Other similar terms are similarly.In addition, in " polymerization
In thing ", also include the concept of " copolymer ".
In the adhesive composition P, (methyl) acrylate polymer (A), as the monomer for forming the polymer
Unit, hydroxyl monomer and carboxyl group-containing monomer are contained with ormal weight, meanwhile, contain structures alone containing ester ring type.This is bonded
Property bonding agent obtained from composition P crosslinking, have cohesive force and stress retentivity concurrently, meanwhile, by the effect of ester ring type structure,
The optical component of polarized light piece etc., the particularly adaptation of the optical component to polycyclic alkene class or nesa coating are uprised,
Therefore excellent in te pins of durability.
In addition, if the adhesive composition P is crosslinked, then the sulfydryl of silane coupler (C) is easily and isocyanates
The NCO of class crosslinking agent (B) forms thiocarbamate key, other isocyanic acids of the isocyanates crosslinking agent (B)
The hydroxyl reaction of ester group and (methyl) acrylate polymer (A), (methyl) acrylate polymer (A) is crosslinked, forms three
Tie up network structure.Moreover, it is assumed that the alkoxysilyl of silane coupler (C) and (methyl) acrylate polymer (A)
Suitable distance is kept, is suspended on (methyl) acrylate polymer (A).Thus, excellent coupling effect is played, it is resulting
Bonding agent, under the high temperature conditions or under wet heat condition, adhesion durability is also excellent.
In addition, in the adhesive composition P, due to (methyl) acrylate polymer (A) as monomeric unit and
The content of the carboxyl group-containing monomer contained suppresses in relatively low degree, thus the attaching object of the bonding agent obtained by can suppressing due to
Unfavorable condition caused by acid, for example, in the case of for nesa coating or metal film etc., can also suppress due to caused by acid this
A little unfavorable conditions.Particularly in the case where attaching object and being nesa coating, the nesa coating can be suppressed and be corroded or be somebody's turn to do
The resistance value of nesa coating changes.
(1) (methyl) acrylate polymer (A)
(methyl) acrylate polymer (A), as form the polymer monomeric unit, except the hydroxyl monomer,
Outside structures alone containing ester ring type and carboxyl group-containing monomer, the carbon number for preferably comprising alkyl is 1~20 (methyl) acrylic acid
Arrcostab, particularly preferably contain as principal component.In addition, as needed, other monomers can also be contained.
(methyl) acrylate polymer (A), pass through (methyl) alkyl acrylate that the carbon number containing alkyl is 1~20
Base ester can show excellent cementability as the monomeric unit for forming the polymer.Carbon number as alkyl is 1~20
(methyl) alkyl acrylate, for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (first can be included
Base) propyl acrylate, (methyl) n-butylacrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid n-hexyl
Ester, (methyl) 2-ethylhexyl acrylate, (methyl) iso-octyl acrylate, (methyl) acrylic acid positive decyl ester, (methyl)
Acrylic acid n-dodecane base ester, (methyl) myristyl base ester, (methyl) acrylic acid palm base ester, (methyl) acrylic acid are hard
Aliphatic radical ester etc..Wherein, from the viewpoint of more cementability is improved, preferably the carbon number of alkyl is 1~8 (methyl) propylene
Acid esters, particularly preferred (methyl) methyl acrylate and (methyl) n-butylacrylate.In addition, these can individually make
With can also be used in combination of two or more.
(methyl) acrylate polymer (A), as form the polymer monomeric unit, preferably comprise 50 mass %~
The carbon number of 98.8 mass % alkyl is 1~20 (methyl) alkyl acrylate, particularly preferably contains 70 mass %~95
The mass % of quality %, further preferably 85.7 mass %~91.9.In addition, if (methyl) containing more than 50 mass %
Alkyl acrylate, then (methyl) acrylate polymer (A) excellent cementability can be endowed.In addition, by containing 98.8
Below quality % (methyl) alkyl acrylate, it can be imported with preferable amount in (methyl) acrylate polymer (A)
His monomer component.
(methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, contain hydroxyl monomer.Should
The NCO reactivity of hydroxyl and isocyanates crosslinking agent (B) is high, and by their reaction, (methyl) acrylate gathers
Compound (A) is crosslinked by isocyanates crosslinking agent (B).By the cross-linked structure, the durability of resulting bonding agent is excellent
It is different.
As hydroxyl monomer, such as (methyl) acrylic acid 2- hydroxyethyls ester, (methyl) acrylic acid 2- can be included
Hydroxy-propyl ester, (methyl) acrylic acid 3- hydroxy-propyl esters, (methyl) acrylic acid 2- hydroxybutyls ester, (methyl) acrylic acid 3- hydroxyls
(methyl) hydroxyalkyl acrylates of base butyl ester, (methyl) acrylic acid 4- hydroxybutyl esters etc. etc..Wherein, from isocyanic acid
The reactive view consideration of esters crosslinking agent (B), preferably (methyl) acrylic acid 2- hydroxyethyls ester or (methyl) acrylic acid 4- hydroxyls
Base butyl ester.These may be used singly or in combination of two or more use.
(methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, containing 1 mass %~5 matter
% hydroxyl monomers are measured, preferably comprise the mass % of 2 mass %~4.The content of hydroxyl monomer is in above range, the then friendship formed
Being coupled structure becomes good, and resulting bonding agent has excellent durability.The content of hydroxyl monomer is if less than 1 matter
% is measured, then crosslinking points are very few, and cohesive force reduces, and resulting bonding agent can not play excellent durability.On the other hand, containing hydroxyl
For the content of base monomer if it exceeds 5 mass %, then crosslinking points are excessive, resulting bonding agent is not soft, and stress retentivity declines,
Thus, the contraction of base material can not be tackled, durability is deteriorated.
(methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, contain the list of structure containing ester ring type
Body.Thus, resulting bonding agent is to the optical component of polarized light piece etc., the optical component particularly to polycyclic alkene class or saturating
The adaptation of bright conducting film uprises, and durability improves.
The carbocyclic ring of ester ring type structure, can be saturated structures, it is possible to have unsaturated bond.In addition, ester ring type structure can
Think monocyclic ester ring type structure, or the polycyclic ester ring type structure such as two rings, three rings.The carbon number of ester ring type structure
Preferably 5~20, particularly preferably 6~15, more preferably 7~12.
