CN103289612B - Adhesive composition and bonding sheet - Google Patents

Adhesive composition and bonding sheet Download PDF

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Publication number
CN103289612B
CN103289612B CN201210585602.9A CN201210585602A CN103289612B CN 103289612 B CN103289612 B CN 103289612B CN 201210585602 A CN201210585602 A CN 201210585602A CN 103289612 B CN103289612 B CN 103289612B
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composition
weight
adhesive composition
parts
compound
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CN103289612A (en
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福元彰朗
荒井隆行
所司悟
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Lintec Corp
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Lintec Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention relates to adhesive composition and bonding sheet.The present invention provides doing over again property and excellent in te pins of durability under regulation environment and adhesive composition to the excellent corrosion resistance of metal and the bonding sheet for having used this adhesive composition.A kind of adhesive composition, it is characterised in that be containing conduct（A）The acrylate copolymer containing cross-linking functional group of composition and conduct（B）The adhesive composition of the crosslinking agent of composition, contains the organosilsesquioxanes compound conduct with reactive group（C）Composition, the reactive group that the organosilsesquioxanes compound has is sulfydryl, makes the organosilsesquioxanes compounds content relative to conduct（A）The parts by weight of acrylate copolymer 100 containing cross-linking functional group of composition are the value in the range of 0.001~1.5 parts by weight.And used the bonding sheet of this adhesive composition.

Description

Adhesive composition and bonding sheet
Technical field
The present invention relates to adhesive composition and bonding sheet.More particularly to doing over again property（The Network of リ ヮ mono-）With regulation environment Under excellent in te pins of durability and being used to constitute the adhesive composition of adhesive phase and make to the excellent corrosion resistance of metal With the bonding sheet of this adhesive composition.
Background technology
In the past, for adhesive composition used in the optical components such as polarizer, fenestrated membrane etc., it is desirable to plastics material can be made Durability is fitted well each other on the surface of material and this unlike material of glass, and when occurring laminating mistake, being capable of adhesive group Compound is peeled off with not ending up at glass surface（Doing over again property）.
Here, being used as the adhesive composition for such use, it is known that addition silane coupler.
That is, silane coupler has alkoxysilyl part and binding affinity group part generally in a molecule, because This alkoxysilyl part can be acted on glass surface, and on the other hand, binding affinity group part can be with adhesive group Polymer in compound etc. react, can through when increase bonding force and to bonding sheet assign as defined in durability.
Therefore, even if the Initial adhesion of bonding sheet is designed to it is relatively low, also can by add silane coupler come through Shi Zengjia bonding forces, and then the doing over again property and durability for the bonding sheet that gets both can be realized.
For example, with provide that doing over again property is good and do not produce peeling, peeling etc. by long-time after coating adhesive yet, it is durable Property excellent adhesive composition for the purpose of, disclose containing organo-functional groups such as sulfydryls and containing defined organic poly- silica Alkane as silane coupler adhesive composition（For example, patent document 1）.
More specifically, organic poly- silica to contain the different a variety of alkoxies of carbon number in an intramolecular is disclosed Alkane is the adhesive composition of required composition.
In addition, to provide doing over again property good and showing money or valuables one carries unintentionally when can suppress to fit in glass substrate, peeling, being used for of peeling off For the purpose of the optical film with adhesive of liquid crystal display device etc., silicone oligomer and acrylic acid tree containing as defined in are disclosed The optical film with adhesive of fat（For example, patent document 2）.
More specifically, the optical film with adhesive containing silicone oligomer and acrylic resin is disclosed, The silicone oligomer has the functional groups such as sulfydryl, epoxy radicals and alkoxy.
On the other hand, it is public for the purpose of the resin combination excellent in adhesion of the inorganic material such as offer and metal material The resin combination containing caged silsesquioxane is opened（For example, patent document 3）.
More specifically, in patent document 3, in order to make distribution in the case where not being roughened to distributing board with viscous The mode for connecing intensity increase is bonded, and is disclosed containing the thermosetting resin as cyanate ester resin, the thermoplastic as polysulfone resin Property resin and by following formulas（2）The resin combination of the caged silsesquioxane of expression.
In addition, to provide the bonding that there is good cohesive and increased substantially by caking intensity in normal temperature For the purpose of agent, the bonding agent formation combination for containing ionizing radiation sensitive ladder polysiloxane as crosslinking agent is disclosed Thing（Such as patent document 4）.
More specifically, in patent document 4, disclose containing the trapezoidal poly- silicon with functional groups such as epoxy radicals, sulfydryls Sesquioxyalkane as crosslinking agent bonding agent formation composition.
In addition, to provide, curability is high, liquid crystal pollution is low and keeps the liquid crystal sealing agent of proper viscosity for a long time as mesh , the liquid crystal sealing agent containing radically curing resin is disclosed, the radically curing resin has 2 in intramolecular Ethylene linkage unsaturated bond more than individual（Such as patent document 5）.
More specifically, in patent document 5, the liquid crystal sealing agent containing Polyorganosilsesquioande is disclosed, The Polyorganosilsesquioande contains the organic group with ethylene linkage unsaturated bond of more than 2.
Prior art literature
Patent document
Patent document 1：No. 2008/090813 publication of International Publication No.（Claim etc.）
Patent document 2：Japanese Unexamined Patent Publication 2008-176173 publications（Claim etc.）
Patent document 3：Japanese Unexamined Patent Publication 2003-49079 publications（Claim, paragraph 0013~0032 etc.）
Patent document 4：Japanese Unexamined Patent Publication 2003-238923 publications（Claim, paragraph 0015~0018 etc.）
Patent document 5：Japanese Unexamined Patent Publication 2009-86291 publications（Claim etc.）
The content of the invention
However, for the component of polymer in the adhesive composition disclosed in patent document 1~2, it was found that by In containing largely, the acrylic acid with carboxyl is as its constituent in the molecule, so entering to adherend such as liquid crystal cells After row laminating, the problem of bonding force excessively rises.
Therefore, propylene is being removed from the constituent of the polymer of adhesive composition to suppress bonding force rising In the case of acid, species, its combination according to the silane coupler used are found, durability is easily significantly reduced or done over again The problem of property becomes insufficient.
In addition, for the cyanate ester resin contained by the resin combination disclosed in patent document 3, finding due to height Valency, and easily hydrolyze, cementability is poor, so while containing caged silsesquioxane compound, being also not used to polarizer Problem.
In addition, the trapezoidal type oligomeric silsesquioxane chemical combination contained by adhesive formation composition disclosed in patent document 4 Thing be as by irradiate ionizing ray improve bonding strength crosslinking agent and the compound that plays a role, but find due to using Ionizing ray, so the problem of restriction on using upper and equipment is more.
Additionally, it was found that the Polyorganosilsesquioande disclosed in liquid crystal sealing agent disclosed in patent document 5 is to be used to carry The radically curing resin of the high adhesive strength with substrate, the problem of without effect as additive.
That is, the silsesquioxane compound disclosed in patent document 3~5 is crosslinking agent, radically curing resin etc., When in adhesive composition as defined in being added to, do not find as imparting durability, the silsesquioxane compound of cohesive Function.
Therefore, the present inventor etc. are in view of as above actual conditions, by further investigation, as a result find by containing acrylic acid Defined organosilsesquioxanes compound is contained with regulation ratio in the adhesive composition of polymer and crosslinking agent, so that The adhesive composition of excellent in te pins of durability to doing over again property and under regulation environment and the excellent corrosion resistance to metal, and then Complete the present invention.
That is, the excellent in te pins of durability it is an object of the invention to provide doing over again property and under regulation environment, and to metal The adhesive composition of excellent corrosion resistance and the bonding sheet using this adhesive composition.
According to the present invention, there is provided a kind of adhesive composition, it is characterised in that is containing conduct（A）Containing for composition is crosslinked The acrylate copolymer of property functional group and conduct（B）The adhesive composition of the crosslinking agent of composition, containing with reactive group Organosilsesquioxanes compound conduct（C）Composition, thus, it is possible to solve the above problems.
That is, due to the present invention adhesive composition with（A）Composition and（B）Composition together, contains what is reacted with crosslinking agent Organosilsesquioxanes compound conduct with reactive group（C）Composition, even if so for example under the conditions of high temperature drying, It is placed under conditions of cryogenic conditions and hot conditions etc. under exacting terms, can also sends out under the conditions of hot and humid or repeatedly Wave excellent durability.
In addition, the bonding force after just being fitted with adherend, can be suppressed to relatively low value, energy by its another aspect Doing over again property as defined in accessing.
In addition, when constituting the adhesive composition of the present invention, preferred organosilsesquioxanes with reactive group The reactive group that compound has is sulfydryl.
