CN105683324B - Optics adhesive, optics adhesive tape and laminated body - Google Patents
Optics adhesive, optics adhesive tape and laminated body Download PDFInfo
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- CN105683324B CN105683324B CN201480059825.9A CN201480059825A CN105683324B CN 105683324 B CN105683324 B CN 105683324B CN 201480059825 A CN201480059825 A CN 201480059825A CN 105683324 B CN105683324 B CN 105683324B
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- Prior art keywords
- methyl
- optics
- acrylate
- adhesive
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Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
Abstract
The object of the present invention is to provide a kind of optics adhesives, will not haze if exposed to after high temperature and humidity, and resistance to foaminess, processability are also excellent, and will not make to be deteriorated by the transparent electrode that ITO etc. is formed.In addition, the object of the present invention is to provide optics adhesive tapes and laminated body that the optics is used to be manufactured with adhesive.The present invention is a kind of optics adhesive, it contains (methyl) acrylic polymer and crosslinking agent, (methyl) acrylic polymer is to be made by active free radical polymerization containing a) have carbon atom number 1~14 alkyl 60~95 parts by weight of (methyl) alkyl acrylate, b) 0.1~1 parts by weight of monomer containing carboxyl, and c) contain hydroxyl, obtained from the monomer mixture copolymerization of 10~30 parts by weight of monomer of amino or amide groups, and the molecular weight distribution (Mw/Mn) of (methyl) acrylic polymer is 1.05~2.5, and, (methyl) alkyl acrylate of alkyl a) with carbon atom number 1~14 includes (methyl) acrylate with twin nuclei.
Description
Technical field
The present invention relates to if exposed to will not haze after high temperature and humidity, resistance to foaminess and processability it is also excellent and
It will not make the optics adhesive deteriorated by the transparent electrode that ITO etc. is formed.Moreover, it relates to it is bonded using the optics
The optics adhesive tape and laminated body of agent manufacture.
Background technology
Adhesive used in optical applications is such as in portable information terminal by display, touch panel to component
It is used when being bonded on housing.Due to clear to display picture requirement, therefore, it is desirable to have if exposed to will not after high temperature and humidity
The adhesive to haze.
In addition, outgassing is generated from adherend sometimes when being exposed under high temperature and humidity in optical applications, with being glued
Bubble is generated in the bonding plane of object.Due to such bubble becomes the clarity that damage shows picture, for bonding
It is excellent that agent also wants to resistance to foaminess.
In addition, demand with the miniaturization of electronic unit in recent years, slimming or lightweight or to economizing on resources
Increase, as adhesive tape used in optical applications, it is desirable to have than previous thinner adhesive tape.However, if it is desired to it is glued with thin
Crossed belt obtains sufficient bonding force, then exist want by adhesive tape be processed as arbitrary shape but can not precision it is excellent cut off and
It deforms or the problem of adhesive tape is shredded.Accordingly it is desirable to have can produce it is excellent viscous thin and its processability
The adhesive of crossed belt.
In patent document 1, describe to include with double using radical polymerization (mono- ラ ジ カ Le coincidence methods of Off リ) method
Adhesive tape of the polyacrylate as principal component obtained by the polymerizable monomer polymerization of the acrylic monomer of ring, the adhesive tape are shown
It shows if exposed to being not easy to the excellent effect of bubble for hazing, being easily worked, bonding plane being inhibited after under high temperature and humidity
Fruit.However, when by the adhesive tape described in patent document 1 in electronic unit, there are when make by tin-doped indium oxide
(ITO) etc. the problem of the transparent electrode deterioration of compositions.Additionally, it is desirable that have the adhesive with superior performance, it is particularly uncommon
Prestige has following adhesive, that is, when in recent years desired adhesive tape thin like that, if exposed under high temperature and humidity
After will not haze, resistance to foaminess is excellent, and processability is also excellent, suitable for optical applications.
Existing technical literature
Patent document
Patent document 1：International Publication No. 2011/007861
Invention content
Problems to be solved by the invention
The object of the present invention is to provide a kind of optics adhesive, if exposed to will not after under high temperature and humidity
It hazes, resistance to foaminess, processability are also excellent, and will not make to be deteriorated by the transparent electrode that ITO etc. is formed.In addition, the present invention
Purpose is, provides the optics adhesive tape and laminated body manufactured using the optics with adhesive.
The method used for solving the problem
The present invention provides a kind of optics adhesive, contains (methyl) acrylic polymer and the crosslinking agent, (first
Base) acrylic polymer is to be made by active free radical polymerization (coincidence of リ ビ Application グ ラ ジ カ Le) containing a) there is carbon atom
60~95 parts by weight of (methyl) alkyl acrylate of the alkyl of number 1~14, b) 0.1~1 parts by weight of monomer containing carboxyl, with
And c) obtained by the monomer mixture copolymerization of 10~30 parts by weight of monomer containing hydroxyl, amino or amide groups, and (the first
Base) acrylic polymer molecular weight distribution (Mw/Mn) for 1.05~2.5, also, described a) there is carbon atom number 1~14
(methyl) alkyl acrylate of alkyl contain (methyl) acrylate with twin nuclei.
Hereinafter, the present invention is described in detail.
As adhesive used in optical applications, generally use through " radical polymerization (mono- ラ ジ カ Le of Off リ
Overlap) " make polymer obtained by the polymerization of the free radical polymerization monomers such as (methyl) acrylic monomer.
However, radical polymerization can not fully control molecular weight and molecular weight distribution, copolymer composition etc., there is generation
Low molecular weight compositions can also generate the shortcomings that homopolymer is such in the case of copolymerization.The inventors of the present invention think such low point
Son amount ingredient or homopolymer become be exposed under high temperature and humidity after adhesive become easily to haze or bonding plane generate bubble,
Or the reason of processability variation.In addition, in polymer used in adhesive, for the mesh that cohesiveness is assigned to adhesive
, it is generally mated the monomers containing carboxyl such as (methyl) acrylic acid.The inventors of the present invention think, are obtained by radical polymerization poly-
It closes in object, the polymer chain comprising the monomer containing carboxyl is with free state by comprising this, which becomes, makes what transparent electrode deteriorated
Reason.The deterioration of transparent electrode in order to prevent, it is contemplated that the use level of the monomer containing carboxyl is reduced, if however reducing and containing carboxylic
The use level of the monomer of base can not then ensure the cohesiveness of the adhesive of gained.
In view of this, the inventors of the present invention have studied use not by radical polymerization but by the way that " living radical gathers
Polymer obtained from conjunction ".
Active free radical polymerization is that polymerisation will not be made point in which interfere by reaction or the side reactions such as chain transfer reaction are terminated
Therefore the polymerization that subchain growth is gone down, is easy to control molecular weight and molecular weight distribution, copolymer composition etc., can be without low point
The generation and copolymerization of son amount ingredient, so as to inhibit the generation of generated homopolymer.In addition, gather by using living radical
It closes, even if reducing the use level of the monomer containing carboxyl, sufficient cohesiveness is also ensured, and free state can be reduced
The polymer chain for including the monomer containing carboxyl, therefore the deterioration of transparent electrode can be prevented.