As ester ring type structure, for example, can enumerate containing cyclohexyl skeleton, dicyclopentadiene skeleton, adamantane framework,
Isoborneol skeleton, cycloalkanes hydrocarbon skeleton (cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, ring hendecane bone
Frame, cyclododecane skeleton etc.), cyclic olefin backbone (cycloheptene skeleton, cyclo-octene skeleton etc.), ENB skeleton, norborneol two
The ester ring type structure of alkene skeleton, polycycle skeleton (cubane skeleton, basket alkane skeleton, room alkane skeleton etc.), spirocyclic ring scaffold etc., its
In, preferably play more excellent raising adaptation, durability effect containing cyclohexyl skeleton, dicyclopentadiene skeleton, Buddha's warrior attendant
Alkane skeleton or isoborneol skeleton person.
As the above-mentioned monomer containing ester ring type structure, (methyl) acrylate monomer of above-mentioned skeleton is preferably comprised, is had
For body, (methyl) cyclohexyl acrylate, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid Buddha's warrior attendant can be included
Arrcostab, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) acrylic acid dicyclopentenyl oxygen
Ethyl ester etc., wherein, preferably play more excellent raising adaptation, (methyl) cyclohexyl acrylate of durability effect, (first
Base) acrylic acid bicyclopentyl ester, (methyl) acrylic acid adamantane esters or (methyl) isobornyl acrylate.These can be independent
Using one kind, can also be used in combination of two or more.
(methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, preferably comprise 0.1 mass %
~20 mass % structures alone containing ester ring type, particularly preferably containing 1 mass %~15 mass %, further preferably 6
The mass % of quality %~10.The content of the structures alone containing ester ring type has excellent in above range, then resulting bonding agent
Adaptation, and excellent durability.The content of the structures alone containing ester ring type then exists resulting if less than 0.1 mass %
Bonding agent adaptation situation about can not fully improve.On the other hand, the content of the structures alone containing ester ring type is if it exceeds 20
Quality %, then that the use level of other compositions is reduced, the durability of resulting bonding agent reduces be present.
(methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, contain carboxyl group-containing monomer.Should
Carboxyl can promote the cross-linking reaction of the hydroxyl and isocyanates crosslinking agent (B) in (methyl) acrylate polymer (A), together
When, carboxyl also crosslinks reaction with isocyanates crosslinking agent (B) in itself.Thus, the journey of the crosslinking of resulting bonding agent
Degree is appropriate, and the crosslinking degree between (methyl) acrylate polymer (A) is impartial, so as to excellent in te pins of durability.
(methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, contain 0.1 mass %~0.8
Quality % carboxyl group-containing monomer, preferably containing 0.1 mass %~0.5 mass %, particularly preferably containing 0.1 mass %~
0.3 mass %.Carboxyl group-containing monomer has excellent durability in above range, then resulting bonding agent.Carboxyl group-containing monomer
Content is deteriorated if less than 0.1 mass %, the then durability of resulting bonding agent.On the other hand, the content of carboxyl group-containing monomer
If it exceeds 0.8 mass %, then in the case where the attaching object of resulting bonding agent is nesa coating etc., electrically conducting transparent
Film etc. can be corroded, or big change occurs for the resistance value of nesa coating.
As the other monomers, even for the hydroxyl without prejudice to the hydroxyl monomer and carboxyl group-containing monomer
The reaction of carboxyl and isocyanates crosslinking agent (B), it is also preferred that do not include has reactivity with isocyanates crosslinking agent (B)
The monomer of functional group.As such other monomers, such as (methyl) methoxyethyl ethyl ester, (methyl) third can be enumerated
(methyl) alkoxyalkyl acrylate of olefin(e) acid ethoxyethyl group ester etc.；Acrylamide, Methacrylamide etc. it is non-crosslinked
The acrylamide of property；(methyl) acrylic acid N, N- dimethyl aminoethyl ester, (methyl) acrylic acid N, N- dimethylaminopropyl
(methyl) acrylate with tertiary amino of the non-crosslinked property of ester etc.；Vinyl acetate etc..These can be used alone, and also may be used
To be used in combination of two or more.
The polymerization methodses of (methyl) acrylate polymer (A), can be random copolymer, or block copolymerization
Thing.
The weight average molecular weight of (methyl) acrylate polymer (A) is 1,400,000~2,500,000, preferably 1,600,000~2,200,000,
Particularly preferably 1,800,000~2,000,000.In addition, the weight average molecular weight in this specification, is according to gel permeation chromatography (GPC)
The value for the polystyrene conversion that method is determined.
The weight average molecular weight of (methyl) acrylate polymer (A) is if less than 1,400,000, then resulting bonding agent is durable
Property be deteriorated.The weight average molecular weight of (methyl) acrylate polymer (A) is if it exceeds 2,500,000, then resulting bonding agent processing
Property be deteriorated.
In addition, in adhesive composition P, (methyl) acrylate polymer (A) can be used alone, can also
It is used in combination of two or more.In addition, adhesive composition P, which can also further contain, does not contain hydroxyl monomer, knot containing ester ring type
Structure monomer or carboxyl group-containing monomer are as (methyl) acrylate polymer for forming monomeric unit.
(2) isocyanates crosslinking agent (B)
Isocyanates crosslinking agent (B) have with (methyl) acrylate polymer (A) possessed by hydroxyl reactivity
And with silane coupler (C) possessed by sulfydryl it is reactive excellent the advantages of.
Isocyanates crosslinking agent (B) is at least crosslinking agent containing polyisocyanate compound.As polyisocyanates
Compound, such as first phenylene diisocyanate, '-diphenylmethane diisocyanate, xylylene diisocyanate etc. can be enumerated
Aromatic polyisocyanate；The aliphatic polyisocyante of hexamethylene diisocyanate etc.；IPDI,
Ester ring type polyisocyanates of hydrogenated diphenyl methane diisocyanate etc. etc., and these biuret body, isocyanuric acid ester body,
It can further enumerate and be lived as with ethylene glycol, propane diols, neopentyl glycol, trimethylolpropane, castor oil etc. containing low molecule
Adduction object of reactant of property hydrogen compound etc., wherein in the case of for polarized light piece, from durability and processability
From the viewpoint of, preferably trimethylolpropane modified aromatic race polyisocyanates, particularly preferably trimethylolpropane are modified
First phenylene diisocyanate.The isocyanates crosslinking agent (B) can be used alone, or can also combine two kinds
It is used above.
In adhesive composition P, the content of isocyanates crosslinking agent (B), relative to 100 mass parts (methyl) acrylic acid
The mass parts of ester polymer (A), preferably 0.01 mass parts~1, the mass parts of particularly preferably 0.05 mass parts~0.5, further
The mass parts of preferably 0.1 mass parts~0.3.It is by making the content of isocyanates crosslinking agent (B) in above range, then resulting
Bonding agent in, the cross-linked structure of stress retentivity and excellent in te pins of durability can be formed.
