CN103289612A - Adhesive composition and adhesive sheet - Google Patents

Adhesive composition and adhesive sheet Download PDF

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Publication number
CN103289612A
CN103289612A CN2012105856029A CN201210585602A CN103289612A CN 103289612 A CN103289612 A CN 103289612A CN 2012105856029 A CN2012105856029 A CN 2012105856029A CN 201210585602 A CN201210585602 A CN 201210585602A CN 103289612 A CN103289612 A CN 103289612A
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Prior art keywords
composition
compound
binder
binder composition
organosilsesquioxanes
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CN103289612B (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

Abstract

The present invention relates to an adhesive composition and an adhesive sheet. The present invention provides the adhesive composition with excellent durability in a defined environment and excellent corrosion resistance to metals, and the adhesive sheet using the adhesive composition. The adhesive composition is characterized in that, the adhesive composition includes crosslinkable functional group-containing acrylic polymer as a component (A), a crosslinking agent as a component (B) and an organic silicon silsesquioxane compound as the component (C) comprising a reactive group of sulfydryl, and the content of the organic silicon silsesquioxane compound relative to 100 parts by weight of the crosslinkable functional group-containing acrylic polymer is 0.001-1.5 parts by weight. The adhesive sheet uses the adhesive composition.

Description

Binder composition and adhesive sheet
Technical field
The present invention relates to binder composition and adhesive sheet.Particularly relate to doing over again property (リ ヮ one Network) and the excellent in te pins of durability under the regulation environment and the excellent corrosion resistance of metal is used for constituting the binder composition of binder layer and the adhesive sheet that uses this binder composition.
Background technology
In the past, for employed binder compositions such as opticses such as polaroid, fenestrated membranes, fit well in the surface that requirement can make plastic material and this unlike material of glass weather resistance each other, and when mistake takes place to fit, can not peel off (doing over again property) by binder composition with not remaining in glass surface.
At this, as the binder composition that is used for such use, known interpolation silane coupling agent.
Namely, silane coupling agent has alkoxysilyl part and bonding group part usually in a part, therefore the alkoxysilyl part can with the glass surface effect, on the other hand, bonding group part can with binder composition in reactions such as polymkeric substance, can through the time increase bounding force and adhesive sheet given the weather resistance of regulation.
Therefore, even if design the initial adhesion power of adhesive sheet lower, also can by add silane coupling agent through the time increase bounding force, and then doing over again property and the weather resistance of the adhesive sheet of can realizing getting both.
For example, with provide behind the good and coating adhesive of doing over again property through do not produce peeling for a long time yet, peel off etc., the binder composition of excellent in te pins of durability is purpose, disclose organo-functional groups such as containing sulfydryl and contained the organopolysiloxane of regulation as the binder composition (for example, patent documentation 1) of silane coupling agent.
More specifically, disclosing with the organopolysiloxane that contains the different multiple alkoxyl group of carbonatoms at a part is the binder composition of essential composition.
In addition, blooming with the band tackiness agent that is used for liquid crystal indicator etc. that good and the showing money or valuables one carries unintentionally can suppress to fit in glass substrate time of doing over again property, peeling is provided, peels off is purpose, the blooming (for example, patent documentation 2) of the band tackiness agent that the organosilicon oligopolymer that contains regulation and acrylic resin form is disclosed.
More specifically, disclose the blooming that contains the band tackiness agent that organosilicon oligopolymer and acrylic resin form, this organosilicon oligopolymer has functional group and alkoxyl groups such as sulfydryl, epoxy group(ing).
On the other hand, be purpose so that the resin combination excellent in adhesion with inorganic materials such as metallic substance to be provided, the resin combination (for example, patent documentation 3) that contains cage shape silicious sesquioxane is disclosed.
More specifically, in patent documentation 3, for under the situation of wiring board not being carried out roughening, make distribution bonding in the mode that bonding strength increases, disclose the thermosetting resin that contains as cyanate ester resin, as the thermoplastic resin of polysulfone resin and the resin combination that formed by the cage shape silicious sesquioxane of following general formula (2) expression.
Figure BDA00002674090100021
In addition, contain ionizing rays susceptibility ladder polysiloxane and form with composition (for example patent documentation 4) as the caking agent that linking agent forms to be provided at that normal temperature has good binding property and to be purpose by the caking agent that caking intensity increases substantially, to disclose.
More specifically, in patent documentation 4, disclose contain have epoxy group(ing), caking agent that the trapezoidal poly-silicious sesquioxane of functional group such as sulfydryl forms as linking agent forms and uses composition.
In addition, be purpose the solidified nature height to be provided, liquid crystal pollution is low and keeps the liquid crystal sealing agent of proper viscosity for a long time, disclose and contained the liquid crystal sealing agent that the radically curing resin forms, this radically curing resin has ethylene linkage unsaturated link(age) (for example patent documentation 5) more than 2 at intramolecularly.
More specifically, in patent documentation 5, disclose and contained the liquid crystal sealing agent that poly organic silicon sesquioxyalkane forms, this poly organic silicon sesquioxyalkane contains the organic group with ethylene linkage unsaturated link(age) more than 2.