The inventors of the present invention have found, if following optics adhesive, that is, containing (methyl) acrylic polymer and
Crosslinking agent, (methyl) acrylic polymer are to make to contain a with specific mixing ratio by active free radical polymerization) tool
Have (methyl) alkyl acrylate, the b of the alkyl of carbon atom number 1~14) monomer and c containing carboxyl) containing hydroxyl, ammonia
Obtained by the monomer mixture copolymerization of the monomer of base or amide groups, and the molecular weight distribution (Mw/Mn) with particular range, and
(methyl) alkyl acrylate of above-mentioned alkyl a) with carbon atom number 1~14 includes (methyl) propylene with twin nuclei
Acid esters, then if exposed to that will not haze after under high temperature and humidity, resistance to foaminess, processability are also excellent, and will not make by ITO
Etc. compositions transparent electrode deterioration, so as to complete the present invention.
The optics adhesive of the present invention contains (methyl) acrylic polymer, (methyl) acrylic polymer
It is that (methyl) alkyl acrylate 60~95 containing alkyl a) with carbon atom number 1~14 is made by active free radical polymerization
Parts by weight, b) 0.1~1 parts by weight of monomer containing carboxyl and c) 10~30 weight of monomer containing hydroxyl, amino or amide groups
Obtained by measuring the monomer mixture copolymerization of part, and the molecular weight distribution (Mw/Mn) of (methyl) acrylic polymer is
1.05~2.5.
It should be noted that so-called (methyl) acrylate, refers to acrylate and methacrylate.
By (methyl) acrylic acid for containing the above-mentioned a) alkyl with carbon atom number 1~14 in above-mentioned monomer mixture
60~95 parts by weight of Arrcostab, so that the raisings such as the cohesiveness of optics adhesive, initial bond, adaptation.It is above-mentioned
The preferred lower limit of the above-mentioned a) content of (methyl) alkyl acrylate of the alkyl with carbon atom number 1~14 of monomer mixture
For 70 parts by weight, preferred upper limit is 90 parts by weight.
(methyl) alkyl acrylate of above-mentioned alkyl a) with carbon atom number 1~14 contains with twin nuclei
(methyl) acrylate.
Above-mentioned twin nuclei is not particularly limited, as the functional group with above-mentioned twin nuclei, for example, double
Ring [1.1.0] butyl, bicyclic [1.1.1] amyl, bicyclic [2.1.0] amyl, bicyclic [3.1.0] hexyl, bicyclic [2.1.1] oneself
It is base, bicyclic [2.2.0] hexyl, bicyclic [2.2.1] heptyl, bicyclic [3.1.1] heptyl, bicyclic [3.2.0] heptyl, bicyclic
[4.1.0] heptyl, bicyclic [2.2.2] octyl group, bicyclic [3.2.1] octyl group, bicyclic [3.3.0] octyl group, bicyclic [4.1.1] octyl group,
Bicyclic [4.2.0] octyl group, bicyclic [5.1.0] octyl group, bicyclic [3.2.2] nonyl, bicyclic [3.3.1] nonyl, bicyclic [4.2.1] nonyl
It is base, bicyclic [4.3.0] nonyl, bicyclic [5.1.1] nonyl, bicyclic [5.2.0] nonyl, bicyclic [6.1.0] nonyl, bicyclic
[4.3.1] decyl and with by the part chain-like alkyl or ring of the hydrogen atom of these functional groups with twin nuclei
Functional group of the alkyl substituted structure of shape etc..It should be noted that above-mentioned substitution can be 1 position or multiple
Position.Wherein, preferably norborny, isobornyl, particularly preferred isobornyl.That is, as the (first with above-mentioned twin nuclei
Base) acrylate, (methyl) isobornyl acrylate particularly preferably with isobornyl and (methyl) acryloyl group.
In above-mentioned a) 60~95 parts by weight of (methyl) alkyl acrylate of the alkyl with carbon atom number 1~14, have
(methyl) acrylate of above-mentioned twin nuclei is preferably 5~55 parts by weight.If (methyl) propylene with above-mentioned twin nuclei
The mixing ratio of acid esters is detached from above range, then optics adhesive becomes to be easily peeled off, and becomes easily to generate gas in bonding plane
Bubble.The mixing ratio of (methyl) acrylate with above-mentioned twin nuclei is more preferably 7~40 parts by weight.
Above-mentioned a other than (methyl) acrylate with above-mentioned twin nuclei) alkyl with carbon atom number 1~14
(methyl) alkyl acrylate in, the alkyl of carbon atom number 1~14 can be long-chain or branch, can also be ring
Shape.As such (methyl) alkyl acrylate, for example, (methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2- ethyl hexyls
Ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid 2- second
Base monooctyl ester, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl
Ester, the different tetradecane base ester of (methyl) acrylic acid etc..Furthermore it is also possible to enumerate with cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl,
(methyl) acrylate of the cyclic alkyls such as suberyl, cyclooctyl.Wherein, it is low, initial stage from low temperature elasticity modulus can be obtained
It sets out in terms of wetability high optics adhesive, is preferably selected from (methyl) 2-EHA, (methyl) acrylic acid
It is at least one kind of in monooctyl ester and (methyl) butyl acrylate.
By including the above-mentioned b) monomer containing carboxyl in above-mentioned monomer mixture, so that optics adhesive
The raisings such as cohesiveness.
As the above-mentioned b) monomer containing carboxyl, for example, (methyl) acrylic acid, phthalic acid, terephthaldehyde
Acid, pyromellitic acid etc..Wherein, preferred acrylic acid.
If the mixing ratio of the above-mentioned b) monomer containing carboxyl is less than 0.1 parts by weight, optics in above-mentioned monomer mixture
Become to be easily peeled off with the cohesiveness deficiency of adhesive, become easily to generate bubble in bonding plane, use optics adhesive
The processability of the adhesive tape of manufacture can also reduce.If the mixing ratio of the above-mentioned b) monomer containing carboxyl is more than 1 parts by weight,
For making to be deteriorated by the transparent electrode that ITO etc. is formed sometimes during electronic unit.In addition, the gel fraction of optics adhesive becomes
Must be excessively high, become to be easily peeled off after being exposed under high temperature and humidity, easily generate bubble in bonding interface, resistance to foaminess becomes to hold
Easily reduce.
By including above-mentioned monomer c) containing hydroxyl, amino or amide groups in above-mentioned monomer mixture, so as to
Optics is hazed with adhesive after preventing in the case where being exposed to high temperature and humidity.
As the monomer containing hydroxyl in above-mentioned monomer c) containing hydroxyl, amino or amide groups, for example,
(methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid 4- hydroxybutyls, is used end (methyl) hydroxypropyl acrylate
Acryl-modified polyethylene glycol, polypropylene glycol that an end has been used acryl-modified etc..Wherein, preferred propylene
Sour hydroxy methacrylate.
As the above-mentioned monomer containing amino, for example, (methyl) acrylate ester, (methyl) third
Olefin(e) acid diethyl amino base ester, (methyl) acrylic-amino methyl esters, (methyl) acrylate, (methyl) acrylic acid dimethyl
Amino ethyl ester etc..Wherein, preferred (methyl) acrylate.
As the above-mentioned monomer containing amide groups, for example, diacetone acrylamide (Diacetone Acrylamide),
N,N-DMAA, N, N- acrylamides, n-isopropyl acrylamide, N- hydroxyethyl acrylamides, third
Acrylamide, Methacrylamide etc..Wherein, preferred diacetone acrylamide.
Above-mentioned monomer c) containing hydroxyl, amino or amide groups both can be used alone, and can also be used together by two or more types.
In the case of being used together by two or more types, preferably used by the monomer containing hydroxyl and containing the combination of monomers of amino or amide groups.