(3) silane coupler (C)
Silane coupler (C) in present embodiment has sulfydryl.The sulfydryl easily with isocyanates crosslinking agent (B)
NCO reacts.As it was previously stated, by inference in the bonding agent for being crosslinked adhesive composition P, silane coupler (C)
Alkoxysilyl keeps suitable distance with (methyl) acrylate polymer (A), i.e. in isocyanates crosslinking agent (B)
Multiple NCOs keep at a distance each other, hang on (methyl) acrylate polymer (A).Like this, alkoxy
Silicyl can be played excellent by keeping suitable distance to exist with (crosslinking) (methyl) acrylate polymer (A)
Coupling effect, thus resulting bonding agent, excellent in adhesion, even if under the high temperature conditions or under wet heat condition, bonding is durable
Property is also excellent.The effect, in the case where the attaching object of bonding agent is the inorganic material such as glass or metal, play especially aobvious
Write.
It is intramolecular at least with a sulfydryl, at least with an alkoxysilyl as silane coupler (C)
Organo-silicon compound, it is good with the compatibility of bonding agent composition, and with photopermeability person, be for example essentially that transparent person is
Preferably.
As the silane coupler (C) concrete example, for example, can include 3-mercaptopropyi trimethoxy silane,
The type of low molecule containing sulfydryl of 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyi dimethoxymethylsilanes etc. is silane coupled
Agent；3-mercaptopropyi trimethoxy silane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyi dimethoxymethylsilanes etc.
Containing mercaptosilane compound and MTES, ethyl triethoxysilane, MTMS, ethyl three
Silane coupler of oligomeric containing sulfydryl of the cocondensation containing alkyl silane cpd of methoxy silane etc. etc. etc..Wherein,
From the viewpoint of durability is improved, the preferably silane coupler of oligomeric containing sulfydryl, particularly preferably containing hydrosulphonyl silane
Compound and the cocondensation containing alkyl silane cpd, more preferably 3-mercaptopropyi trimethoxy silane and the second of methyl three
The cocondensation of TMOS.These can be used alone, and can also be used in combination of two or more.
The content of silane coupler (C) in adhesive composition P, relative to 100 mass parts (methyl) acrylic ester polymerization
The mass parts of thing (A), preferably 0.01 mass parts~0.4, the mass parts of particularly preferably 0.1 mass parts~0.3.Silane coupler
(C) content then has if less than 0.01 mass parts and is difficult to obtain the situation by effect caused by silane coupler (C).Separately
On the one hand, the content of silane coupler (C) is if it exceeds 0.4 mass parts, then isocyanates crosslinking agent (B) and (methyl) propylene
The reaction of acid ester polymer (A) has situation hindered.
(4) various additives
Adhesive composition P, as needed, usually used various additions in acrylic-based adhesives can be added
Agent, for example, antistatic agent, tackifier, antioxidant, ultra-violet absorber, light stabilizer, softening agent, filler, refractive index are adjusted
Whole dose etc..
As the specific example of antistatic agent, can enumerate N- butyl -4- picolines hexafluorophosphate, N- hexyls -
It is 4- picolines hexafluorophosphate, N- butyl -2- hexyl pyridines perchlorate, double (fluorine sulfimide) potassium (KFSI), double
(trifluoro methylsulfonimide) potassium (KTFSI), double (fluorine sulfimide) lithiums (LiFSI), double (trifluoromethanesulfonimide) lithiums
(LiTFSI), double (trifyl) imines of N- butyl -2- hexyls pyridine etc..These antistatic agents, can be used alone
One kind, it can also be used in combination of two or more.
(manufacture method of adhesive composition)
Adhesive composition P can be by manufacturing (methyl) acrylate polymer (A), by resulting (methyl) propylene
Acid ester polymer (A), isocyanates crosslinking agent (B) and silane coupler (C) are mixed, meanwhile, as needed, addition adds
Add agent to manufacture.
(methyl) acrylate polymer (A), it can will form the list of polymer by using common radical polymerization
The mixture of body unit polymerize to manufacture.The polymerization of (methyl) acrylate polymer (A), it can be triggered as needed using polymerization
Agent, carried out by solution polymerization process etc..As polymer solvent, such as ethyl acetate, ro-butyl acetate, Sucrose Acetate can be enumerated
Base ester, toluene, acetone, hexane, methyl ethyl ketone etc., can be simultaneously using two or more.
As polymerization initiator, azo compound, organic peroxide etc. can be enumerated, can simultaneously using two kinds with
On.As azo compound, such as 2 can be enumerated, 2 '-azobis isobutyronitrile, 2,2 '-azo double (2- methylbutyronitriles), 1,
1 '-azo double (hexamethylene 1- formonitrile HCNs), 2,2 '-azo double (2,4- methyl pentane nitriles), the double (2,4- dimethyl -4- of 2,2 '-azo
Methoxyl-valeronitrile), dimethyl 2,2 '-azo double (2 Methylpropionic acid ester), 4,4 '-azo double (4- cyano group valeric acids), 2,2 '-it is even
Nitrogen double (2- hydroxymethyls propionitrile), 2,2 '-azo double (2- (2- imidazoline -2- bases) propane) etc..
As organic peroxide, for example, benzoyl peroxide, peroxybenzoate, mistake can be included
Hydrogen oxide isopropylbenzene, diisopropyl peroxydicarbonate, diη-propyl peroxy dicarbonate, two (2- ethoxyethyl groups) mistakes
Aoxidize two carbonic esters, peroxidating neodecanoic acid tertiary butyl ester, peroxidating pivalic acid tertiary butyl ester, (3,5,5- trimethyl acetyls base) mistake
Oxide, two propionyl peroxide, diacetyl peroxide etc..
In addition, in above-mentioned polymerization process, by coordinating the chain-transferring agent of 2 mercapto ethanol etc., polymerization that can be to obtaining
The weight average molecular weight of thing is adjusted.
After obtaining (methyl) acrylate polymer (A), in the solution of (methyl) acrylate polymer (A), addition
Isocyanates crosslinking agent (B), silane coupler (C), retarder thinner and additive is added as needed on, carried out fully mixed
Close, obtain the adhesive composition P (coating solution) diluted with solvent.