In addition, when constituting the adhesive composition of the present invention, preferably making the organosilsesquioxanes with reactive group The content of compound is relative to conduct（A）The parts by weight of acrylate copolymer 100 containing cross-linking functional group of composition be 0.001~ Value in the range of 1.5 parts by weight.
This is due to, by so constituting, the interaction of balance can be obtained to the performance of both adhesive and glass.
In addition, when constituting the adhesive composition of the present invention, preferably characterized in that, conduct（A）Composition contain bridging property The acrylate copolymer of functional group is from as the following of monomer component（a）~（c）The polymer of composition.
（a）It is 1~20 alkyl with carbon number（Methyl）Alkyl acrylate：100 parts by weight
（b）There is the compound containing unsaturated double-bond of hydroxyl in intramolecular：0.5~10 parts by weight
（c）There is the compound containing unsaturated double-bond of carboxyl in intramolecular：0 parts by weight or 0~0.1 parts by weight（Wherein, 0 parts by weight refer to not contain.）
By so constituting, so that conduct（A）The acrylate copolymer containing cross-linking functional group of composition is used as monomer Composition contains substantially no the compound containing unsaturated double-bond for having carboxyl in intramolecular, so even liquid crystal cells etc. are attached In the case that body has by nesa coating of formation such as metal evaporation etc., also can stable against acid corrosion generation.
Although in addition,（A）Composition contains substantially no the conduct of compound containing unsaturated double-bond for having carboxyl in intramolecular Monomer component, but for example under the conditions of high temperature drying, it is hot and humid under the conditions of or be placed in cryogenic conditions and high temperature bar repeatedly Under exacting terms as defined in being waited under conditions of part, excellent durability can be also played.
In addition, the bonding force after just being fitted with adherend, can be suppressed to relatively low value, energy by its another aspect Doing over again property as defined in accessing.
In addition, when constituting the adhesive composition of the present invention, preferably as（B）The crosslinking agent of composition is handed over for isocyanates system Join agent, make its content relative to conduct（A）The parts by weight of acrylate copolymer 100 containing cross-linking functional group of composition be 0.05~ Value in the range of 5 parts by weight.
By so constituting, so as to improve the cohesiveness of adhesive composition, doing over again property is improved and in regulation environment Under durability.
In addition, when constituting the adhesive composition of the present invention, preferably further containing antistatic additive conduct（D）Composition.
By so constituting, so as to make solidifying the adhesive composition of the present invention as the adhesive of film laminating Used time, even if in the case of the adherend stripping film, also can effectively suppress the generation of electrostatic, on the other hand, Neng Goujin One step improves doing over again property and the durability under regulation environment.
In addition, another mode of the present invention is a kind of bonding sheet, it is characterised in that be viscous with coming from base material The bonding sheet of the adhesive phase of mixture composite, described adhesive composition contains conduct（A）Composition contain cross-linking functional group Acrylate copolymer and conduct（B）The crosslinking agent of composition, adhesive composition contains the organosilicon with reactive group times Half siloxane compound conduct（C）Composition.
That is, due to the present invention bonding sheet possess defined adhesive composition as adhesive phase, so doing over again property with Excellent in te pins of durability under regulation environment, even and if having in adherend such as liquid crystal cells by formation such as metal evaporations In the case of nesa coating etc., also can stable against acid corrosion generation.
In addition, when constituting the bonding sheet of the present invention, preferred substrates are optical film, and at least one side of the optical film Possesses adhesive phase.
, should the bonding sheet with optical film so as to obtain the following bonding sheet with optical film by so constituting Doing over again property and the excellent in te pins of durability under regulation environment, even and if in the case where liquid crystal cells have nesa coating, Corrosion resistance is also excellent.
In addition, when constituting the bonding sheet of the present invention, preferred substrates are stripping film, and in adhesive phase and the stripping film Other stripping films are laminated in opposite one side.
By so constituting, so as to improve the operability of bonding sheet.
Brief description of the drawings
Fig. 1 is the content and patch for illustrating the organosilsesquioxanes compound with different types of reactive group The figure of the relation of bonding force after attached 1 day.
Fig. 2 is the content and patch for illustrating the organosilsesquioxanes compound with different types of reactive group The figure of the relation of bonding force after attached 21 days.
Fig. 3 be for illustrate the content of the organosilsesquioxanes compound containing sulfydryl with attach 1 day after and attaching 21 days The figure of the relation of bonding force afterwards.
Fig. 4 is the content and the relation of Gel fraction for illustrating the organosilsesquioxanes compound containing sulfydryl Figure.
Fig. 5（a）~（d）It is the signal for illustrating the occupation mode of adhesive composition etc. and the manufacture method of bonding sheet Figure.
Fig. 6 is another schematic diagram for illustrating the occupation mode of adhesive composition etc..
Symbol description
1：The coating layer of adhesive composition, 2：Stripping film, 10：Adhesive phase, 100：Bonding sheet, 101：Base material, 200： Adherend
Embodiment
[the 1st embodiment]
Embodiments of the present invention are a kind of adhesive compositions, it is characterised in that be containing conduct（A）Containing for composition is handed over The acrylate copolymer of Lian Xing functional groups and conduct（B）The adhesive composition of the crosslinking agent of composition；Containing with reactive base The organosilsesquioxanes compound conduct of group（C）Composition.
Hereinafter, suitably referring to the drawings, the 1st embodiment of the present invention is illustrated.
1.（A）Composition：Acrylate copolymer containing cross-linking functional group
（1）Monomer component
（1）- 1 monomer component（a）
As（A）The acrylate copolymer containing cross-linking functional group of composition is preferably comprised with carbon number 1~20 Alkyl（Methyl）Alkyl acrylate is used as monomer component during polymerization（a）.
If it is value more than 20 that its reason, which is the carbon number of abovementioned alkyl, side chain oriented crystalline each other sometimes, The cohesive reduction of thus obtained adhesive composition.
Therefore, the carbon number for more preferably making the alkyl in the acrylate copolymer containing cross-linking functional group is 1~10 model Enclose the value in the range of interior value, more preferably 4~8.
In addition, being the value in the range of 1~20 as the carbon number of alkyl（Methyl）Alkyl acrylate, for example, can Enumerate（Methyl）Methyl acrylate,（Methyl）Ethyl acrylate,（Methyl）Propyl acrylate,（Methyl）Butyl acrylate,（First Base）Amyl acrylate,（Methyl）Hexyl 2-propenoate,（Methyl）Cyclohexyl acrylate,（Methyl）2-EHA,（First Base）Isooctyl acrylate monomer,（Methyl）Decyl acrylate and（Methyl）Dodecylacrylate,（Methyl）The acrylic acid tetradecane Base ester,（Methyl）Aliphatic acrylate,（Methyl）Independent a kind of in octadecyl acrylate etc. or more than two kinds Combination.
Further, since being used as monomer component（a）'s（Methyl）Acrylate is composition conduct（A）The official containing bridging property of composition The principal component for the acrylate copolymer that can be rolled into a ball, it is generally preferred that to constitute（A）More than the 50 weight % of the total monomer composition of composition Value, the value in the range of more preferably 60~99.5 weight %, the value in the range of more preferably 85~99 weight %.
（1）- 2 monomer components（b）
In addition, conduct（A）The acrylate copolymer containing cross-linking functional group of composition is preferably comprised has hydroxyl in intramolecular The compound containing unsaturated double-bond of base is used as monomer component during polymerization（b）.
Its reason is by containing above-mentioned monomer component（b）, so that the hydroxyl turns into bridging property in acrylate copolymer Functional group.That is, when adding crosslinking agent to adhesive composition, conduct can effectively be carried out（A）Third containing functional group of composition The mutual crosslinking of olefin(e) acid polymer, it is possible to increase the cohesiveness of obtained adhesive, easily carries out bonding force, the tune of storage modulus It is whole.
In addition, there is the compound containing unsaturated double-bond of hydroxyl as in intramolecular, for example, it is preferable to enumerate hydroxyethyl second The vinyl ethers such as alkene ether, hydroxybutyl vinyl ether, cyclohexane dimethanol mono vinyl ether, allyl alcohol, allyl ethyl glycol, The allyl ethers such as pi-allyl diethylene glycol,（Methyl）Acrylic acid 2- hydroxy methacrylates,（Methyl）Acrylic acid 2- hydroxy propyl esters,（Methyl） Acrylic acid 3- hydroxy propyl esters,（Methyl）Acrylic acid 2- hydroxybutyls,（Methyl）Acrylic acid 3- hydroxybutyls,（Methyl）Acrylic acid 4- Hydroxybutyl etc.（Methyl）Independent a kind of in the monomers such as hydroxyalkyl acrylates or more than two kinds of combination.
In addition, if considering to constitute with being used as（Methyl）The principal component of acrylate polymer（Methyl）Acrylate list The intermiscibility of body, then further preferably（Methyl）Hydroxyalkyl acrylates, particularly preferably（Methyl）Acrylic acid 2- hydroxy methacrylates With（Methyl）Any of acrylic acid 4- hydroxybutyls.