If the mixing ratio of above-mentioned monomer c) containing hydroxyl, amino or amide groups is less than 10 weights in above-mentioned monomer mixture
Part is measured, then optics becomes easily to haze with adhesive after being exposed under high temperature and humidity.It is if above-mentioned c) containing hydroxyl, amino or amide
The mixing ratio of the monomer of base is more than 30 parts by weight, then viscosity when being coated with is excessively high and is difficult to be coated with, and generates be coated with sometimes
Optics adhesive uneven thickness.
Above-mentioned monomer mixture can also be in (methyl) acrylic acid alkyl of the above-mentioned a) alkyl with carbon atom number 1~14
Other than ester, the above-mentioned b) monomer containing carboxyl and above-mentioned monomer c) containing hydroxyl, amino or amide groups, also containing can
The monomer being copolymerized with them.The above-mentioned monomer that can be copolymerized is not particularly limited, for example, (methyl) acrylate, second
Alkenyl compound etc..
Above-mentioned (methyl) acrylate is not particularly limited, and can enumerate the different myristin of (methyl) acrylic acid, (methyl)
Stearyl acrylate etc. (methyl) alkyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2- butoxyethyls,
(methyl) acrylic acid 2- phenoxy ethyls, (methyl) glycidyl acrylate, (methyl) tetrahydrofurfuryl acrylate, polypropylene glycol
Single (methyl) acrylate etc..These (methyl) acrylate both can be used alone, and can also be used together by two or more types.
Above-mentioned vinyl compound is not particularly limited, for example, N- caprolactams, N- vinylpyridines
Pyrrolidone, N- vinyl acetamides, N- acryloyl morpholines, acrylonitrile, styrene, vinyl acetate etc..These are vinylated
It closes object both to can be used alone, can also be used together by two or more types.
Above-mentioned (methyl) acrylic polymer is to obtain above-mentioned monomer mixture copolymerization by active free radical polymerization
(methyl) acrylic polymer, make preferably by the active free radical polymerization for having used organic tellurium polymerization initiator above-mentioned
(methyl) acrylic polymer obtained by monomer mixture copolymerization.
Active free radical polymerization is that polymerisation will not be made point in which interfere by reaction or the side reactions such as chain transfer reaction are terminated
The polymerization that subchain growth is gone down, therefore molecular weight and molecular weight distribution, copolymer composition etc. are easy to control, can there is no low molecule
The generation and copolymerization of ingredient are measured, so as to inhibit the generation of generated homopolymer.Therefore, by containing above-mentioned (methyl) acrylic acid
Type of Collective object, even if optics adhesive of the invention will not haze after being exposed under high temperature and humidity, resistance to foaminess is excellent,
And processability is also excellent.In addition, by using active free radical polymerization, so that even if reducing the monomer containing carboxyl
Sufficient cohesiveness is also ensured in use level, and can reduce the polymer for including the monomer containing carboxyl of free state
Chain, therefore the deterioration of transparent electrode can be prevented.
The schematic diagram illustrated to active free radical polymerization is shown in Fig. 1.
Active free radical polymerization is that polymerisation will not be made point in which interfere by reaction or the side reactions such as chain transfer reaction are terminated
The polymerization that subchain growth is gone down.In active free radical polymerization, it will not inactivated in growth end free base and in the reaction also not
In the case of new free radical kind can be generated, reacted.In the reaction way, all polymer chains on one side equably with list
Body carries out reaction and is polymerize on one side, and the composition of all polymer is close to uniformly.Therefore, containing comprising cross-linking functional group
The monomer 12 of hydroxyl, amino or amide groups, the monomer 13 containing carboxyl are comprised in (first obtained by progress active free radical polymerization
Base) acrylic polymer 1 whole polymer in.If by (methyl) acrylic acid obtained by such progress active free radical polymerization
Type of Collective object 1 utilizes cross-linking agents, then substantially all of polymer can be participated in the crosslinking between polymer chain.
Shown in Fig. 2 to will as obtained from active free radical polymerization the crosslinked situation of (methyl) acrylic polymer
The schematic diagram illustrated.In (methyl) acrylic polymer as obtained from active free radical polymerization, whole is poly-
The composition for closing object is uniform, and containing the monomer containing hydroxyl, amino or amide groups comprising cross-linking functional group, therefore whole is poly-
Object chain is closed to participate in crosslinking (it should be noted that the example in Fig. 2 as cross-linking functional group describes hydroxyl.).So
Described, substantially all of polymer can participate in the crosslinking between polymer chain, therefore not have the life of low molecular weight compositions
Into and copolymerization, so as to the generation of homopolymer caused by inhibiting, excellent resistance to foaminess, processability can have been given play to.This
Outside, even if reducing the use level of the monomer containing carboxyl, sufficient cohesiveness is also ensured, and essentially free of free
The polymer chain for including the monomer containing carboxyl of state, therefore the deterioration of transparent electrode can be prevented.
It can not the effect of the present invention is even if using the previous acrylic acid series polymeric compounds as obtained from radical polymerization yet
It obtains.
The schematic diagram illustrated to radical polymerization is shown in Fig. 3.
In radical polymerization, continuously generate free radicals plant and addition is polymerize in monomer in the reaction.Therefore, exist
In radical polymerization, growth end free base has inactivated in the reaction polymer 24 and newly generated using in reaction are generated
Free radical kind and the polymer 25 that grows.Therefore, if manufacturing (methyl) acrylic polymer using radical polymerization,
It can then generate that not contain monomer 22 the, molecular weight containing hydroxyl, amino or amide groups comprising cross-linking functional group relatively low
Polymer.Even if (methyl) acrylic polymer 2 obtained by such progress radical polymerization using cross-linking agents, is not wrapped
Polymer containing the monomer containing hydroxyl, amino or amide groups can not be also participated in the crosslinking between polymer chain.
It shows to say the crosslinked situation of (methyl) acrylic polymer obtained by carrying out radical polymerization in Fig. 4
Bright schematic diagram.In (methyl) acrylic polymer obtained by radical polymerization is carried out, since the composition of polymer is uneven
One, containing the relatively low polymer of the molecular weight not comprising the monomer containing hydroxyl, amino or amide groups, therefore presence can not participate in
Crosslinked polymer chain is (it should be noted that the example in Fig. 4 as cross-linking functional group describes hydroxyl.).In addition, also contain
There is the polymer chain for including the monomer containing carboxyl of free state.(methyl) propylene obtained by progress radical polymerization is used
In the case of acids polymers, due to the relatively low ingredient of the molecular weight not being crosslinked, and bubble or processability are generated in bonding plane
It is deteriorated.In addition, needing to coordinate the relatively large number of monomer containing carboxyl in order to ensure cohesiveness, thus transparent electricity can not be prevented
The deterioration of pole.In addition, the polymer chain comprising the monomer containing carboxyl of free state also becomes the reason of transparent electrode deterioration.
In active free radical polymerization, the active free radical polymerization of organic tellurium polymerization initiator and others activity have been used
Free radical polymerization is different, for functional groups such as carboxyl, hydroxyl, epoxy group, amino, isocyanate group, amide groups, itrile groups
Monomer be not protected in the case of, polymerize using identical initiator and can be obtained with uniform molecular weight
And the polymer of composition.Therefore, the monomer with such functional group can be easily copolymerized.