As for being diluted to adhesive composition P, the retarder thinner of coating solution is obtained, such as oneself can be used
The aliphatic hydrocarbon of alkane, heptane, hexamethylene etc.；The aromatic hydrocarbon of toluene, dimethylbenzene etc.；The halo of dichloromethane, dichloroethanes etc.
Hydrocarbon；The alcohol of methanol, ethanol, propyl alcohol, butanol, 1- methoxy-2-propanols etc.；Acetone, methyl ethyl ketone, 2 pentanone, isophorone,
The ketone of cyclohexanone etc.；The ester of ethyl acetate, acetic acid butyl ester etc.；Cellosolve type solvents of ethyl cellosolve etc. etc..
Concentration, viscosity as the coating solution so modulated, as long as possible scope is being coated with, without special
Limitation, according to circumstances can suitably be selected.For example, adhesive composition P concentration can be diluted to 10 mass %~40
Quality %.In addition, when obtaining coating solution, the addition of retarder thinner etc. not necessarily condition, as long as adhesive composition P is applied
Possible viscosity of cloth etc., can not also add retarder thinner.In this case, adhesive composition P turns into (methyl) acrylate
Coating solution of the polymer solvent of polymer (A) directly as retarder thinner.
(bonding agent)
Bonding agent described in present embodiment, for adhesive composition P crosslinkings are formed.Adhesive composition P crosslinking can
Carried out by heating.In addition, the heating can also be also used as volatilizing to adhesive composition P retarder thinner etc.
When drying process.
In the case where being heated, heating-up temperature is preferably 50 DEG C~150 DEG C, particularly preferably 70 DEG C~120
℃.In addition, the heat time is preferably 30 seconds~10 minutes, particularly preferably 50 seconds~2 minutes., can be according to need after heating
Will, during the maturation of 1~2 week or so is set under normal temperature (for example, 23 DEG C, 50%RH).In the case of needing during the maturation,
Bond layer is formed after during the maturation；In the case of not needing during maturation, bonding is formed after heating terminates
Oxidant layer.
By above-mentioned heating (and maturation), pass through isocyanates crosslinking agent (B), (methyl) acrylic ester polymerization
Thing (A) is crosslinked, and forms three-dimensional net structure.In addition, the sulfydryl of silane coupler (C) easily with isocyanates crosslinking agent (B)
NCO reaction, the alkoxysilyl of the silane coupler (C) passes through the isocyanates crosslinking agent by inference
(B) suitable distance is kept with the three-dimensional net structure with (methyl) acrylate polymer (A), further and is existed, is played
Excellent coupling effect.
It is possessed by (methyl) acrylate polymer (A) by the bonding agent obtained by adhesive composition P crosslinkings
The effect of ester ring type structure and silane coupler (C), optical component to polarized light piece etc., particularly to polycyclic alkene system
The adaptation of optical component or nesa coating is high, and under the high temperature conditions or under wet heat condition, it is resistance to can also to play excellent bonding
Long property.For example, in the case of placement 250 is small under 85 DEG C of hot conditions or under 60 DEG C of 90%RH wet heat condition,
It can prevent from/suppress floating, peel off, the generation of bubble etc..
The gel fraction of bonding agent described in present embodiment, preferably 55%~90%, particularly preferably 60%~80%.
Gel fraction is if less than 55%, then the cohesive force deficiency of bonding agent, there is durability and the situation of re-workability reduction.Especially
It is in the case of being used for COP polarized light pieces, at high temperature, to there is the situation that cannot get sufficient adhesion durability.On the other hand, coagulate
Glue divides rate if it exceeds 90%, then stress retentivity becomes too low, there is the situation that durability reduces.
(adhesive sheet)
As shown in figure 1, adhesive sheet 1A described in the 1st embodiment, according to order from the bottom up, by stripping film 12, stacking
Formed in the bond layer 11 in the release surface of stripping film 12 and the base material 13 being laminated on bond layer 11.
In addition, as shown in Fig. 2 adhesive sheet 1B described in the 2nd embodiment, by two panels stripping film 12a, 12b, and with this
The mode that two panels stripping film 12a, 12b release surface connect, by the institute of bond layer 11 clamped by this two panels stripping film 12a, 12b
Form.In addition, in this specification so-called stripping film release surface, refer in stripping film have fissility face, including implement
The face of lift-off processing and even if be not carried out lift-off processing also show that fissility face any one.
In any one of adhesive sheet 1A, 1B, bond layer 11 all contains form above-mentioned adhesive composition P crosslinkings
Bonding agent.
The thickness of bond layer 11, is suitably determined according to the application target of adhesive sheet 1A, 1B, but usually 5 μm~100
μm, preferably 10 μm~60 μm of scope, for example, as optical component, especially as the bond layer of polarized light piece
In the case of use, preferably 10 μm~50 μm, particularly preferably 15 μm~30 μm.
As base material 13, have no particular limits, can as base material used in the substrate sheets of common adhesive sheet
Use.For example, in addition to desired optical component, it can also include and use artificial silk, acrylic acid (ester), polyester etc.
Fiber weave cotton cloth or non-woven fabrics；Synthetic paper；Good quality paper, glassine, the stationery containing impregnated paper, art paper etc.；The gold of aluminium, copper etc.
Belong to paper tinsel；The foaming body of polyurethane foaming body, foam polyethylene etc.；Polyethylene terephthalate, poly terephthalic acid fourth
The polyester film of diol ester, PEN etc.；Polyurethane film, polyethylene film, polypropylene film, three acetic acid are fine
Tie up the cellophane of element etc.；Polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethane-acetic acid ethyenyl ester
Copolymer film, polystyrene film, polycarbonate film, acrylic resin films, norbornene resin film, cycloolefin
The plastic sheeting of resin film etc.；These two or more layered products etc..Plastic sheeting can be uniaxial tension film or
The biaxial stretch-formed film of person.
As optical component, such as polarized light piece (polarized light film), polarizer, polarizer (phase can be included
Poor film), angle of visual field compensation film, improve brightness film, improve contrast film, liquid crystal polymer film, diffusion film, half
Saturating half antiferromagnetic thin film etc..Wherein, polarized light piece (polarized light film) easily shrinks, and change in size is big, therefore from requiring durability
Viewpoint considers, the suitable base material as the bonding agent (bond layer 11) for forming present embodiment.In addition, particularly polycyclic
Olefin-based film or the polarized light piece (COP polarized light pieces) for possessing the film, not only easily shrink, change in size is big, Er Qiejie
Feeler is big, and adaptation is low, therefore from the viewpoint of cementability, adhesion durability is required, is suitably used as and forms present embodiment
Bonding agent (bond layer 11) base material.