Additionally, it is preferred that making monomer component（b）Use level relative to monomer component（a）100 parts by weight are 0.5~10 weight Value in the range of part.
The reason is if monomer component（b）Use level be less than 0.5 parts by weight value, then sometimes（A）Between composition Crosslinking becomes insufficient, and the durability under regulation environment is deteriorated.
On the other hand, if monomer component（b）Use level be value more than 10 parts by weight, then adhesive composition sometimes Cohesive excessively reduce.
Therefore, monomer component is more preferably made（b）Use level relative to monomer component（a）100 parts by weight are 1~5 weight Value in the range of part.
（1）- 3 monomer components（c）
Additionally, it is preferred that conduct（A）The acrylate copolymer containing functional group of composition is contained substantially no to be had in intramolecular The compound containing unsaturated double-bond of carboxyl is used as monomer component during polymerization（c）.
More specifically, preferably in polymerization conduct（A）During the acrylate copolymer containing cross-linking functional group of composition, monomer Composition（c）Use level relative to above-mentioned monomer component（a）100 parts by weight are 0 parts by weight or 0~0.1 parts by weight（Wherein, 0 Parts by weight refer to not contain）In the range of value.
The reason is if above-mentioned monomer component（c）Use level be more than 0.1 parts by weight value, then in liquid crystal cells etc. In the case that adherend has by nesa coatings of formation such as metal evaporation etc., then it is difficult to sometimes stable against sour The generation of erosion.
In addition, reason be the bonding force of adhesive composition sometimes after being fitted to adherend, easily drastically increase Greatly, it is difficult to the doing over again property played stably.
Therefore, monomer component is being coordinated（c）In the case of, more preferably make monomer component（c）Use level relative to monomer Composition（a）100 parts by weight are the value in the range of 0.0001~0.1 parts by weight, more preferably 0.001~0.05 parts by weight In the range of value.
It should illustrate, be used as monomer component（c）Species, as long as intramolecular have carboxyl contain unsaturated double-bond Compound is just not particularly limited, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid can be enumerated Deng.
（1）- 4 other monomer components（d）
In addition, it is also preferred that conduct（A）The acrylate copolymer containing functional group of composition contains（a）Containing in addition is non-crosslinked Property group monomer be used as polymerization when other monomer components（d）.
The reason is conduct（A）The acrylate copolymer containing functional group of composition by containing（a）In addition containing it is non-hand over The monomer of connection property group, so as to be sometimes prone to adjust the cohesive of adhesive composition.
Therefore,（A）Contain monomer component in composition（d）During as Component units, it is usually preferred to make monomer component（d）Match somebody with somebody Resultant is relative to composition（A）The total monomer of composition is below 49.5 weight % value, in the range of more preferably 5~20 weight % Value.
In addition, as above-mentioned（a）The monomer containing non-crosslinked property group in addition, for example, can enumerate vinyl acetate, （Methyl）The acid amides such as acrylamide, acryloyl morpholine system monomer, for example, N- can be enumerated（Methyl）Acryloyl-oxy methylene succinyl Imines, N-（Methyl）The succinimide system monomers such as acryloyl -6- oxygen hexa-methylene succinimides, for example, N- second can be enumerated The vinyl monomers such as vinyl pyrrolidone, styrene, for example, organosilicon can be enumerated（Methyl）Acrylate, fluorine（Methyl）Propylene Acrylic ester monomer such as acid esters etc..
（2）Weight average molecular weight
Preferably make conduct in addition（A）The weight average molecular weight of the acrylate copolymer containing functional group of composition is 1,000,000~220 Value in the range of ten thousand.
If the reason is above-mentioned weight average molecular weight for the value less than 1,000,000, sometimes the doing over again property of adhesive composition, Durability becomes insufficient.On the other hand, if above-mentioned weight average molecular weight is value more than 2,200,000, be difficult to suppress sometimes by The reduction of suitability is processed caused by viscosity increase of adhesive composition etc..
Therefore, conduct is more preferably made（A）The weight average molecular weight of the acrylate copolymer containing functional group of composition be 1,200,000~ Value in the range of 1800000, the value in the range of more preferably 1,400,000~1,600,000.
It should illustrate, above-mentioned weight average molecular weight can be by the gel permeation chromatography that is converted based on polystyrene（GPC）Method To determine.
2.（C）Composition：Organosilsesquioxanes compound with reactive group
（1）Species
The adhesive composition of the present invention, it is characterised in that contain conduct（C）Composition have reactive group it is organic Silsesquioxane compound, the organosilsesquioxanes compound is preferably comprised by following formulas（1）The structure of expression.
The reason is used as by containing（C）The compound with specific structure of composition, so as to adhesive and The performance of both glass obtains the interaction of balance.
Therefore, even if conduct（A）The acrylate copolymer with cross-linking functional group of composition, which is contained substantially no, to be divided In the case that the compound containing unsaturated double-bond with carboxyl is as monomer composition in sub, it can also improve under regulation environment Durability and doing over again property.
[RSiO3/2]n (1)
（Formula（1）In, R is hydrogen atom, the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, carbon number Any one in 6~20 aryl, halogen atom or reactive group, multiple R can be with identical, can also be mutually different, wherein At least one is reactive group, in addition at least another be hydrogen atom, the alkoxy of carbon number 1~4 and halogen atom in Any one, n be 2~50 integer.）
In addition, being used as n, preferably 6~20 integer, more preferably 8~14 integer.
If the reason is n for the integer more than 50, be difficult to adjust viscosity sometimes, or with other resins, solvent Intermiscibility is deteriorated.
Therefore, by making condensation degree be the value in above range, so that organosilsesquioxanes have higher structure, can The rigid molecular structure of alternatively acquisition of occurred conformation, can not obtain the phase of balance to the performance of both adhesive and glass Interaction.
In addition, refer to have in end can be with for reactive group（A）Cross-linking functional group in composition directly or via The formation chemical bond such as crosslinking agent（For example, covalent bond, ionic bond etc.）Functional group group.As the functional group, for example, can be with It is preferred that enumerating the functional group containing hydroxyl, epoxy radicals, sulfydryl etc..Wherein, further preferably sulfydryl.
In addition, can also can be entered between the functional group and silicon atom with Direct Bonding via alkyl, alkoxy, aryl etc. Line unit is closed.
It should illustrate, by the functional group using sulfydryl is contained as reactive group, so that conduct（A）The acrylic acid of composition The cross-linking functional group of polymer even general silane coupler is difficult to the hydroxyl acted on, if for example, using described later As（B）The isocyanates system crosslinking agent of composition, can also play excellent coupling effect.
Speculate that this is due to the following reasons：The NCO of sulfydryl and isocyanates system crosslinking agent easily forms thio ammonia Base Ethyl formate key, the other end of the isocyanates system crosslinking agent is bonded with the hydroxyl of acrylate copolymer, thus should（C）Composition There is appropriately distance with acrylate copolymer, and form sagging structure.
Therefore, although conduct（A）The acrylate copolymer with cross-linking functional group of composition, which is contained substantially no, to be divided The unsaturated double-bond compound with carboxyl is as monomer composition in sub, can also improve durability under regulation environment and Doing over again property.
More specifically, as shown in figure 1, to the organosilsesquioxanes compound with different types of reactive group Content illustrated with the relation of bonding force after attaching 1 day.
I.e., in Fig. 1, characteristic curve A is respectively illustrated（Figure ◆）, characteristic curve B（Scheme ■）With characteristic curve C（Figure ▲）, the characteristic curve A（Figure ◆）Be use relative to（A）The parts by weight of composition 100, organosilicon sesquialter oxygen with sulfydryl Hydride compounds I（N=12）Content（Parts by weight）As transverse axis, using viscous after the attaching 1 day of obtained adhesive composition With joint efforts（N/25mm）It is depicted as the longitudinal axis；The characteristic curve B（Scheme ■）Be use relative to（A）The weight of composition 100 Part, organosilsesquioxanes compound II with epoxy radicals（N=10）Content（Parts by weight）As transverse axis, using obtaining Adhesive composition attaching 1 day after bonding force（N/25mm）It is depicted as the longitudinal axis；The characteristic curve C（Figure ▲）Be use relative to（A）The parts by weight of composition 100, organosilsesquioxanes compound III with epoxy radicals（N=4~6 Mixture）Content（Parts by weight）As transverse axis, using the bonding force after the attaching 1 day of obtained adhesive composition（N/ 25mm）It is depicted as the longitudinal axis.
In addition, in fig. 2, to the content of the organosilsesquioxanes compound with different types of reactive group with The relation of bonding force after attaching 21 days is illustrated.