As long as general organic tellurium polymerization initiator used in above-mentioned organic tellurium polymerization initiator active free radical polymerization,
It is just not particularly limited, for example, Organic Tellurium Compounds, organic tellurides compound (having Machine テ Le リ De compound)
Deng.
As above-mentioned Organic Tellurium Compounds, for example, (methyl hydrogen telluro (tellanyl)-methyl) benzene, (1- first
Base hydrogen telluro-ethyl) benzene, (2- methyl hydrogens telluro-propyl) benzene, the chloro- 4- of 1- (methyl hydrogen telluro-methyl) benzene, 1- hydroxyls -4-
(methyl hydrogen telluro-methyl) benzene, 1- methoxyl groups -4- (methyl hydrogen telluro-methyl) benzene, 1- amino -4- (methyl hydrogen telluro-methyl)
Benzene, 1- nitros -4- (methyl hydrogen telluro-methyl) benzene, 1- cyano -4- (methyl hydrogen telluro-methyl) benzene, 1- methyl carbonyl -4- (first
Base hydrogen telluro-methyl) benzene, 1- phenylcarbonyl groups -4- (methyl hydrogen telluro-methyl) benzene, 1- methoxycarbonyls -4- (methyl hydrogen telluro -
Methyl) benzene, 1- phenyloxycarbonyls -4- (methyl hydrogen telluro-methyl) benzene, 1- sulfonyls -4- (methyl hydrogen telluro-methyl) benzene, 1-
Trifluoromethyl -4- (methyl hydrogen telluro-methyl) benzene, the chloro- 4- of 1- (1- methyl hydrogens telluro-ethyl) benzene, 1- hydroxyls -4- (1- methyl
Hydrogen telluro-ethyl) benzene, 1- methoxyl groups -4- (1- methyl hydrogens telluro-ethyl) benzene, 1- amino -4- (1- methyl hydrogens telluro-ethyl)
Benzene, 1- nitros -4- (1- methyl hydrogens telluro-ethyl) benzene, 1- cyano -4- (1- methyl hydrogens telluro-ethyl) benzene, 1- methyl carbonyl -
4- (1- methyl hydrogens telluro-ethyl) benzene, 1- phenylcarbonyl groups -4- (1- methyl hydrogens telluro-ethyl) benzene, 1- methoxycarbonyl -4- (1-
Methyl hydrogen telluro-ethyl) benzene, 1- phenyloxycarbonyls -4- (1- methyl hydrogens telluro-ethyl) benzene, 1- sulfonyls -4- (1- methyl hydrogens
Telluro-ethyl) benzene, 1- trifluoromethyls -4- (1- methyl hydrogens telluro-ethyl) benzene, the chloro- 4- of 1- (2- methyl hydrogens telluro-propyl) benzene,
1- hydroxyls -4- (2- methyl hydrogens telluro-propyl) benzene, 1- methoxyl groups -4- (2- methyl hydrogens telluro-propyl) benzene, 1- amino -4- (2-
Methyl hydrogen telluro-propyl) benzene, 1- nitros -4- (2- methyl hydrogens telluro-propyl) benzene, 1- cyano -4- (2- methyl hydrogens telluros-the third
Base) benzene, 1- methyl carbonyls -4- (2- methyl hydrogens telluro-propyl) benzene, 1- phenylcarbonyl groups -4- (2- methyl hydrogens telluro-propyl) benzene,
1- methoxycarbonyls -4- (2- methyl hydrogens telluro-propyl) benzene, 1- phenyloxycarbonyls -4- (2- methyl hydrogens telluro-propyl) benzene, 1-
Sulfonyl -4- (2- methyl hydrogens telluro-propyl) benzene, 1- trifluoromethyls -4- (2- methyl hydrogens telluro-propyl) benzene, 2- (methyl hydrogen telluriums
Base-methyl) pyridine, 2- (1- methyl hydrogens telluro-ethyl) pyridine, 2- (2- methyl hydrogens telluro-propyl) pyridine, 2- methyl hydrogen telluriums
Base-ethanetricarboxylic acid methyl esters, 2- methyl hydrogens telluro-methyl propionate, 2- methyl hydrogens telluro -2 Methylpropionic acid methyl esters, 2- methyl hydrogens telluro -
Ethane acetoacetic ester, 2- methyl hydrogens telluro-ethyl propionate, 2- methyl hydrogens telluro -2 Methylpropionic acid ethyl ester, 2- methyl hydrogen telluro second
Nitrile, 2- methyl hydrogen telluros propionitrile, 2- methyl -2- methyl hydrogen telluro propionitrile etc..Methyl hydrogen telluro in these Organic Tellurium Compounds
Can be ethyl hydrogen telluro, n-propyl hydrogen telluro, isopropyl hydrogen telluro, normal-butyl hydrogen telluro, isobutyl group hydrogen telluro, tertiary butyl hydrogen
Telluro, phenyl hydrogen telluro etc., in addition, these Organic Tellurium Compounds can be used alone, can also be used together by two or more types.
As above-mentioned organic tellurides compound, for example, two tellurides of dimethyl, two tellurides of diethyl, two
Two tellurides of n-propyl, two tellurides of diisopropyl, two tellurides of Bicyclopropyl, two tellurides of di-n-butyl, di-sec-butyl two
Tellurides, two tellurides of di-t-butyl, two cyclobutyl, two tellurides, two tellurides of diphenyl, bis- (p-methoxyphenyl) two telluriums
It is compound, bis- (p-aminophenyl) two tellurides, bis- (p-nitrophenyl) two tellurides, bis- (to cyano-phenyl) two tellurides, double
(to sulfonvlphenyl) two tellurides, two tellurides of dinaphthyl, two tellurides of bipyridyl etc..These organic tellurides compounds
Both it can be used alone, can also be used together by two or more types.Wherein, preferably two tellurides of dimethyl, two tellurides of diethyl, two are being just
Two tellurides of propyl, two tellurides of di-n-butyl, two tellurides of diphenyl.
It should be noted that it can also polymerize in above-mentioned organic tellurium and cause within the scope of the effect of the invention
Other than agent, for the purpose for promoting polymerization speed, using azo-compound as polymerization initiator.
As long as general azo-compound used in above-mentioned azo-compound free radical polymerization, there is no particular limitation,
For example, 2,2 '-azodiisobutyronitrile, 2,2 '-azo bis- (2- methylbutyronitriles), 2, bis- (2, the 4- dimethyl of 2 '-azo
Valeronitrile), 2,2 '-azo bis- (4- methoxyl groups -2,4- methyl pentane nitriles), 1,1- azos bis- (hexamethylene -1- formonitrile HCNs), 1- [(1- cyanogen
Base -1- Methylethyls) azo] formamide, 4,4 '-azo bis- (4- cyanopentanoic acids), 2, bis- (2 Methylpropionic acid) diformazans of 2 '-azo
Ester, 1, bis- (1- naphthenic acids) dimethyl esters of 1 '-azo, 2, bis- { 2- methyl-N- [1,1 '-two (the hydroxymethyl) -2- of 2 '-azo
Hydroxyethyl] propionamide, 2,2 '-azo bis- [2- methyl-N- (2- hydroxyethyls) propionamides], 2, the bis- [N- (2- third of 2 '-azo
Alkenyl) -2- methyl propanamides], 2,2 '-azo bis- (N- butyl -2- methyl propanamides), 2, the bis- (N- cyclohexyl -2- of 2 '-azo
Methyl propanamide), 2, bis- [2- (2- imidazoline -2- bases) propane] dihydrochlorides of 2 '-azo, 2, bis- { 2- [1- (the 2- hydroxyls of 2 '-azo
Base ethyl) -2- imidazoline -2- bases] propane dihydrochloride, 2,2 '-azo bis- [2- (2- imidazoline -2- bases) propane], 2,2 ' -
Bis- (2- amidine propanes) dihydrochlorides of azo, 2, bis- [N- (2- the carboxy ethyls) -2- methyl-props amidine] tetrahydrates of 2 '-azo, 2,
Bis- (1- imino group -1- pyrrolidines -2- methylpropanes) dihydrochlorides of 2 '-azo, 2,2 '-azo is bis- (2,4,4- trimethylpentane)
Deng.These azo-compounds both can be used alone, and can also be used together by two or more types.