The thickness of base material 13, it is different according to its species, for example, in the case of optical component, usually 10 μm
~500 μm, preferably 50 μm~300 μm, particularly preferably 80 μm~150 μm.
As stripping film 12,12a, 12b, such as polyethylene film, polypropylene film, polybutene film, poly- can be used
Butadiene film, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate
Film, polyethylene naphthalate film, polybutylene terephthalate (PBT) film, polyurethane film, ethylene vinyl acetate base
Ester film, ionomer resin film, ethene-(methyl) acrylic copolymer film, ethene-(methyl) acrylate copolymer are thin
Film, polystyrene film, polycarbonate film, Kapton, fluorine resin film etc..In addition, it is possible to use these friendship
Join film.Further, or these laminate film.
The release surface (face particularly to connect with bond layer 11) of the stripping film, is preferably implemented with lift-off processing.
As remover used in lift-off processing, such as alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, polyolefin can be enumerated
The remover of class, wax class.
On stripping film 12,12a, 12b thickness, have no particular limits, usually 20 μm~150 μm or so.
To manufacture the adhesive sheet 1A, the solution (coating solution) containing the adhesive composition is coated on stripping film
In 12 release surface, heated, after forming film, be laminated base material 13 on the film.The film, not
In the case of needing during maturation, be directly becoming bond layer 11, in the case of during needing maturation, during the maturation after
As bond layer 11.It is as described above on heating and maturation condition.
In addition, to manufacture the adhesive sheet 1B, the coating solution containing the adhesive composition is coated on a stripping
In release surface from piece 12a (or 12b), heated, after forming film, on the film, by another stripping film
12b (or 12a) release surface is overlapping.The film, in the case of during not needing maturation, it is directly becoming bond layer
11, in the case of during needing maturation, during the maturation after turn into bond layer 11.
As the method for being coated with above-mentioned coating solution, for example, can utilize rod coating method, scraper for coating method, roller rubbing method,
Plate rubbing method, die coating methods, gravure coating method etc..
Bond layer 11 in adhesive sheet 1A, 1B, haze value (are based on JIS K7136：The value of 2000 measure) be preferably
Less than 1.0%, particularly preferably less than 0.9%, more preferably less than 0.8%.Haze value is if less than 1.0%, then
The transparency is high, is suitable for use as optical applications.
Here, for example, to manufacture the liquid crystal display device being made up of liquid crystal cells and polarized light piece, as adhesive sheet 1A
Base material 13, using polarized light piece, adhesive sheet 1A stripping film 12 is peeled off, the bond layer 11 and liquid crystal cells that will expose
It is bonded.
In addition, for example, be configured between liquid crystal cells and polarized light piece the liquid crystal display device of polarizer to manufacture,
As one, first, an adhesive sheet 1B stripping film 12a (or 12b) is peeled off, the bond layer that adhesive sheet 1B is exposed
11 are bonded with polarizer.Then, the stripping film 12 for the adhesive sheet 1A that polarized light piece has been used as base material 13 is peeled off,
The bond layer 11 that adhesive sheet 1A exposes is bonded with above-mentioned polarizer.In addition, the bond layer from above-mentioned adhesive sheet B
11, another stripping film 12b (or 12a) is peeled off, bond layer 11 and liquid crystal cells that adhesive sheet B exposes are pasted
Close.
Adhesive sheet 1A, 1B more than, the excellent in te pins of durability of bond layer 11, therefore it is even if under the high temperature conditions or wet
Under heat condition, prevented also from/suppress to produce between base material 13 or bonded object float, peel off, bubble etc..Particularly by base material
13 as in the case of COP polarized light pieces, also can by due to the deformation of COP polarized light pieces and issuable stress by bonding agent
Layer 11 absorbs, relaxed, and thus plays excellent durability.
Adhesive sheet 1A, 1B described in present embodiment, it is also preferred that using nesa coating as bonded object.Adhesive composition
The amount of the carboxyl group-containing monomer included in (methyl) acrylate polymer (A) in P as monomeric unit is as described above few
Amount, therefore the harmful effect brought due to sour composition to nesa coating can be suppressed.Specifically, nesa coating can be suppressed
It is corroded, or the resistance value of nesa coating changes.
As above-mentioned nesa coating, such as can include by the metal of platinum, gold, silver, copper etc.；Tin oxide, indium oxide,
The oxide of cadmium oxide, zinc oxide, zinc oxide etc.；Tin-doped indium oxide (ITO), Zinc oxide doped indium oxide, Fluorin doped oxygen
Change the composite oxides of indium, antimony-doped tin oxide, fluorine-doped tin oxide, aluminium-doped zinc oxide etc.；Chalkogenide, lanthanum hexaboride,
The nesa coating that non-oxidized compound of titanium nitride, titanium carbide etc. etc. is formed.
The resistance change of the nesa coating is specifically described, to using adhesive sheet 1A described in present embodiment
Or adhesive sheet 1B bond layer 11 is bonded with nesa coating obtained from layered product, carry out the atmosphere in 65 DEG C, 95%RH
Under expose to the open air 500 hours damp and hot promotion experiment when, the resistance value increment rate calculated according to following formula of nesa coating is preferred
For less than 15%, particularly preferably less than 10%.
Resistance value increment rate (%)={ (R-R0)/R0}×100
(in formula, R0Promote the initial resistivity value (Ω) before testing to be damp and hot, R is the damp and hot resistance value promoted after experiment
(Ω)。)
In addition, the details on the assay method of the resistance value increment rate of nesa coating is as described later.
The adhesive sheet 1A for having used polarized light piece as base material 13 (has referred to as " polarized light piece for having bond layer " below
Situation.), relative to the bonding force of alkali-free glass, preferably 0.1N/25mm~20N/25mm, particularly preferably 0.5N/25mm
~10N/25mm, more preferably 1N/25mm~5N/25mm.Bonding force by within the above range, can prevent with glass
Floating between the bonded object of glass plate etc. is peeled off.In addition, bonding force mentioned here, substantially refer to by based on
JIS Z0237：The bonding force that 2009 180 ° of stripping methods are determined, but determination sample is cut into wide 25mm, long 100mm, make
The determination sample is pressurizeed at 0.5MPa, 50 DEG C 20 minutes relative to bonded object attach after, in normal pressure, 23 DEG C, 50%RH
Under conditions of place 24 hours after, resulting bonding force is measured with peeling rate 300mm/min.