I.e., in fig. 2, characteristic curve D is respectively illustrated（Figure ◆）, characteristic curve E（Scheme ■）With characteristic curve F（Figure ▲）, the characteristic curve D（Figure ◆）Be use relative to（A）The parts by weight of composition 100, organosilicon sesquialter oxygen with sulfydryl Hydride compounds I（N=12）Content（Parts by weight）As transverse axis, using viscous after the attaching 21 days of obtained adhesive composition With joint efforts（N/25mm）It is depicted as the longitudinal axis；The characteristic curve E（Scheme ■）Be use relative to（A）The weight of composition 100 Part, organosilsesquioxanes compound II with epoxy radicals（N=10）Content（Parts by weight）As transverse axis, using obtaining Adhesive composition attaching 21 days after bonding force（N/25mm）It is depicted as the longitudinal axis；The characteristic curve F（Figure ▲）Be use relative to（A）The parts by weight of composition 100, organosilsesquioxanes compound III with epoxy radicals（N=4~6 Mixture）Content（Parts by weight）As transverse axis, using the bonding force after the attaching 21 days of obtained adhesive composition（N/ 25mm）It is depicted as the longitudinal axis.
It should illustrate, the composition of adhesive composition, condition determination of bonding force etc. are documented in embodiment.
First, it was found from characteristic curve A and D, with the organosilsesquioxanes compound I that sulfydryl n is 12 as it contains Amount increase, attach 1 day after bonding force and attach 21 days after bonding force uniformity increase after, reduce.
On the other hand, so that characteristic curve B and E are understood, with the organosilsesquioxanes compound II that epoxy radicals n is 10 With the increase of its content, the bonding force after attaching 1 day is reduced with the bonding force after attaching 21 days.
In addition, it was found from characteristic curve C and F, with organosilsesquioxanes chemical combination of the epoxy radicals n for 4~6 mixture Thing III is with the increase of its content, and the bonding force after attaching 1 day is greatly lowered with the bonding force after attaching 21 days.
Therefore, it is known that for the bonding force of the lowest limit requirement that is maintained as adhesive composition, on the other hand, in order to Doing over again property as defined in obtaining, preferably as（C）The reactive group of the organosilsesquioxanes compound of composition is to contain sulfydryl Reactive group.
（2）Content
Additionally, it is preferred that making conduct（C）The content phase of the organosilsesquioxanes compound with reactive group of composition For conduct（A）The parts by weight of acrylate copolymer 100 containing cross-linking functional group of composition are 0.001~1.50 parts by weight scope Interior value.
The reason is by making to be used as（C）The content of the organosilsesquioxanes compound with reactive group of composition For the value in above range, so as to obtain the interaction of balance to the performance of both adhesive and glass.
As a result, doing over again property and the durability under regulation environment can be improved further.
That is, if（C）The content of composition is the value less than 0.001 parts by weight, then sometimes（C）The absolute magnitude of composition is not enough, It is difficult to give full play to its effect, it is difficult to obtain sufficient durability.On the other hand, if（C）The content of composition is more than 1.5 weight Part, then sometimes for both adhesive and glass, the interaction for obtaining balance is disturbed, and durability, doing over again property are deteriorated.
Therefore, conduct is more preferably made（C）The content of the organosilsesquioxanes compound with reactive group of composition Relative to conduct（A）The parts by weight of acrylate copolymer 100 containing cross-linking functional group of composition are 0.01~1.0 parts by weight scope Interior value, is further preferred that the value in the range of 0.1~0.5 parts by weight.
Then, using Fig. 3, to the content of the organosilsesquioxanes compound containing sulfydryl with attach 1 day after and attaching 21 The relation of bonding force after it is illustrated.
I.e., in figure 3, characteristic curve A is respectively illustrated（Scheme ◇）With characteristic curve D（Scheme ■）, the characteristic curve A （Scheme ◇）Be use relative to（A）The parts by weight of composition 100, formula（1）The contained compound of sesquioxyalkane containing mercaptoorganosilicon I Content（Parts by weight）As transverse axis, using the bonding force after the attaching 1 day of obtained adhesive composition（N/25mm）As The longitudinal axis and be depicted as；Characteristic curve D（Scheme ■）Be use relative to（A）The parts by weight of composition 100, formula（1）Contained contains Mercaptoorganosilicon sesquioxyalkane compound I content（Parts by weight）As transverse axis, using the attaching of obtained adhesive composition Bonding force after 21 days（N/25mm）It is depicted as the longitudinal axis.
It should illustrate, the composition of adhesive composition, condition determination of bonding force etc. are documented in embodiment.
First, it was found from characteristic curve A and D, with organosilsesquioxanes compound I content increase, after attaching 1 day Bonding force and attach 21 days after bonding force uniformity increase after, reduce.
More specifically, it is known that in characteristic curve A, when organosilsesquioxanes compound I content is 0 parts by weight, Bonding force after attaching 1 day is 3.4N/25mm, and with compound I increase, bonding force is sharply increased, and compound I content is During 0.1 parts by weight, the bonding force after attaching 1 day is shown as 5.3N/25mm value.
On the other hand, it is known that if the content of compound is more than 0.1 parts by weight, the bonding force after attaching 1 day starts to delay Slowly reduce, be continued for reducing thereafter.
In addition, understanding in characteristic curve D, if become after attaching 21 days, organosilsesquioxanes compound I's contains The change of amount brings very big influence to bonding force, in order to obtain the bonding force in preferred scope, preferably makes organosilicon sesquialter oxygen Hydride compounds I content is the value in defined scope.
More specifically, it is known that when organosilsesquioxanes compound I content is 0 parts by weight, it is viscous after attaching 21 days It is with joint efforts 7.8N/25mm, with compound I increase, bonding force is sharply increased, when compound I content is 0.1 parts by weight, Bonding force after attaching 21 days is shown as 11.4N/25mm value.
On the other hand, it is known that if the content of compound is the value more than 0.1 parts by weight, the bonding force after attaching 21 days Start to reduce, be continued for reducing thereafter.
Therefore, it is known that for the bonding force of the lowest limit requirement that is maintained as adhesive composition, on the other hand, in order to Doing over again property as defined in obtaining, preferably makes conduct（C）The organosilsesquioxanes compound with reactive group of composition contains Amount is relative to conduct（A）The parts by weight of acrylate copolymer 100 containing cross-linking functional group of composition are 0.001~1.5 parts by weight In the range of value.
Then, using Fig. 4, the content of organosilsesquioxanes compound and the relation of Gel fraction containing sulfydryl are entered Row explanation.
I.e., in Fig. 4, using relative to（A）The parts by weight of composition 100, formula（1）Contained organosilsesquioxanes Compound I content（Parts by weight）As transverse axis, the obtained Gel fraction of adhesive composition is shown（%）It is used as the longitudinal axis.
It should illustrate, the composition of adhesive composition, condition determination of Gel fraction etc. are documented in embodiment.
First, it was found from characteristic curve, with organosilsesquioxanes compound I content increase, Gel fraction one After degree increase, reduce.
More specifically, it is known that when organosilsesquioxanes compound I content is 0 parts by weight, Gel fraction is 79.6%, with compound I increase, Gel fraction is sharply increased, when compound I content is 0.1 parts by weight, gel hundred Fraction is shown as 81.6% value.
On the other hand, it is known that if the content of compound is the value more than 0.1 parts by weight, Gel fraction starts drastically Reduce, be continued for reducing thereafter.
Therefore, it is known that in order to increase the cohesiveness of adhesive composition, in order to improve doing over again property and under regulation environment Durability, preferably makes conduct（C）The content of the organosilsesquioxanes compound with reactive group of composition is relative to work For（A）The parts by weight of acrylate copolymer 100 containing cross-linking functional group of composition is in the range of 0.001~1.5 parts by weight Value.
（3）Action effect
Here, obtained effect is illustrated during to coordinating organic silsesquioxane compound I.
More specifically, the shape with the organoalkoxysilane compounds with reactive group or as its condensation product Into organosiloxane oligomers be compared.
Organoalkoxysilane compounds with reactive group have a silicon atom in 1 molecule, generally, with silicon The alkoxy of atomistic binding and the silanol base of glass surface are condensed, organic with reactive group with silicon atom bonding in addition With the cross-linking functional group in adhesive condensation reaction or addition reaction occur for side chain, and glass and adhesive are via organic alkoxy Silane compound is connected by covalent bond, shows strong adhesive effect.
In addition, for organosiloxane oligomers, in glass surface and adhesive, each molecule is relative to crosslinking The number of the reaction site of property functional group is more than organoalkoxysilane compounds, thus with organoalkoxysilane compounds ratio Compared with can expect to play stronger effect, thus it is speculated that because siloxane main chain can obtain various conformations, so obtaining organic Side chain is each other or alkoxy is each other in the higher structure of intramolecular uneven distribution.For example, being used as an example of higher structure Son, can be enumerated in the way of organic side chain is towards outside and the construction of siloxane main chain formation spiral.Now, thus it is speculated that for organic For siloxane oligomer, in the silanol base with the organic side chain of cross-linking functional group's reaction in adhesive and with glass surface In both alkoxies of reaction, an only side more uneven surface for being present in higher structure, with adhesive and glass In a side be more strongly bonded, adhesive effect is relatively weak compared with organoalkoxysilane compounds.