As the method for above-mentioned active free radical polymerization, it can make by a conventionally known method, for example, solution
Polymerization (boiling point polymerize or constant temperature polymerization), emulsion polymerization, suspension polymerisation, bulk polymerization etc..
Using in the case of polymer solvent in above-mentioned active free radical polymerization, which is not particularly limited, example
Such as can use hexane, hexamethylene, octane, toluene, dimethylbenzene nonpolar solvent or water, methanol, ethyl alcohol, propyl alcohol, butanol,
The high polar solvent such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), tetrahydrofuran, dioxane, n,N-Dimethylformamide.These are poly-
Bonding solvent both can be used alone, and can also be used together by two or more types.
In addition, polymerization temperature is preferably 0~110 DEG C from the viewpoint of polymerization speed.
The molecular weight distribution (Mw/Mn) of above-mentioned (methyl) acrylic polymer is 1.05~2.5.
If above-mentioned molecular weight distribution is more than 2.5, the increasings such as low molecular weight compositions generated in above-mentioned active free radical polymerization
Add, therefore optics is easily hazed with adhesive, easily generates bubble in bonding plane, makes after generating in the case where being exposed to high temperature and humidity
Arbitrary problem in being reduced with optics with the processability of adhesive tape that adhesive manufactures.The preferred upper limit of above-mentioned molecular weight distribution
It is 2.0, the preferred upper limit is 1.8.
The preferred lower limit of the weight average molecular weight (Mw) of above-mentioned (methyl) acrylic polymer is 100,000, and preferred upper limit is
2000000.If above-mentioned weight average molecular weight is more than 100,000, high-fire resistance can be obtained.It should be noted that if it is above-mentioned it is heavy divide equally
Son amount is more than 2,000,000, then viscosity when being coated with is excessively high and becomes difficult to be coated with, and can generate the thickness of be coated with optics adhesive
Degree is uneven.The more preferable lower limit of above-mentioned weight average molecular weight is 200,000.
It should be noted that molecular weight distribution (Mw/Mn) is the ratio between weight average molecular weight (Mw) and number-average molecular weight (Mn).
Weight average molecular weight (Mw) and number-average molecular weight (Mn) are converted by the use of gel permeation chromatography (GPC) method as polystyrene
Molecular weight and measure.Specifically, weight average molecular weight (Mw) and number-average molecular weight (Mn) are by (methyl) acrylic polymer
With tetrahydrofuran (THF) dilute 50 times, the dilution of gained is filtered with filter, the filtrate obtained by use using GPC method with
Polystyrene conversion molecular weight form and measure.In GPC method, such as 2690Separations Model can be used
(Waters corporations) etc..
The present invention optics be with the preferred lower limit of the content of above-mentioned (methyl) acrylic polymer in adhesive
50 weight %, preferred lower limit are 70 weight %, and preferred lower limit is 90 weight %.
The optics adhesive of the present invention contains crosslinking agent.By suitably adjusting the type or amount of crosslinking agent, can adjust
The gel fraction of the optics adhesive of whole gained.Carry out active free radical polymerization obtained by (methyl) acrylic polymer by
It is uniform in the composition of contained whole polymer, and with the cross-linking functional groups such as hydroxyl, therefore whole polymer can be with
Participate in the crosslinking between polymer chain.Thus, it is possible to play excellent resistance to foaminess, processability, and transparent electrode can be prevented
Deterioration.
Above-mentioned crosslinking agent is not particularly limited, can be according to the cross-linking functional group of above-mentioned (methyl) acrylic polymer
Type, such as selection using isocyanates system crosslinking agent, aziridine system crosslinking agent, epoxy crosslinking agent, metallo-chelate type
Crosslinking agent etc..
For example, in above-mentioned (methyl) acrylic polymer as cross-linking functional group and in the case that there is hydroxyl, lead to
It crosses as crosslinking agent and uses such as isocyanates system crosslinking agent, so as to so that above-mentioned (methyl) acrylic polymer is handed over
Connection.
As above-mentioned isocyanates system crosslinking agent, for example, CORONATE HX (Japanese polyurethane industrial groups
System), CORONATE L (Japanese polyurethane industrial group system), MITEC NY260A (Mitsubishi Chemical Ind's system) etc..
The use level of above-mentioned crosslinking agent relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer be preferably 0.01~
5 parts by weight, more preferably 0.1~3 parts by weight.In the range, above-mentioned adhesive phase can be adjusted in appropriate range
Gel fraction.
The optics of the present invention can also also contain tackifying resin with adhesive in the range for not damaging the transparency.
As above-mentioned tackifying resin, for example, hydrogenated rosin ester resin, hydrogenated terpene phenol resin etc..
The optics adhesive of the present invention can also be as needed, is not damaging in the range of the transparency, also containing plasticising
Agent, emulsifier, softening agent, particle, filler, pigment, dyestuff, silane coupling agent, antioxidant, surfactant, paraffin etc.
Well known additive.
In addition, with adhesive tape it is also this hair with the optics of adhesive phase that is formed with adhesive of optics by the present invention
It is one of bright.
The gel fraction of above-mentioned adhesive phase is preferably 70~95 weight %.If above-mentioned gel fraction is less than 70 weight %,
Then above-mentioned adhesive phase becomes excessively soft sometimes, can generate foaming.If above-mentioned gel fraction is more than 95 weight %, glue sometimes
Relay can be insufficient.The preferred lower limit of above-mentioned gel fraction is 80 weight %, and the preferred upper limit is 93 weight %.
It should be noted that gel fraction can measure as shown below.First, optics is cut with adhesive tape as 50mm
The flat rectangular of × 100mm and make test film, by test film in ethyl acetate 23 DEG C dipping 24 hours after, from acetic acid
It is taken out in ethyl ester, it is 1 hour dry under conditions of 110 DEG C.The weight of dried test film is measured, is calculated using following formula (1)
Go out gel fraction.It should be noted that test film could be used without being laminated for protect adhesive phase mold release film test film.
Gel fraction (weight %)=100 × (W2-W0)/(W1-W0) (1)
(W0：The weight of base material, W1：The weight of test film before dipping, W2：The weight of dipping, dried test film)
Even the optics of the present invention is not easy to remove, therefore can be thinned according to purposes with the thin adhesive tape of adhesive tape
State adhesive phase and aftermentioned base material.
The thickness of above-mentioned adhesive phase can be set according to purposes, therefore be not particularly limited, however preferred lower limit is 1
μm, the preferred upper limit is 100 μm.If above-mentioned thickness is less than 1 μm, optics adhesive tape becomes to be easily peeled off, and becomes easily to exist
Bonding plane generates bubble.If above-mentioned thickness is more than 100 μm, thin adhesive tape can not be obtained.Above-mentioned thickness it is preferred under
25 μm are limited to, the preferred upper limit is 75 μm.