Embodiments described above, it is to be described for ease of understanding the present invention, is not that the present invention is limited
Fixed and progress description.Therefore, each key element disclosed in above-mentioned embodiment, also include belonging to technical scope of the invention
All design alterations and equipollent.
For example, adhesive sheet 1A stripping film 12 can omit, any one of stripping film 12a, 12b in adhesive sheet 1B
It can omit.
Embodiment
Hereinafter, further the present invention is specifically described by embodiment etc., but the scope of the present invention is not by this
The restriction of a little embodiments etc..
(embodiment 1)
The modulation of (1. methyl) acrylate polymer
By 76.9 mass parts n-butylacrylates, 10 mass parts methyl acrylates, 10 mass parts isobomyl acrylates
Ester, 3 mass parts acrylic acid 2- hydroxyethyls esters and 0.1 mass parts acrylic acid copolymer close, and modulate (methyl) acrylic ester polymerization
Thing (A).The molecular weight of (methyl) acrylate polymer (A) will be somebody's turn to do, will be determined with aftermentioned method, as a result weight average molecular weight is 180
Ten thousand.
2. the modulation of adhesive composition
By 100 mass parts (solid constituent scaled value；It is as follows) in middle (methyl) acrylate obtained of above-mentioned operation (1)
Polymer (A), 0.1 mass parts are modified the isocyanic acid of first phenylene two as the trimethylolpropane of isocyanates crosslinking agent (B)
Ester (Japanese polyurethane industrial group system, trade name " CORONATE L "), 0.3 mass parts are as the silane coupler with sulfydryl
(C) 3-mercaptopropyi trimethoxy silane and cocondensation (chemical industrial company of SHIN-ETSU HANTOTAI system, the business of MTES
The name of an article " X-411-1810 ", mercapto equivalents：450g/ moles) mixing, fully stir, be diluted by using ethyl acetate, obtained
Obtain the coating solution of adhesive composition.
Here, the cooperation of the adhesive composition is shown in table 1.In addition, the details of dummy suffix notation described in table 1 etc.
As described below.
[(methyl) acrylate polymer]
BA：N-butylacrylate
MA：Methyl acrylate
HEA：Acrylic acid 2- hydroxyethyl esters
AA：Acrylic acid
IBXA：Isobornyl acrylate
PhEA：Acrylic acid 2- phenoxyethyl acrylates
ADMMA：Adamantylmethacrylate
DCPA：The ring pentyl ester of acrylic acid two
CHA：Cyclohexyl acrylate
3. the manufacture of the polarized light piece with bond layer
By the coating solution of resulting adhesive composition, by a face of pet film
Stripping film (Lin get Ke company systems, SP-PET3811, the thickness of lift-off processing have been carried out with silicone remover：38 μm) stripping
In process face, it is coated with Scraper applicator, it is 25 μm to make dried thickness, carries out heating for 1 minute afterwards at 90 DEG C
Handle and form the film of adhesive composition.
Then, by with a face of the polarizer that is formed of cellulose triacetate film protection polyvinyl alcohol film, use ring
The COP polarized light pieces that olefin polymer films protect the thickness obtained by another face to be 100 μm are bonded with above-mentioned film, are made above-mentioned
The exposed surface of film is in contact with the surface of cyclic olefin polymer film, and maturation in 7 days is carried out under 23 DEG C, 50%RH, is obtained attached
There is the polarized light piece of bond layer.
(embodiment 2~12, comparative example 1~4)
Except will form (methyl) acrylate polymer (A) each monomer species and ratio, (methyl) acrylate
The use level of the weight average molecular weight of polymer (A), the use level of isocyanates crosslinking agent (B) and silane coupler (C), is pressed
Outside being changed shown in table 1, operated similarly to Example 1, polarized light piece of the manufacture with bond layer.In addition,
In embodiment 9, in the modulation of adhesive composition, as antistatic agent, double (the fluoroform sulphonyl of 1.8 mass parts are coordinated
Imines) lithium and tetraethyleneglycol dimethyl ether equimolar melange (three Optical Chemical Company's systems, trade name " SANKONOL TGR ").
Here, above-mentioned weight average molecular weight (Mw), to be determined under the following conditions using gel permeation chromatography (GPC)
The weight average molecular weight of the polystyrene conversion of (GPC measure).
＜ condition determinations ＞
GPC determines device：TOSOH company systems, HLC-8020
GPC posts (pass through) in the following order：TOSOH company systems
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Determine solvent：Tetrahydrofuran
Measurement temperature：40℃
(test example 1) (measure of gel fraction)
Instead of making polarized light piece used in the polarized light piece for having bond layer in embodiment or comparative example, general is used
One face of pet film has carried out stripping film (the Lin get Ke public affairs of lift-off processing with silicone remover
Department's system, SP-PET3801, thickness：38 μm), carry out the making of adhesive sheet.Specifically, in the manufacture with embodiment or comparative example
On the film exposed for the composition body that the film of stripping film/adhesive composition obtained by process is formed, so that at stripping
The mode that reason surface side connects, above-mentioned stripping film is laminated, maturation in 7 days is carried out under conditions of 23 DEG C, 50%RH.Thus,
To make with stripping film (SP-PET3801)/bond layer (thickness：25 μm) structure of/stripping film (SP-PET3811) formed
Adhesive sheet.
Obtained adhesive sheet is made to the sample of 80mm × 80mm sizes, by its bond layer polyester net (mesh chi
It is very little 200) to wrap up, weigh the single quality of bonding agent with accurate Libra.Using quality now as M1.
Then, the bonding agent above-mentioned polyester net wrapped up, under room temperature (23 DEG C), is carried out 24 hours in ethyl acetate
Dipping.Bonding agent is taken out afterwards, in the environment of 23 DEG C of temperature, relative humidity 50%, air-dry within 24 hours, further exists
Drying in 12 hours is carried out in 80 DEG C of baking oven.The dried single quality of bonding agent is weighed with accurate Libra.By matter now
Amount is used as M2.Gel fraction (%) is represented with (M2/M1) × 100.Show the result in table 2.
(test example 2) (measure of haze value)
As determination sample, prepare the adhesive sheet same with determining adhesive sheet used in gel fraction.For the bonding
Bond layer (the thickness of piece：25 μm), using haze measurement meter (Japanese electricity Se industrial groups system, NDH2000), based on JIS
K7136：2000, haze value (%) is measured.Show the result in table 2.
(test example 3) (measure of resistance value increment rate)
The polarized light piece with bond layer that will be obtained in embodiment or comparative example, according to following test method,
The resistance value of ito film is determined, calculates resistance value increment rate.