Therefore, by the adhesive effect in adhesive than it is desired much higher when add organosiloxane oligomers, from And doing over again property can be assigned in the case where not hindering its adhesive effect significantly.
On the other hand, organosilsesquioxanes compound I has rigid molecular configuration, does not occur on higher structure surface The uneven distribution of functional group as caused by the change of conformation.
I.e., it is believed that compared with organoalkoxysilane compounds, per molecule more has effective reaction site number, with Organosiloxane oligomers are compared, and the interaction of balance is obtained to the performance of both adhesive and glass.
Therefore, in order to obtain the interaction balanced to the performance of both adhesive and glass, for being added to adhesive For organosilsesquioxanes compound in composition, reactive organo-functional group is relative to alkoxysilyl and silanol The mol ratio of base is preferably 1.5~4.0, and more preferably 2.5~3.0.
3.（B）Composition：Crosslinking agent
In addition, when constituting the adhesive composition of the present invention, it is characterised in that contain crosslinking agent conduct（B）Composition.
The reason be by the use of as（B）The crosslinking agent of composition, as（A）The acrylate copolymer containing functional group of composition that This crosslinking, the cohesiveness thus, it is possible to increase adhesive composition improves doing over again property and the durability under regulation environment.
（1）Species
In addition, as above-mentioned crosslinking agent, can preferably enumerate isocyanates system crosslinking agent, aziridine system crosslinking agent, epoxy It is crosslinking agent, metallo-chelate system crosslinking agent.
The reason is by that containing these crosslinking agents, can arrive the bonding force of adhesive composition, storage modulus regulation Preferred scope.
Wherein, isocyanates system crosslinking agent is preferably used.This is due to the following reasons：If isocyanates system is crosslinked Agent, then the acrylate copolymer containing cross-linking functional group can be with being used as monomer component（b）Intramolecular have hydroxyl containing not The hydroxyl reaction of saturation double bond compound, makes the acrylate copolymer containing cross-linking functional group carry out chemical friendship effectively with each other Connection.
In addition, as the concrete example of above-mentioned isocyanates system crosslinking agent, for example, can enumerate trimethylene diisocyanate, Tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, the isocyanic acid of 1,2- propylidene two Ester, 1,2- tetramethylene diisocyanates, 2,3- tetramethylene diisocyanates, 1,3- tetramethylene diisocyanates, 2,4,4- or 2, The aliphatic diisocyanates such as 2,4- trimethyl hexamethylene diisocyanates, 2,6- diisocyanate methylhexanoic acid esters, for example, 1,3- pentamethylene diisocyanate, 1,4- cyclohexane diisocyanates, 1,3- cyclohexane diisocyanates, 3- isocyanic acids can be enumerated METH -3,5,5- trimethylcyclohexylisocyanates, 4,4 '-di-2-ethylhexylphosphine oxide（Cyclohexyl isocyanate）, methyl -2,4- hexamethylenes Alkane diisocyanate, methyl -2,6- cyclohexane diisocyanates, 1,4- are double（Isocyanatomethyl）Hexamethylene, 1,3- are double（Isocyanide Acid esters methyl）The alicyclic diisocyanates such as hexamethylene, for example, metaphenylene diisocyanate can be enumerated, it is different to phenylene two Cyanate, 4,4 '-diphenyl diisocyanate, 1,5- naphthalene diisocyanates, 4,4 '-methyl diphenylene diisocyanate, 2,4- Or 2,6- toluene di-isocyanate(TDI)s or its mixture, 4,4 '-toluidine diisocyanate, dianisidine diisocyanate, 4,4 '- The aromatic diisocyanates such as diphenyl ether diisocyanate, for example, 1,3- or the isocyanic acid of Isosorbide-5-Nitrae-xylylene two can be enumerated Ester or its mixture, ω, ω '-diisocyanate -1,4- diethylbenzenes, 1,3- or 1,4- are double（1- isocyanates -1- methyl second Base）The araliphatic diisocyanate such as benzene or its mixture, for example, triphenyl methane -4 can be enumerated, 4 ', 4 "-three isocyanic acids Ester, 1, the triisocyanate such as 3,5- triisocyanate benzene, 2,4,6- triisocyanate toluene, 1,3,5- triisocyanate hexanes, For example, 4 can be enumerated, 4 '-diphenyldimethyhnethane -2,2 ' -5, the polyisocynate monomer such as 5 '-tetraisocyanate, by above-mentioned Dimer derived from polyisocynate monomer, tripolymer, biuret, allophanate, by carbon dioxide and above-mentioned polyisocyanic acid What ester monomer was obtained has 2,4,6-The polyisocyanates of diazine triketone ring, for example, ethylene glycol, propane diols, fourth two can be enumerated Alcohol, neopentyl glycol, 1,6-HD, 3- methyl isophthalic acids, 5- pentanediols, 3,3 '-dihydroxymethyl heptane, cyclohexanedimethanol, diethyl The weight average molecular weight such as glycol, triethylene glycol, DPG, glycerine, trimethylolpropane, pentaerythrite, D-sorbite are less than 200 Low molecular weight polyols to the addition products of above-mentioned various isocyanates, for example, it is 200~200000 that can enumerate above-mentioned molecular weight PEPA, PPG, polyester ether polylol, polyester amide polyol, polycaprolactone polyol, poly- valerolactone it is many First alcohol, acrylic polyol, polycarbonate polyol, poly- hydroxyl alkane, castor oil, polyurethane polyol etc. are to above-mentioned various isocyanides Addition product of acid esters etc..
（2）Content
Additionally, it is preferred that making conduct（B）The content of the crosslinking agent of composition is relative to conduct（A）Composition contain cross-linking functional group The parts by weight of acrylate copolymer 100 be 0.05~5 parts by weight in the range of value.
If it is the value less than 0.05 parts by weight that the reason, which is the content of above-mentioned crosslinking agent, it is used as by adding（C） The additive with particular configuration of composition and in the case of cohesiveness reduction, be difficult to obtain sufficient bonding force, energy storage sometimes Modulus.On the other hand, if the content of above-mentioned crosslinking agent is the value more than 5 parts by weight, sometimes conduct（A）Containing for composition is crosslinked Property functional group the mutual crosslinking of acrylate copolymer it is excessive, on the contrary, bonding force is easily reduced.
Therefore, conduct is more preferably made（B）The content of the crosslinking agent of composition is relative to conduct（A）The function containing bridging property of composition The parts by weight of acrylate copolymer 100 of group are the value in the range of 0.05~3 parts by weight, more preferably 0.1~1 parts by weight In the range of value.
4. retarder thinner
Appropriate glue is adjusted to from the dispersiveness for improving each composition or when to the coating adhesive composition such as stripping film From the viewpoint of degree, solvent can be used in the adhesive composition of the present invention.
As above-mentioned solvent, for example, it is preferable to the aliphatic hydrocarbon such as hexane, heptane, the aromatic hydrocarbon, dichloro such as toluene, dimethylbenzene The halogenated hydrocarbons such as methane, dichloroethanes, the alcohol, acetone, MEK, 2 pentanone, isophorone, ring such as methanol, ethanol, propyl alcohol, butanol The ketone such as hexanone, the ester such as ethyl acetate, butyl acetate, the cellosolve series solvent such as ethyl cellosolve, the glycol such as propylene glycol monomethyl ether Ether series solvent etc., the concentration of adhesive composition when adding solvent is preferably the value in the range of 10~40 weight %.
5. additive
As other additives, preferably in adhesive composition containing tackifier, antioxidant, ultra-violet absorber, Light stabilizer, softening agent, filler, high index of refraction agent, diffusant, antistatic additive etc..
In addition, now, even if depending on the species of additive, it is also preferred that making its content relative to conduct（A）The third of composition The parts by weight of olefin(e) acid polymer 100 are the value in the range of 0.1~20 parts by weight.
［ the 2nd embodiment ］
The 2nd embodiment of the present invention is a kind of bonding sheet, it is characterised in that be to have to come from adhesive on base material The bonding sheet of the adhesive phase of composition, described adhesive composition contains conduct（A）Third containing cross-linking functional group of composition Olefin(e) acid polymer and conduct（B）The crosslinking agent of composition, adhesive composition contains the organosilicon sesquialter oxygen with reactive group Hydride compounds conduct（C）Composition.
Hereinafter, reference picture 5, the 2nd embodiment to the present invention centered on the point different from the 1st embodiment has Body explanation.