The optics adhesive tape of the present invention either support type with base material or without base material without branch
Support type.In the case of support type, above-mentioned adhesive phase can be formed in the one side of base material, can also be formed on two sides above-mentioned viscous
Mixture layer.
As long as base material of the above-mentioned base material with the transparency, there is no particular limitation, for example, by acrylic compounds
Resin, polyolefin-based resins, makrolon, polyvinyl chloride, acronitrile-butadiene-styrene (ABS) resin, poly terephthalic acid
The base material of the formation such as glycol ester (PET), polyethylene naphthalate (PEN), nylon, polyurethane, polyimides.
The thickness of above-mentioned base material can be set according to purposes, therefore be not particularly limited, however for example in the feelings of film base material
It is preferably 1~100 μm, more preferably 5~75 μm under condition.If the thickness of above-mentioned base material is less than 1 μm, sometimes optics adhesive tape
Mechanical strength can reduce.If the thickness of above-mentioned base material is more than 100 μm, the anti sag property (waist) of optics adhesive tape becomes sometimes
It is too strong, it is difficult to snugly be bonded along the shape of adherend sometimes.
The manufacturing method of the optics adhesive tape of the present invention is not particularly limited, for example, following method etc.,
It is that is, above-mentioned (methyl) acrylic polymer is other with synthesis with above-mentioned tackifying resin, above-mentioned crosslinking agent etc. as needed
Divide and be mixed together, stir and prepare binder solution, demoulding processing has been carried out next, the binder solution is coated on
On PET film and dry and form adhesive phase, the method that the adhesive phase of gained is transferred to the one or both sides of base material；Directly
It is coated on method on base material and dried etc..Binder solution can also be coated on the PET film for having carried out demoulding processing simultaneously
It is dry, by resulting adhesive phase without base material and directly as the optics adhesive tape of no support type.
As long as the purposes optical applications of the optics adhesive of the present invention and the optics adhesive tape of the present invention, just
It is not particularly limited, it is (such as portable phone, portable to be preferred for the e-machine equipped with image display device or input unit
Information terminal etc.) assembling etc. in.Wherein it is possible to by the optics adhesive of the present invention in the figure for manufacturing portable information terminal etc.
For surface protection board to be bonded with display during as display device, furthermore it is possible in the input of manufacture portable information terminal etc.
It is used to touch panel being bonded with display during device.
In addition, following laminated body is also one of present invention, that is, is (such as to form above-mentioned electronics at least two adherend
Component of machine etc.) between be configured with the laminated body of adhesive phase, wherein, at least one in above-mentioned adherend is transparent quilt
Viscous object, above-mentioned adhesive phase are formed by the optics of the present invention with adhesive.
Invention effect
According to the present invention it is possible to a kind of optics adhesive is provided, even if will not after being exposed under high temperature and humidity
It hazes, resistance to foaminess, processability are also excellent, and will not make to be deteriorated by the transparent electrode that ITO etc. is formed.In addition, according to this hair
It is bright, the optics adhesive tape and laminated body manufactured using the optics with adhesive can be provided.
Description of the drawings
Fig. 1 is the schematic diagram illustrated to active free radical polymerization.
Fig. 2 is that the crosslinked situation of (methyl) acrylic polymer obtained by carrying out active free radical polymerization is said
Bright schematic diagram.
Fig. 3 is the schematic diagram illustrated to radical polymerization.
Fig. 4 illustrates the crosslinked situation of (methyl) acrylic polymer obtained by carrying out radical polymerization
Schematic diagram.
Specific embodiment
Embodiment will be enumerated below, and the present invention will be described in more detail, however the present invention is not limited to these realities
Apply example.
(Examples 1 to 3, comparative example 1~3)
(1) synthesis of active free radical polymerization polymer (LRP)
Tellurium (40 mesh (mesh), metallic tellurium, Aldrich system) 6.38g (50mmol) is made to be suspended in tetrahydrochysene furan
It mutters in (THF) 50mL, the n-BuLi/hexane solution (Aldrich for the 1.6mol/L that drips at leisure thereto at room temperature
System) 34.4mL (55mmol).The reaction solution is stirred to metallic tellurium and is completely disappeared.It is added at room temperature into the reaction solution
The bromo- ethyl isobutyrate 10.7g (55mmol) of 2- are stirred 2 hours.After reaction, solvent is concentrated under reduced pressure, followed by
Vacuum distillation, obtains 2- methyl -2- normal-butyls hydrogen telluro-ethyl propionate of yellow oil.
In the glove box for having carried out argon gas displacement, into reaction vessel, put into the 2- methyl that is obtained using aforesaid operations-
2- normal-butyls hydrogen telluro -38 μ L of ethyl propionate, V-60 (2,2 '-azodiisobutyronitrile and Wako Pure Chemical Industries corporation) 2.8mg,
After ethyl acetate 1mL, closed reaction vessel takes out reaction vessel from glove box.Next, being flowed into reaction vessel
While argon gas, into reaction vessel, total 100g, the ethyl acetate as polymer solvent of the monomer shown in input table 1
66.5g carries out 20 hours polymerisations at 60 DEG C, obtains the solution containing active free radical polymerization polymer (LRP).
The active free radical polymerization polymer (LRP) of gained tetrahydrofuran (THF) is diluted 50 times, by the dilution of gained
Liquid filter (material：Polytetrafluoroethylene (PTFE), aperture：0.2 μm) filtering, by the filtrate of gained to gel permeation chromatography (Waters
Corporation, 2690Separations Model) supply, GPC surveys are carried out under conditions of sample flow 1mL/min, 40 DEG C of column temperature
It is fixed, the polystyrene conversion molecular weight of polymer is determined, molecular weight distribution (Mw/Mn) is obtained.As chromatographic column, use
GPC KF-806L (Showa electrician corporation), as detector, have used differential refractometer.
(2) manufacture of double-faced adhesive tape
Into the solution containing active free radical polymerization polymer (LRP) obtained using aforesaid operations, relative to copolymerization
100 parts by weight of object solid constituent add MITEC NY260A (gas chemical company of Mitsubishi system) 0.2 weight as crosslinking agent
Part, after stirring, it is coated in the demoulding process face of demoulding polyethylene terephthalate (PET) film, it is 10 points dry at 110 DEG C
Thus clock removes ethyl acetate, form adhesive phase 50 μm thick.It should be noted that on the surface of the both sides of adhesive phase,
Progress 50 μm thick has been laminated and has demoulded the PET film handled in order to protect adhesive phase.
(embodiment 4)
After producing the solution containing active free radical polymerization polymer (LRP) same as Example 1ly, relative to copolymerization
100 parts by weight of object solid constituent add MITEC NY260A (gas chemical company of Mitsubishi system) 1.5 weight as crosslinking agent
Part, after stirring, it is coated in the demoulding process face of demoulding polyethylene terephthalate (PET) film, it is 10 points dry at 110 DEG C
Thus clock removes ethyl acetate, form adhesive phase 50 μm thick.It should be noted that on the surface of the both sides of adhesive phase,
The mold release film for protecting adhesive phase has been laminated.