As shown in figure 3, the profile for resistance value determination sample S.It is ready to pass through sputtering on a face 21a and is provided with
Polyethylene terephthalate (PET) film 21 of ito film 22, with jointing tape 24 (Lin get Ke company systems, trade name
" TACKLINER TL-70 "), the face 21b that ito film 22 is not provided with PET film 21 and glass plate 23 a face 23a are connect
Close.
Then, in the reverse side (hereinafter referred to as " face " in the face to connect with PET film 21 with ito film 22.) on 22a,
By the electroconductive resin material containing silver, (Teng Cang is melted into company system, trade name " FA-301CA ", DOTITE contact panel circuits
Type) be coated into 20mm × 5mm rectangular electrodes shape after, being heated at 80 DEG C of temperature makes its drying for 20 minutes, forms two
As the electrode 25 of resistance value measuring point.Now, the position of two electrodes 25,25 is adjusted, is slightly larger than the distance between its
20mm。
On the other hand, by the polarized light piece 1A ' with bond layer resulting in embodiment or comparative example, it is cut into 20mm
× 250mm sizes, it (now, the polarized light piece 1A ' with bond layer, is by polarized light piece 13 ' and bonding that stripping film, which is peeled off,
The layered product that oxidant layer 11 is formed).Afterwards, the bond layer 11 of the polarized light piece 1A ' with bond layer is along two electrodes
25th, 25 side (not contacting just), on a face 22a of ito film 22, the polarised light with bond layer is attached
Piece 1A ', make resistance value test sample S as shown in Figure 3.
Afterwards, as shown in figure 4, utilizing digital multimeter (Zhi Motor Corporations system, trade name " 3802-50 ") 30, measure
Initial resistivity value R between electrode 25,250(Ω).And by resistance value test sample S, in the environment of 60 DEG C, 90%RH
After placing 500 hours, the resistance value R (Ω) after damp and hot promotion is determined.According to resulting initial resistivity value R0And damp and hot rush
Resistance value R after entering, resistance value test sample S resistance value increment rate is calculated as follows.Show the result in table 2.
Resistance value increment rate (%)={ (R-R0)/R0}×100
(test example 4) (durability evaluation)
By the polarized light piece severing with bond layer obtained by embodiment or comparative example, making 150mm ×
The sample of 200mm sizes.Stripping film is peeled off from the sample, by the bond layer exposed, in alkali-free glass (corning
Company system, Eagle XG) on attached after, make made autoclave with chestnut is former, pressurizeed 20 points at 0.5MPa, 50 DEG C
Clock.
Afterwards, put into the environment of following durable condition, after 250 hours, using 10 times of magnifying glasses, float to whetheing there is
Or peel off and confirmed.Metewand is as follows.Show the result in table 2.
◎：Do not confirm and float or peel off.
○：Confirm floating or peel off less than or equal to 0.5mm sizes.
△：Confirm and be less than or equal to floating or peeling off for 1.0mm sizes more than 0.5mm.
×：Confirm floating or peel off more than 1.0mm sizes.
The durable condition ＞ of ＜
85 DEG C of dryings
60 DEG C, relative humidity 90%RH
(test example 5) (measure of the sheet resistance value of bond layer)
By the resulting polarized light piece with bond layer in embodiment 9,50mm × 50mm sizes are cut into, by institute
Obtained sample is placed 24 hours under 23 DEG C of temperature, humidity 50%RH.Afterwards, stripping film is peeled off, to the bonding agent exposed
Layer surface, with resistivity meter (Mitsubishi Chemical's analytical technology company system, HIRESTA UP MCP-HT450 types), based on JIS
K6911, measure sheet resistance value (Ω/sq).Show the result in table 2.
In addition, sheet resistance value is preferably 3.0 × 1011Ω/below sq, particularly preferably 1.0 × 1011Ω/below sq,
More preferably 8.0 × 1010Ω/below sq.By making sheet resistance value to play good antistatic below above-mentioned value
Property.
Table 1
Table 2
As shown in Table 2, the bonding agent of bond layer resulting in embodiment is while excellent in te pins of durability, as quilt
The resistance value of the nesa coating of sticky object is not easy to be changed.
Industrial utilizability
The bonding agent and adhesive sheet of the present invention, it is suitable for nesa coating, particularly by tin-doped indium oxide (ITO)
It is the nesa coating formed and optical component, particularly bonding with polarized light piece.
Symbol description
1A, 1B ... adhesive sheet
Polarized light pieces of the 1A ' ... with bond layer
11 ... bond layers
12nd, 12a, 12b ... stripping film
13 ... base materials
13 ' ... polarized light pieces
21 ... PET films
21a, 21b ... face
22 ... ito films
22a ... faces
23 ... glass plates
23a ... faces
24 ... jointing tapes
25 ... electrodes
30 ... digital multimeter
S ... resistance value test samples
Claims (13)
1. a kind of adhesive composition, it contains：
(methyl) acrylate polymer (A), weight average molecular weight is 1,600,000~2,500,000, as the monomeric unit for forming polymer
Containing the monomer with hydroxyl, the monomer with ester ring type structure and the monomer with carboxyl,
Isocyanates crosslinking agent (B), and
Silane coupler (C) with sulfydryl；
(methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, containing 1 mass %~5 matter
Measuring has the monomer of hydroxyl described in %, containing 0.1 mass %~0.8 monomer described in mass % with carboxyl.
2. adhesive composition according to claim 1, it is characterised in that the isocyanates crosslinking agent (B) is three
Hydroxymethyl-propane is modified first phenylene diisocyanate.
3. adhesive composition according to claim 1, it is characterised in that in the adhesive composition, the isocyanide
The content of esters of gallic acid crosslinking agent (B), it is 0.01 mass parts relative to (methyl) acrylate polymer (A) described in 100 mass parts
~1 mass parts.
4. adhesive composition according to claim 1, it is characterised in that in the adhesive composition, the silane
The content of coupling agent (C), it is 0.01 mass parts~0.4 relative to (methyl) acrylate polymer (A) described in 100 mass parts
Mass parts.
5. adhesive composition according to claim 1, it is characterised in that the ester ring type structure includes cyclohexyl bone
Frame, dicyclopentadiene skeleton, adamantane framework or isoborneol skeleton.
6. adhesive composition according to claim 1, it is characterised in that (methyl) acrylate polymer (A),
As the monomeric unit for forming the polymer, containing 0.1 mass %~20 monomers described in mass % with ester ring type structure.