1. adhesive phase
Adhesive composition can be via following processes（1）~（3）And as the adhesive phase with predetermined characteristic.
（1）Preparation contains（A）、（B）And（C）The process of the defined adhesive composition of composition
（2）Adhesive composition is applied on stripping film, the process for forming coating layer
（3）Make binder composition cross-links, coating layer is turned into the process of adhesive phase
Pair hereinafter, suitably referring to the drawings, until the process for constituting adhesive phase is specifically described.
（1）Process（1）（The preparatory process of adhesive composition）
Process（1）It is to prepare to contain（A）、（B）And（C）The process of the defined adhesive composition of composition.
More specifically, preferably will（A）Composition is diluted with the retarder thinner such as ethyl acetate according to demand, is added under stirring Plus（C）Composition, is made uniform mixed liquor.
Additionally, it is preferred that at the same time, into mixed liquor, addition（B）Composition, further adds other additions according to demand After agent, while being stirred until homogeneous, side further adds retarder thinner until becoming the viscosity of demand as needed, is thus bonded The solution of agent composition.
It should illustrate, detail and mixing ratio of each composition etc. are omitted as described in the 1st embodiment.
（2）Process（2）（The painting process of adhesive composition）
Such as Fig. 5（a）It is shown, process（2）It is that adhesive composition is applied to the process that coating layer 1 is formed on stripping film 2.
As stripping film, for example, the stripping film for being coated with remover to film and setting peel ply can be enumerated, the film is poly- pair The polyester films such as PET, polybutylene terephthalate (PBT), PEN, polypropylene, poly- second The polyolefin films such as alkene, the remover is silicone resin, fluororesin, alkyd resin etc..
It should illustrate, the thickness of above-mentioned stripping film is preferably generally the value in 20~150 μ ms.
In addition, as the method for the coating adhesive composition on stripping film, for example, it is preferable to using stick coating method, scrape cutter painting Method, rolling method, scraper plate rubbing method, die coating methods, gravure coating process etc. are coated with the adhesive composition for adding solvent, are formed Coating layer（Film）Afterwards, dry it.
Now, according to benchmark when drying, the thickness for preferably making coating layer is the value in the range of 5~100 μm, more preferably Value in the range of 10~50 μm, the value in the range of more preferably 15~30 μm.
If the reason is that the thickness of coating layer is excessively thin, it cannot get abundant adhesion characteristic sometimes, if opposite blocked up, Sometimes residual solvent turns into problem.
In addition, as drying condition, generally, it is preferred in the range of 50~120 DEG C, 10 seconds~10 minutes.
（3）Process（3）（The cross-linking process step of coating layer）
Process（3）It is that the coating layer for making adhesive composition is crosslinked, coating layer is turned into the process of adhesive phase.
That is, such as Fig. 5（b）It is shown, the base materials such as optical film 101 is layered in the coating layer 1 of drying regime on stripping film 2 Surface, be crosslinked coating layer 1 with the state, formed adhesive phase 10.
Or, the coating layer for the adhesive composition being coated with stripping film can also be made to be crosslinked in advance, adhesive is formed After layer, it is laminated with the base material such as optical film.
In addition, it is also preferred that base material is stripping film, and the mode of another stripping film is laminated to the exposed surface of adhesive phase.
That is, as shown in fig. 6, it is also preferred that the bonding sheet 100b formed as follows, i.e. to the coating adhesive composition of stripping film 2 And dry it, formed coating layer 1 after, another stripping film 2 is layered on coating layer 1, be crosslinked, thus with The mode that the peel ply side of 2 stripping films 2 connects with adhesive phase 10 respectively, which is clamped, to be formed.
In addition, the bonding sheet 100b of aforesaid way can also be the bonding sheet formed in the following way, i.e. to stripping film 2 form the coating layer 1 of adhesive composition, after it is dried and is crosslinked, another stripping film 2 is layered in as viscous On the adhesive composition of mixture layer 10, thus clamped and form by 2 stripping films 2.
Additionally, it is preferred that the peeling force of the side in 2 stripping films is different from the peeling force of the opposing party.
The reason is different by peeling force, during thereby using obtained bonding sheet, is shelled with can not damaging adhesive phase Remove the stripping film of a side.
In addition, the bonding sheet of aforesaid way can by peel off a side stripping film, make the adhesive phase exposed snugly Fit on the base materials such as optical film, thus obtain the bonding sheet for base material with optical film etc..
Now, according to demand, in order to improve the adaptation with base material, can to adhesive aspect carry out sided corona treatment, etc. The surface treatment such as gas ions processing and saponification process.
Aforesaid way due to adhesive phase manufacture and above-mentioned adhesive phase use be different places carry out etc., for Situation of adhesive phase etc., which must only be conveyed, becomes necessary.
In addition, as other modes, adhesive directly can not also be formed on the base materials such as optical film via stripping film The coating layer of composition, thus obtains bonding sheet.
Now, the surface side of exposing of the coating layer of adhesive composition is protected and used by being laminated stripping film after the drying When.
It should illustrate, the crosslinking in the coating layer of adhesive composition is by above-mentioned drying process and air-dries （seasoning）Process is carried out.
As the condition of above-mentioned air-dried process, coating layer, base material never to adhesive composition cause to damage and make to glue The coating layer of mixture composite is carried out from the viewpoint of being equably crosslinked, and is preferably set to 20~50 DEG C, is more preferably set to 23~30 ℃。
In addition, as humidity, being preferably set to 30~75%RH, being more preferably set to 45~65%RH.
Also, during, it is preferably set to 3~20 days, is more preferably set to 5~14 days.
（4）Bonding force
In addition, on the polarizer with adhesive phase that base material is polarizer, preferably making to adherend（Glass surface） Bonding force after attaching 1 day is more than 1N/25mm and less than or equal to the value in the range of 10N/mm.
If the reason is the value that above-mentioned bonding force is below 1N/25mm, durability under prescribed conditions becomes sometimes Obtain insufficient.On the other hand, if above-mentioned bonding force is the value more than 10N/25mm, releasable is excessively reduced sometimes.
Therefore, the bonding force for more preferably making the polarizer with adhesive phase is more than 2.5N/25mm and less than or equal to 8N/ Value in the range of 25mm, further preferably greater than 3.5N/25mm and the value being less than or equal in the range of 5.5N/25mm.
In addition, from the same reason, it is more than 3N/25mm preferably to make the bonding force after being attached 21 days to adherend And less than or equal to the value in the range of 30N/25mm, more preferably higher than 4N/25mm and less than or equal in the range of 20N/25mm Value, further preferably greater than 5N/25mm and less than or equal to the value in the range of 15N/25mm.
It should illustrate, the assay method of bonding force is documented in embodiment.
2. base material
In the present invention, it is preferred to possess above-mentioned adhesive phase at least one side of base material and form bonding sheet.
As shown in figure 5, as the base material 101 in the bonding sheet 100 of the present invention, being not particularly limited, for example, it is preferable to enumerate Polyvinyl alcohol, polyethylene terephthalate, triacetyl cellulose, makrolon, liquid crystal polymer, cycloolefin, polyamides are sub- Amine, polyamide, polyamidoimide, polyphenylene oxide, polyether-ketone, polyether-ether-ketone, polysulfones, polyether sulfone, polyphenylene sulfide, polyarylate, third The overlays such as olefin(e) acid system resin, the polymer of the structure containing ester ring type, fragrant family polymer.
In addition, if in terms of purposes illustrate, then preferably enumerate polarizer, polarizing layer diaphragm, the angle of visual field expand film, The optical film used in antiglare film, polarizer etc., liquid crystal display etc..
For example, according to the present invention, even if in the case that base material is polarizer, can also obtain effectively suppressing light leak The advantage of generation.
In addition, according to the present invention, due to also can be closely sealed well to polariscope etc., so the raw material of polarizer will be used as The extension of polyvinyl alcohol resin containing iodine and the polariscope that is made can also turn into the base material 101 in the bonding sheet 100 of the present invention in itself. Also, polariscope that the one side of polariscope is covered by diaphragms such as triacetyl cellulose, polyethylene terephthalates etc. Equally turn into object.
It should illustrate, bonding sheet during by base material for polarizer is referred to as the polarizer with adhesive phase.
In addition, being not particularly limited as the thickness of base material, it is often preferred that the value in the range of 1~1000 μm.
If the thickness that the reason is above-mentioned base material is less than 1 μm, sometimes the excessively reduction of mechanical strength, operability, or It is difficult to form uniform thickness.On the other hand, if the thickness of above-mentioned base material is more than 1000 μm, operability excessively drops sometimes It is low, it is unfavorable to economy.
Therefore, the thickness for more preferably making base material is the value in the range of 5~500 μm, more preferably 10~200 μm In the range of value.
It should illustrate, in the case that base material is stripping film, it is often preferred that the value in the range of 20~150 μm.