(comparative example 4)
(1) synthesis of radical polymerization polymer (FRP)
Into reaction vessel, the ethyl acetate 50g as polymer solvent is added in, after carrying out bubbling with nitrogen, is flowing into nitrogen
Reaction vessel is heated while gas and starts to flow back.Next, as polymerization initiator and by V-60 (2,2 '-azo, two isobutyls
Nitrile and Wako Pure Chemical Industries corporation) 10 times of ethyl acetate dilutions of 0.15g, the polymerization initiator solution of gained is put into reaction
In container, with total 100g of 2 hours monomers shown in addition table 1 that drip.After dripping, as polymerization initiator by V-
60 (2,2 '-azodiisobutyronitrile and Wako Pure Chemical Industries corporation) 0.15g dilute 10 times with ethyl acetate, by the polymerization of gained
Initiator solution is put into reaction vessel again, is carried out 4 hours polymerisations, is obtained containing radical polymerization polymer (FRP)
Solution.It is operated in the same manner with the situation of active free radical polymerization polymer (LRP), molecular weight distribution (Mw/Mn) is obtained.
(2) manufacture of double-faced adhesive tape
It is operated in the same manner with the situation of active free radical polymerization polymer (LRP), obtains double-faced adhesive tape.
(comparative example 5)
Other than the monomer shown in table 1 has been used in the synthesis in radical polymerization polymer (FRP), with comparative example 4
It operates in the same manner, obtains double-faced adhesive tape.
<Evaluation>
To the double-faced adhesive tape obtained in embodiment, comparative example, following evaluations has been carried out.It shows the result in table 1.
(1) cutting off processing experiment (state of double-faced adhesive tape end face)
For double-faced adhesive tape, 40 blanking operations are carried out using cutting blade, are visually observed because adhesive is attached
The wire drawing phenomenon of the adhesive when blade dirt and blanking operation generated on cutting blade.
By the blade dirt that can't see because being generated during adhesive attachment and also can't see adhesive wire drawing phenomenon situation
"○" is set as, it will be observed that a little blade dirt but can't see the situation of wire drawing phenomenon and be set as " △ ", it will be observed that blade
Dirt and it can also be seen that the situation of wire drawing phenomenon is set as "×", has rated cutting off processing.
(2) transparency after being exposed under high temperature and humidity
Double-faced adhesive tape is cut as the flat shape with 45mm × 60mm.By the one of the double-faced adhesive tape cut out
The demoulding polyethylene terephthalate film stripping of side, attaches transparent poly terephthalic acid second on the adhesive phase of exposing
Then diol ester film, removes the demoulding polyethylene terephthalate film of the opposing party, the adhesive phase of exposing is fitted in load
On slide (trade name " S-1214 " MATSUNAMI corporations), produce with polyethylene terephthalate film/double-sided adhesive
The test film of the layer structure of crossed belt/glass slide.Using haze meter the mist after test film just makes is measured according to JIS K 7105
Angle value (%), then by the test film 85 DEG C of temperature, humidity 85RH% Constant Temperature and Humidity Chambers in place 24 hours, then take out examination
It tests piece and determines haze value immediately.Δ haze value is calculated using following formula (2).
Δ haze value (%)={ haze value (%) of the test film after placing 24 hours }-{ after test film just makes
Haze value (%) } (2)
The situation that Δ haze value is less than 0.3 is set as " transparent ", situation of the Δ haze value more than 0.3 is set as " white
It is turbid ", have rated the transparency.
(3) bubble generates state (resistance to foaminess experiment)
Double-faced adhesive tape is cut as the flat shape with 45mm × 60mm.By the one of the double-faced adhesive tape cut out
The demoulding polyethylene terephthalate film stripping of side, exposes adhesive phase.Then, it is carrying for 0.18mm in thickness
On the ito film face of the film of ITO, it is bonded the face of the exposing of double-faced adhesive tape.Then, the demoulding of the opposing party of double-faced adhesive tape is removed
Polyethylene terephthalate film exposes adhesive phase, in the polycarbonate plate with flat shape that thickness is 2.0mm
The face of the exposing of double-faced adhesive tape is bonded in (PC plate), thus obtains having stacked gradually double-sided adhesive on polycarbonate plate (PC plate)
The laminated body of crossed belt and film with ITO.Thereafter, the laminated body of gained is carried out 15 points in 23 DEG C, the autoclave of 0.5MPa
After clock processing, 500 hours are stood under conditions of 85 DEG C of temperature, relative humidity (RH) 85%, obtains test specimen.Visually
The bubble observed in the bonding interface of the test specimen of gained generates state.
The situation of the bubble for the size for not observing more than 0.01mm completely is set as "○", it will be in every 1 test specimen
It observes that the situation of the bubble of the size of 1~5 more than 0.01mm is set as "×", has rated bubble and generate state.
(4) transparent electrode corrosion test
Double-faced adhesive tape is cut as the flat shape with long 40mm × wide 60mm.It then, will be adjacent in width direction
2 angles respectively using from the length that angle is counted as 10mm, the width counted from angle for the size of 10mm flat shape cut off, obtain
To the adhesive tape of convex.
The demoulding polyethylene terephthalate film of a side of the adhesive tape of convex is removed, by the dew of the adhesive tape of convex
The face paste gone out is attached on polyethylene terephthalate.Then, the demoulding for removing the opposing party of the adhesive tape of convex gathers to benzene
The face of the exposing of the adhesive tape of convex is fitted in the flat shape with 40mm × wide 60mm by naphthalate film
On the ito film face of ito film.It just obtains being sequentially laminated with double-faced adhesive tape on the ito film face of ito film as a result, and gather to benzene two
The conductive film laminated body of formic acid glycol ester.
First, the initial stage resistance value of the conductive film laminated body of gained is determined.Then, by conductive film laminated body 60
DEG C, stand 360 hours under the high temperature and humidity of relative humidity 90RH% after, using amorphous property ito film (tail vat industrial group system),
Determine the resistance value of conductive film laminated body postponed in high temperature and humidity decentralization.It should be noted that by two-terminal resistance value
The terminal of analyzer is tightly attached in the exposed surface in ito film face of the size of 10mm × 10mm, determines resistance value.
According to the resistance value that the decentralization of the initial stage resistance value and high temperature and humidity of gained postpones, resistance change is calculated using following formula
Rate (%).The situation of resistance change rate (%) less than 3 of gained is evaluated as "○", 3 are commented less than 10 situation
Valency is " △ ", and more than 10 situation is evaluated as "×".
Resistance change rate (%)=(resistance value-initial stage resistance value that high temperature and humidity decentralization postpones)/initial stage resistance value ×
100
[table 1]
Industrial availability
According to the present invention it is possible to a kind of optics adhesive is provided, even if will not after being exposed under high temperature and humidity
It hazes, resistance to foaminess, processability are also excellent, and will not make to be deteriorated by the transparent electrode that ITO etc. is formed.In addition, according to this hair
It is bright, the optics adhesive tape and laminated body manufactured using the optics with adhesive can be provided.