7. a kind of bonding agent, the adhesive composition crosslinking described in any one in 1~claim 6 of claim is formed.
8. bonding agent according to claim 7, it is characterised in that gel fraction is 55%~90%.
A kind of 9. adhesive sheet, it is characterised in that
It possesses base material and bond layer,
The bond layer contains the bonding agent described in claim 7.
10. adhesive sheet according to claim 9, it is characterised in that the base material is optical component.
11. adhesive sheet according to claim 10, it is characterised in that the optical component is polarized light piece.
12. a kind of adhesive sheet, it is characterised in that it possesses：
Two panels stripping film, and
The bond layer clamped in a manner of the release surface with the two panels stripping film connects by the stripping film；
The bond layer contains the bonding agent described in claim 7.
13. adhesive sheet according to claim 9, it is characterised in that the stacking to the bond layer and nesa coating
Body, when exposed to the open air under 65 DEG C, 95%RH atmosphere the damp and hot promotion experiment of 500 hours, the basis of the nesa coating
The resistance value increment rate that following formula calculates is less than 15%,
Resistance value increment rate (%)={ (R-R0)/R0}×100
In formula, R0Promote the initial resistivity value before testing to be damp and hot, R is the damp and hot resistance value promoted after experiment.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2013-137539 | 2013-06-28 | ||
| JP2013137539A JP6114649B2 (en) | 2013-06-28 | 2013-06-28 | Adhesive composition, adhesive and adhesive sheet |
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| CN104250537A CN104250537A (en) | 2014-12-31 |
| CN104250537B true CN104250537B (en) | 2017-11-24 |
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| CN201410284016.XA Active CN104250537B (en) | 2013-06-28 | 2014-06-23 | Adhesive composition, bonding agent and adhesive sheet |
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|---|---|
| JP (1) | JP6114649B2 (en) |
| KR (1) | KR102269915B1 (en) |
| CN (1) | CN104250537B (en) |
| TW (1) | TWI623599B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101496617B1 (en) * | 2013-09-30 | 2015-02-25 | 주식회사 엘지화학 | Polarizing Plate |
| JP6325481B2 (en) * | 2015-03-31 | 2018-05-16 | リンテック株式会社 | Adhesive sheet |
| KR102350144B1 (en) * | 2015-06-30 | 2022-01-11 | 린텍 가부시키가이샤 | Adhesive composition, adhesive, adhesive sheet and display element |
| JP6826362B2 (en) * | 2015-06-30 | 2021-02-03 | リンテック株式会社 | Adhesive sheet |
| JP6330776B2 (en) * | 2015-10-02 | 2018-05-30 | 東洋インキＳｃホールディングス株式会社 | Adhesive and adhesive sheet using the same |
| JP6738598B2 (en) * | 2015-10-28 | 2020-08-12 | リンテック株式会社 | Adhesive composition, adhesive, adhesive sheet and display |
| JP6632350B2 (en) * | 2015-11-27 | 2020-01-22 | 三星エスディアイ株式会社ＳＡＭＳＵＮＧ ＳＤＩ Ｃｏ．， ＬＴＤ． | Pressure-sensitive adhesive for optical film, pressure-sensitive adhesive layer, optical member, and image display device |
| JP6632349B2 (en) * | 2015-11-27 | 2020-01-22 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Pressure sensitive adhesive for optical film, pressure sensitive adhesive layer for optical film, optical member and image display device |
| JP6837282B2 (en) * | 2016-01-25 | 2021-03-03 | リンテック株式会社 | Optical film with adhesive layer |
| JP7153459B2 (en) * | 2018-03-28 | 2022-10-14 | 日東電工株式会社 | Adhesive layer, piece protective polarizing film with adhesive layer, image display device and continuous production method thereof |
| TWI756400B (en) * | 2017-03-29 | 2022-03-01 | 日商日東電工股份有限公司 | Adhesive layer, single-sided protective polarizing film with adhesive layer, image display device and continuous manufacturing method thereof |
| JP6688822B2 (en) * | 2017-03-29 | 2020-04-28 | 日東電工株式会社 | One-sided protective polarizing film with adhesive layer, image display device and continuous production method thereof |
| JP2018150536A (en) * | 2018-04-02 | 2018-09-27 | 東洋インキＳｃホールディングス株式会社 | Adhesive and adhesive sheet prepared therewith |
| WO2023136052A1 (en) * | 2022-01-12 | 2023-07-20 | 綜研化学株式会社 | Pressure-sensitive adhesive composition for polarizing plate, and polarizing plate with pressure-sensitive adhesive layer |
| CN114854336B (en) * | 2022-05-12 | 2024-06-11 | 上海甘戎新材料有限公司 | Adhesive composition, adhesive film, and preparation method and application thereof |
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| CN1690097A (en) * | 2004-04-27 | 2005-11-02 | 住友化学株式会社 | Acrylic |
| CN102585713A (en) * | 2010-12-31 | 2012-07-18 | 第一毛织株式会社 | Optical adhesive composition for displays, optical adhesive film prepared from the same, and display panel including the same |
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| JP4381686B2 (en) * | 2003-01-22 | 2009-12-09 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition for polarizing film |
| JP5048994B2 (en) | 2006-10-20 | 2012-10-17 | サイデン化学株式会社 | Adhesive composition and optical functional film |
| JP5346220B2 (en) | 2009-02-03 | 2013-11-20 | リンテック株式会社 | Adhesive and adhesive sheet |
| JP5588755B2 (en) | 2010-06-18 | 2014-09-10 | 株式会社寺岡製作所 | Adhesive for optical members |
| KR20120001647A (en) | 2010-06-28 | 2012-01-04 | 주식회사 누마스타세척기 | Hand washer |
| JP5607565B2 (en) * | 2011-03-28 | 2014-10-15 | リンテック株式会社 | Adhesive and adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1690097A (en) * | 2004-04-27 | 2005-11-02 | 住友化学株式会社 | Acrylic |
| CN102585713A (en) * | 2010-12-31 | 2012-07-18 | 第一毛织株式会社 | Optical adhesive composition for displays, optical adhesive film prepared from the same, and display panel including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104250537A (en) | 2014-12-31 |
| KR20150002460A (en) | 2015-01-07 |
| TW201504375A (en) | 2015-02-01 |
| JP6114649B2 (en) | 2017-04-12 |
| JP2015010193A (en) | 2015-01-19 |
| TWI623599B (en) | 2018-05-11 |
| KR102269915B1 (en) | 2021-06-25 |
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