In addition, from the viewpoint of the adaptation with adhesive phase is improved, the face of the formation coating layer of preferred pair base material 101 Implement surface treatment in side.
As this surface treatment, for example, linging processing, sided corona treatment, flame treatment, saponification process etc. can be enumerated, it is special Not preferred linging processing.
The reason is by using the base material for foring this priming coat, so as to improve and bond with not damaging base material The adaptation of oxidant layer.
It should illustrate, as the material for constituting this priming coat, cellulose esters can be enumerated（For example, cellulose acetate, second Acid-cellulose propionate, cellulose acetate butyrate (CAB), nitrocellulose and combinations thereof）, polyacrylic acid, polyurethane, poly- second Enol, polyvinyl ester, polyvinyl acetal, polyvinylether, polyethylene ketone, polyvinylcarbazole, polyvinyl butyral resin and Combinations thereof.
In addition, the thickness of priming coat is also not particularly limited, generally, it is preferred to be the value in the range of 0.05 μm~10 μm.
It should illustrate, as the method that the bonding sheet finally given is fitted in adherend, preferably such as Fig. 5（c）~（d） It is shown, first, the stripping film 2 being layered on adhesive phase 10 is peeled off, then, is sealed at the surface of the adhesive phase 10 exposed Adherend 200 and fitted.
Embodiment
Hereinafter, with reference to embodiment, the present invention is further described.
［ embodiment 1 ］
1. the preparation of adhesive composition
Prepare by following 100 parts by weight conducts（A）The acrylate copolymer with cross-linking functional group, 0.15 weight of composition Measure part conduct（B）The crosslinking agent of composition and 0.20 parts by weight conduct（C）It is viscous that the organosilsesquioxanes compound of composition is constituted Mixture composite.
It should illustrate, the numerical value in table 1 represents to have carried out the value of solid constituent conversion.
In addition, in table 1, the use level of monomer component refers to integrally regard monomer component as parts by weight during 100 parts by weight.
Additionally as（B）The crosslinking agent of composition and conduct（C）The content of the organosilsesquioxanes compound of composition refers to Will（A）Composition is used as parts by weight during 100 parts by weight.
（1）On（A）Composition
Under nitrogen environment, 99.0 parts by weight are stored in container as monomer component（a）N-butyl acrylate（BA）、 1.0 parts by weight are used as monomer component（b）Acrylic acid 4- hydroxybutyls（4HBA）, 0.3 parts by weight as polymerization initiator idol Nitrogen bis-isobutyronitrile and 150 weight part of ethylacetate.
Then, it is polymerize under conditions of 60 DEG C, 8 hours, obtains conduct（A）The weight average molecular weight 1,500,000 of composition The ethyl acetate solution of acrylate copolymer.It should illustrate, the weight average molecular weight of acrylate copolymer is to utilize gel infiltration color Spectrometry（Hreinafter referred to as GPC method）Determine.
I.e., first, calibration curve is made using polystyrene.Hereinafter, weight average molecular weight is represented with polystyrene scaled value. Then, the concentration for preparing the measure objects such as acrylate copolymer is 1 weight % tetrahydrofuran（THF）Solution, utilizes TOSOH plants Formula commercial firm GEL PER MEATION CHROMATOGRAPH HLC-8020（By TSKGEL GMHXL、TSKGEL GMHXL、TSKGEL G2000HXL3 columnss in series constituted）Weight average molecular weight is determined with 40 DEG C, THF solvents, the condition of 1ml/ minutes.Also, use TOSOH Co. Ltd. system TSK GUARD COLUMN are used as guard column.
（2）On（B）Composition
To the conduct of the obtained parts by weight of solid constituent 100（A）The acroleic acid polymerization with cross-linking functional group of composition Added in thing solution using solid constituent convert be calculated as 0.15 parts by weight as（B）The isocyanates system crosslinking agent of composition（TD- 75）（Soken Chemical ＆ Engineering Co., Ltd.'s system, the weight % of solid constituent 75, ethyl acetate solution）.
（3）On（C）Composition
Then, to the conduct of the parts by weight of solid constituent 100（A）The acrylate copolymer with cross-linking functional group of composition It is above-mentioned with adding in solution（B）The conduct of 0.20 parts by weight is added while composition（C）The organosilicon sesquialter containing sulfydryl of composition Siloxane compound I（HBSQ-105-7）（Arakawa Chemical Industries, Ltd.'s system, n=12）.
Then, uniform mixing, with ethyl acetate dilution until solid component concentration becomes 20 weight %, obtains adhesive group Polymer solution.
2. the coating of adhesive composition solution
Then, to the polyethylene terephthalate stripping film of 38 μm of the thickness as stripping film（LINTEC plants of formulas Commercial firm's system, SP-PET3811）Lift-off processing face, be coated with by dried thickness in the way of 25 μm using scraper coating machine Obtained adhesive composition solution, forms coating layer.
Then, obtained coating layer is fitted after 90 DEG C are implemented drying process in 1 minute with 180 μm of polarizer of thickness, Pressurizeed 20 minutes under conditions of 23 DEG C, 0.5MPa with autoclave, obtain the coating layer and polarizer structure by adhesive composition Into layered product.
3. adhesive composition is air-dried
Then, obtained layered product is placed 7 days under conditions of 23 DEG C, 50%RH（Air-dry）, fill adhesive composition Divide crosslinking, obtain the polarizer with adhesive phase of embodiment 1.
4. evaluate
（1）The evaluation of bonding force
The bonding since the polarizer with adhesive phase behind being fitted with adherend 1 day and after 21 days is determined respectively Power.
That is, using cutting device（Reed open country makes institute's Co. Ltd. system, SUPER CUTTER）, by obtained band adhesive phase Polarizer be cut into width 25mm × length 100mm size, measure sample is made.
Then, peeled off from obtained measure sample after stripping film, be fitted in alkali-free glass（Corning Co. Ltd. systems, EAGLE XG）.
Then, the alkali-free glass for measure sample of having fitted is put into autoclave（Chestnut original makes institute's Co. Ltd. system）, 0.5MPa, under conditions of 50 DEG C after pressurization 20 minutes, placed 1 day under conditions of 23 DEG C, 50%RH.
Then, using cupping machine（ORIENTEC Co. Ltd. systems, TENSILON）, with following conditions to determining sample Bonding force is determined, is evaluated according to following benchmark.It the obtained results are shown in table 1.
Peeling rate：300mm/ minutes
Peel angle：180°
◎：The value of bonding force is the value more than 3.5 and less than or equal to 5.5N/25mm.
○：The value of bonding force is the value more than 2.5 and less than or equal to 3.5N/25mm, or more than 5.5 and to be less than or equal to 8.0N/25mm value.
△：The value of bonding force is the value more than 1.0 and less than or equal to 2.5N/25mm, or more than 8.0 and to be less than or equal to 10.0N/25mm value.
×：The value of bonding force is below 1.0N/25mm value, or is the value more than 10.0N/25mm.
In addition, will similarly determine sample application in after alkali-free glass, placed 21 days under conditions of 23 DEG C, 50%RH （504 hours）, the bonding force of the situation is determined, is evaluated according to following benchmark.It the obtained results are shown in table 1.
◎：The value of bonding force is 5.0~20N/25mm value.
○：The value of bonding force is 3.0 values less than 5.0N/25mm.
×：The value of bonding force is the value less than 3.0N/25mm, or is the value more than 20N/25mm.
（2）The evaluation of durability
Evaluate the durability of the polarizer with adhesive phase under prescribed conditions.
That is, using cutting device（Reed open country makes institute's Co. Ltd. system, SUPER CUTTER）, by obtained band adhesive phase Polarizer be cut into 233mm × 309mm size, measure sample is made.
Then, peeled off from obtained measure sample after stripping film, fit in alkali-free glass（Corning Co. Ltd. systems, EAGLE XG）.
Then, the alkali-free glass for measure sample of having fitted is put into autoclave（Chestnut original makes institute's Co. Ltd. system）In, Under conditions of 0.5MPa, 50 DEG C after pressurization 20 minutes, 80 DEG C under drying, 60 DEG C/90%RH and thermal shock（HS）Condition（1 The individual cycle is -35 DEG C（30 minutes）/70℃（30 minutes））It is each it is durable under the conditions of put into after, place 100 hours.
Then, the state for determining sample is observed using 10 times of magnifying glasses, according to following benchmark, evaluates durability. It the obtained results are shown in table 1.
◎：Peeling completely without polarizer is peeled off.
○：There is peeling stripping away from below end 0.5mm.（Using end as starting point, do not risen in the position more than 0.5mm Skin is peeled off）
△：There is peeling stripping away from below end 1.0mm.（Using end as starting point, do not risen in the position more than 1.0mm Skin is peeled off）
×：There is peeling stripping more than 1.0mm away from end.