Symbol description
1st, (methyl) acrylic polymer obtained by carrying out active free radical polymerization
11st, (methyl) alkyl acrylate of the alkyl with carbon atom number 1~14
12nd, the monomer containing hydroxyl, amino or amide groups
13rd, the monomer containing carboxyl
2nd, (methyl) acrylic polymer obtained by carrying out radical polymerization
21st, (methyl) alkyl acrylate of the alkyl with carbon atom number 1~14
22nd, the monomer containing hydroxyl, amino or amide groups
23rd, the monomer containing carboxyl
24th, the polymer that end free base has inactivated is grown in the way of reaction
25th, the polymer grown in the reaction using newly generated free radical kind
Claims (12)
1. a kind of optics adhesive, which is characterized in that
Containing (methyl) acrylic polymer and crosslinking agent, (methyl) acrylic polymer is to pass through living radical
Polymerization makes 60~95 parts by weight of (methyl) alkyl acrylate comprising alkyl a) with carbon atom number 1~14, b) contain carboxylic
The monomer mixing of 0.1~1 parts by weight of monomer of base and c) 10~30 parts by weight of monomer containing hydroxyl, amino or amide groups
Obtained from object copolymerization, and the molecular weight distribution of (methyl) acrylic polymer is expressed as 1.05~2.5 with Mw/Mn,
Also,
(methyl) alkyl acrylate of alkyl a) with carbon atom number 1~14 includes (methyl) with twin nuclei
Acrylate.
2. optics adhesive according to claim 1, which is characterized in that
In a) there are 60~95 parts by weight of (methyl) alkyl acrylate of alkyl of carbon atom number 1~14, there is tomfool's knot
(methyl) acrylate of structure is 5~55 parts by weight.
3. optics adhesive according to claim 1, which is characterized in that
(methyl) acrylate with twin nuclei is (methyl) isobornyl acrylate.
4. optics adhesive according to claim 1, which is characterized in that
Monomer containing hydroxyl is Hydroxyethyl Acrylate or hydroxy butyl acrylate.
5. optics adhesive according to claim 1, which is characterized in that
Monomer containing amino is (methyl) acrylate.
6. optics adhesive according to claim 1, which is characterized in that
Monomer containing amide groups is diacetone acrylamide.
7. optics adhesive according to claim 1, which is characterized in that
The molecular weight distribution of (methyl) acrylic polymer is expressed as 1.05~1.8 with Mw/Mn.
8. optics adhesive according to claim 1, which is characterized in that
The weight average molecular weight of (methyl) acrylic polymer is expressed as 100,000~2,000,000 with Mw.
9. optics adhesive according to claim 1, which is characterized in that
Relative to 100 parts by weight of (methyl) acrylic polymer, contain 0.01~5 parts by weight of crosslinking agent.
10. a kind of optics adhesive tape, which is characterized in that
With the adhesive phase formed by optics described in claim 1 adhesive.
11. adhesive tape according to claim 10, which is characterized in that
The gel fraction of adhesive phase is 70~95 weight %.
12. a kind of laminated body is the laminated body that adhesive phase is configured between at least two adherend, which is characterized in that
At least one in the adherend is transparent adherend, and described adhesive layer is used viscous by optics described in claim 1
Mixture is formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-272091 | 2013-12-27 | ||
| JP2013272091 | 2013-12-27 | ||
| PCT/JP2014/083660 WO2015098727A1 (en) | 2013-12-27 | 2014-12-19 | Optical adhesive, optical adhesive tape, and layered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105683324A CN105683324A (en) | 2016-06-15 |
| CN105683324B true CN105683324B (en) | 2018-06-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480059825.9A Expired - Fee Related CN105683324B (en) | 2013-12-27 | 2014-12-19 | Optics adhesive, optics adhesive tape and laminated body |
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| Country | Link |
|---|---|
| JP (2) | JP5860566B2 (en) |
| KR (1) | KR20160104613A (en) |
| CN (1) | CN105683324B (en) |
| TW (1) | TWI649386B (en) |
| WO (1) | WO2015098727A1 (en) |
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| JP7010242B2 (en) * | 2016-12-22 | 2022-01-26 | 日本ゼオン株式会社 | A method for producing a terminal-modified acrylic rubber, an acrylic rubber composition, an acrylic rubber crosslinked product, and a terminal-modified acrylic rubber. |
| CN108047965A (en) * | 2017-12-26 | 2018-05-18 | 苏州凡赛特材料科技有限公司 | A kind of preparation method of optical cement, optics of liquids adhesive and Curved screen optical adhesive tape |
| CN111886310B (en) * | 2018-06-01 | 2023-04-18 | 积水化学工业株式会社 | Adhesive sheet |
| US20210395575A1 (en) * | 2018-06-19 | 2021-12-23 | Sekisui Chemical Co., Ltd. | Adhesive agent, adhesive tape, and method for affixing electronic components or vehicle-mounted components |
| JP7220633B2 (en) * | 2019-07-19 | 2023-02-10 | 株式会社日本触媒 | Adhesive composition and its use |
| WO2021200647A1 (en) * | 2020-03-31 | 2021-10-07 | 東レ株式会社 | Polymer particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421312A (en) * | 2006-04-14 | 2009-04-29 | 大塚化学株式会社 | Resin composition and heat-resistant adhesive |
| CN102471657A (en) * | 2009-07-16 | 2012-05-23 | 积水化学工业株式会社 | Pressure-sensitive adhesive tape, laminate, and image display device |
| CN102791817A (en) * | 2010-03-18 | 2012-11-21 | 积水化学工业株式会社 | Pressure-sensitive adhesive composition for optical members and pressure-sensitive adhesive tape for optical members |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10234246A1 (en) * | 2002-07-27 | 2004-02-05 | Tesa Ag | Pressure-sensitive adhesive material for bonding transparent substrates, e.g. in liquid crystal displays and other optical applications, comprises block copolymers with blocks of different refractive index |
| JP5627961B2 (en) * | 2009-09-07 | 2014-11-19 | リンテック株式会社 | Protective film and method for producing protective film |
| JP5614328B2 (en) * | 2011-02-25 | 2014-10-29 | 藤倉化成株式会社 | Adhesive composition, adhesive film, and optical component |
| JP5840200B2 (en) * | 2011-03-31 | 2016-01-06 | 株式会社クラレ | Transparent double-sided adhesive sheet and image display device with touch panel |
| JP2012237965A (en) * | 2011-04-27 | 2012-12-06 | Nitto Denko Corp | Adhesive layer, optical film and image display device |
-
2014
- 2014-12-19 CN CN201480059825.9A patent/CN105683324B/en not_active Expired - Fee Related
- 2014-12-19 WO PCT/JP2014/083660 patent/WO2015098727A1/en active Application Filing
- 2014-12-19 JP JP2015505358A patent/JP5860566B2/en active Active
- 2014-12-19 KR KR1020167007184A patent/KR20160104613A/en not_active Application Discontinuation
- 2014-12-23 TW TW103144889A patent/TWI649386B/en not_active IP Right Cessation
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421312A (en) * | 2006-04-14 | 2009-04-29 | 大塚化学株式会社 | Resin composition and heat-resistant adhesive |
| CN102471657A (en) * | 2009-07-16 | 2012-05-23 | 积水化学工业株式会社 | Pressure-sensitive adhesive tape, laminate, and image display device |
| CN102791817A (en) * | 2010-03-18 | 2012-11-21 | 积水化学工业株式会社 | Pressure-sensitive adhesive composition for optical members and pressure-sensitive adhesive tape for optical members |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201533191A (en) | 2015-09-01 |
| TWI649386B (en) | 2019-02-01 |
| JP6457922B2 (en) | 2019-01-23 |
| WO2015098727A1 (en) | 2015-07-02 |
| CN105683324A (en) | 2016-06-15 |
| JPWO2015098727A1 (en) | 2017-03-23 |
| KR20160104613A (en) | 2016-09-05 |
| JP5860566B2 (en) | 2016-02-16 |
| JP2016094616A (en) | 2016-05-26 |
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