In addition, will similarly determine sample application in after alkali-free glass, autoclave is put into（Chestnut original makes Co., Ltd. of institute System）In, under conditions of 0.5MPa, 50 DEG C after pressurization 20 minutes, 80 DEG C under drying, 60 DEG C/90%RH and thermal shock（HS） Condition（1 cycle is -35 DEG C（30 minutes）/70℃（30 minutes））It is each it is durable under the conditions of put into after, place 500 hours.
Then, the state for determining sample is observed using 10 times of magnifying glasses, according to following benchmark, evaluates durability. It the obtained results are shown in table 1.
◎：Peeling completely without polarizer is peeled off.
○：There is peeling stripping away from below end 0.5mm.
△：There is peeling stripping away from below end 1.0mm.
×：There is peeling stripping more than 1.0mm away from end.
（3）The evaluation of Gel fraction
Evaluate the Gel fraction of adhesive composition.
That is, according to the process of above-mentioned " coatings of 2. adhesive composition solution ", it is coated with the peel ply of stripping film viscous Mixture composite, after 90 DEG C are implemented to heat for 1 minute, 38 μm of the thickness of another stripping film will be used as instead of polarizer Polyethylene terephthalate stripping film（LINTEC Co. Ltd. systems, SP-PET3801）The side connected with its peel ply Formula fits in coating layer.
Then, the polarizer with adhesive phase is placed 12 days under conditions of 23 DEG C, 50%RH（Air-dry）And bonded Piece.
Then, the stripping film on the two sides of obtained bonding sheet is peeled off, the adhesive composition for taking out about 0.1g is wrapped into TETORON screen clothes（#200）, it is solvent based on Soxhlet extraction device to use using ethyl acetate（Tokyo glass apparatus strain formula meeting Society's system, extraction equipment for fat）Backflow, extract the non-gel component of adhesive composition, it is solidifying using being calculated with the ratio between initial mass Glue percentage.It the obtained results are shown in table 1.
（4）The evaluation of haze value
Evaluate the haze value of adhesive phase.
That is, according to the process of above-mentioned " coatings of 2. adhesive composition solution ", it is coated with the peel ply of stripping film viscous Mixture composite, after 90 DEG C are implemented to heat for 1 minute, 38 μm of the thickness of another stripping film will be used as instead of polarizer Polyethylene terephthalate stripping film（LINTEC Co. Ltd. systems, SP-PET3801）The side connected with its peel ply Formula fits in coating layer.
Then, by being air-dried under conditions of same when with obtaining the polarizer with adhesive phase, bonding sheet is obtained.
Then, the stripping film on the two sides of obtained bonding sheet is peeled off, measure sample is made, is transmitted using integrating sphere type light Rate determines device（Electricity Se Industrial Co., Ltd of Japan system, NDH-2000）, based on JIS K7105, obtained measure sample is surveyed Determine diffused transmission rate（Td%）With full light transmittance（Tt%）, use following formula（3）Calculate haze value.It the obtained results are shown in table 1.
Haze value=（Td/Tt）×100 （3）
［ embodiment 2~4 ］
In embodiment 2~4, make conduct（C）The content of the organosilsesquioxanes compound containing sulfydryl of composition is relative In conduct（A）The parts by weight of acrylate copolymer 100 with cross-linking functional group of composition are respectively 0.1 parts by weight, 0.3 weight Part and 1.0 parts by weight, in addition, are made the polarizer with adhesive phase, are evaluated similarly to Example 1.Will To result be shown in table 1.
［ embodiment 5~7 ］
In embodiment 5~7, using as（C）The organosilsesquioxanes compound containing sulfydryl of composition be changed to containing The organosilsesquioxanes compound II of epoxy radicals（SQ-506（Arakawa Chemical Industries, Ltd.'s system, n=10）, and make each From addition relative to conduct（A）The parts by weight of acrylate copolymer 100 with cross-linking functional group of composition are 0.10 weight Part, 0.30 parts by weight and 1.00 parts by weight are measured, in addition, the polarizer with adhesive phase are made similarly to Example 1, Evaluated.It the obtained results are shown in table 1.
［ comparative example 1 ］
In comparative example 1, without conduct（C）The organosilsesquioxanes compound containing sulfydryl of composition, in addition, The polarizer with adhesive phase is made similarly to Example 1, is evaluated.It the obtained results are shown in table 1.
［ comparative example 2 ］
In comparative example 2, using as（C）The organosilsesquioxanes compound containing sulfydryl of composition is changed to by formula（4） The organoalkoxysilane compounds IV of expression（KBM-803（Shin-Etsu Chemial Co., Ltd's system））, in addition, respectively with The polarizer with adhesive phase is similarly made in embodiment 1, is evaluated.It the obtained results are shown in table 1.
［ comparative example 3 ］
In comparative example 3, using as（C）The organosilsesquioxanes compound containing sulfydryl of composition is changed to as by upper State formula（4）The linear siloxanes oligomer compounds V of the condensation product of the organoalkoxysilane compounds of expression（X-41-1805 （Shin-Etsu Chemial Co., Ltd's system））, in addition, the polarizer with adhesive phase is made similarly to Example 1 respectively, Evaluated.It the obtained results are shown in table 1.
Table 1
Industrial applicability
More than, as being described in detail, according to the present invention, by being provided in the acrylate copolymer containing cross-linking functional group Ratio contains crosslinking agent and the organosilsesquioxanes compound with specific structure, so as to obtain doing over again property and in regulation environment Under excellent in te pins of durability and excellent corrosion resistance to metal adhesive composition.
Therefore, it can expect that adhesive composition of the present invention etc. is clearly helpful for liquid crystal display device, plasma display The optical film of showing device, Organnic electroluminescent device, inorganic electroluminescent device etc. is the high-quality of the various films of representative.

Claims (9)

1. a kind of adhesive composition, it is characterised in that be containing the acrylate copolymer as A compositions and as B component The adhesive composition of crosslinking agent, the acrylate copolymer contains the hydroxyl for belonging to cross-linking functional group,
Contain the organosilsesquioxanes compound with reactive group of following formulas (1) expression as C compositions,
[RSiO3/2]n (1)
In formula (1), R is hydrogen atom, the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, carbon number 6~20 Aryl, halogen atom or reactive group in any one, multiple R are identical or mutually different, wherein at least one for reaction Property group, in addition at least another be hydrogen atom, the alkoxy of carbon number 1~4 and halogen atom in any one, n be 2~ 50 integer.
2. adhesive composition according to claim 1, it is characterised in that there is reactive base as the C compositions The organosilsesquioxanes compound of group is the organosilsesquioxanes compound containing sulfydryl.
3. adhesive composition according to claim 1, it is characterised in that make the organosilsesquioxanes compound Content is 0.001~1.5 parts by weight scope relative to the parts by weight of acrylate copolymer 100 of the hydroxyl as the A compositions Interior value.
4. adhesive composition according to claim 1, it is characterised in that be used as the propylene of the hydroxyl of the A compositions Acid polymer is the polymer from following (a)~(c) compositions as monomer component,
(a) there is (methyl) alkyl acrylate of carbon number for 1~20 alkyl：100 parts by weight,
(b) intramolecular has the compound containing unsaturated double-bond of hydroxyl：0.5~10 parts by weight,
(c) intramolecular has the compound containing unsaturated double-bond of carboxyl：0 parts by weight or more than 0 parts by weight and less than or equal to 0.1 Parts by weight.
5. adhesive composition according to claim 1, it is characterised in that as the crosslinking agent of the B component be isocyanide Acid esters system crosslinking agent, it is 0.05~5 relative to the parts by weight of acrylate copolymer 100 of the hydroxyl as A compositions to make its content Value in the range of parts by weight.
6. adhesive composition according to claim 1, it is characterised in that further contain antistatic additive as D compositions.
7. a kind of bonding sheet, it is characterised in that be the bonding on base material with the adhesive phase for coming from adhesive composition Piece, described adhesive composition contains the acrylate copolymer as A compositions and the crosslinking agent as B component, the acrylic acid Polymer contains the hydroxyl for belonging to cross-linking functional group,
Described adhesive composition contains the organosilsesquioxanes compound with reactive group of following formulas (1) expression As C compositions,
[RSiO3/2]n (1)
In formula (1), R is hydrogen atom, the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, carbon number 6~20 Aryl, halogen atom or reactive group in any one, multiple R are identical or mutually different, wherein at least one for reaction Property group, in addition at least another be hydrogen atom, the alkoxy of carbon number 1~4 and halogen atom in any one, n be 2~ 50 integer.
8. bonding sheet according to claim 7, it is characterised in that the base material is optical film, and in the optical film At least one side possesses described adhesive layer.
9. bonding sheet according to claim 7, it is characterised in that the base material is stripping film, and in described adhesive The one side opposite with the stripping film of layer is laminated other stripping films.
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