The prior art document
Patent documentation
Patent documentation 1: international No. 2008/090813 communique (claim etc.) that disclose
Patent documentation 2: TOHKEMY 2008-176173 communique (claim etc.)
Patent documentation 3: TOHKEMY 2003-49079 communique (claim, paragraph 0013～0032 etc.)
Patent documentation 4: TOHKEMY 2003-238923 communique (claim, paragraph 0015～0018 etc.)
Patent documentation 5: TOHKEMY 2009-86291 communique (claim etc.)
Summary of the invention
Yet, for the component of polymer in the disclosed binder composition in the patent documentation 1～2, found since contain in molecule, have a carboxyl in a large number vinylformic acid as its constituent, so after liquid crystal cells etc. is fitted by adherend, the problem that bonding force excessively rises.
Therefore, removing under acrylic acid situation from the constituent of the polymkeric substance of binder composition in order to suppress that bounding force rises, discovery is according to kind, its array mode of the silane coupling agent that uses, inadequate problem that weather resistance significantly reduces easily or doing over again property becomes.
In addition, for the contained cyanate ester resin of disclosed resin combination in the patent documentation 3, find because high price, and hydrolysis easily, cementability is poor, so although contain cage shape silsesquioxane compound, also can't be used for the problem of polaroid.
In addition, disclosed tackiness agent formation is the compound that plays a role as the linking agent that improves bond strength by the irradiation ionizing ray with the poly-silsesquioxane compound of the contained trapezoidal type of composition in the patent documentation 4, but find owing to use ionizing ray, thus in the use with equipment on the many problems of restriction.
In addition, find in the patent documentation 5 that disclosed poly organic silicon sesquioxyalkane in the disclosed liquid crystal sealing agent is for the radically curing resin that improves with the bonding strength of substrate, does not have the problem as the effect of additive.
That is, disclosed silsesquioxane compound is linking agent, radically curing resin etc. in the patent documentation 3～5, in the time of in adding the binder composition of regulation to, the function of not finding as giving weather resistance, fusible silsesquioxane compound.
Therefore, the inventor etc. are in view of as above practical situation, through further investigation, found that by in the binder composition that contains acrylate copolymer and linking agent, contain the organosilsesquioxanes compound of regulation with the regulation ratio, thereby obtain doing over again property and the excellent in te pins of durability under the regulation environment and to the binder composition of the excellent corrosion resistance of metal, and then finished the present invention.
That is, the object of the present invention is to provide doing over again property and the excellent in te pins of durability under the regulation environment, and to the binder composition of the excellent corrosion resistance of metal with use the adhesive sheet of this binder composition.
According to the present invention, a kind of binder composition is provided, it is characterized in that, be to contain as the acrylate copolymer that contains bridging property functional group of (A) composition with as the binder composition of the linking agent of (B) composition, contain organosilsesquioxanes compound conduct (C) composition with reactive group, can address the above problem thus.
Namely, because binder composition of the present invention is with (A) composition and (B) composition, contain organosilsesquioxanes compound conduct (C) composition with reactive group with the linking agent reaction, even if so for example under the high temperature drying condition, under the hot and humid condition or place repeatedly under the inferior exacting terms of condition of cold condition and hot conditions, also can bring into play excellent weather resistance.
In addition, it can access the doing over again property of regulation with just suppressing to be lower value with the bounding force afterwards of being fitted by adherend on the other hand.
In addition, when constituting binder composition of the present invention, preferably having the reactive group that the organosilsesquioxanes compound of reactive group has is sulfydryl.
In addition, when constituting binder composition of the present invention, the content that preferably makes the organosilsesquioxanes compound with reactive group is value in 0.001～1.5 weight part scope with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as (A) composition.
This is because by constituting like this, the interaction that can average out to tackiness agent and the two performance of glass.
In addition, when constituting binder composition of the present invention, preferably it is characterized in that, is from the polymkeric substance as following (a)～(c) composition of monomer component as the acrylate copolymer that contains bridging property functional group of (A) composition.
(a) has (methyl) alkyl acrylate that carbonatoms is 1～20 alkyl: 100 weight parts
(b) contain the unsaturated double-bond compound what intramolecularly had a hydroxyl: 0.5～10 weight part
(c) contain the unsaturated double-bond compound what intramolecularly had a carboxyl: (wherein, 0 weight part refers to not contain for 0 weight part or 0～0.1 weight part.）
By such formation, thereby do not contain in fact what intramolecularly had a carboxyl as the monomer whose composition as the acrylate copolymer that contains bridging property functional group of (A) composition and to contain the unsaturated double-bond compound, therefore even if liquid crystal cells etc. is had by adherend under the situation of the nesa coating that forms by metal evaporation etc. etc., also can stably prevent the generation of acid corrosion.
In addition, although (A) composition does not contain in fact what intramolecularly had a carboxyl and contains the unsaturated double-bond compound as monomer component, but for example under the high temperature drying condition, under the hot and humid condition or placing repeatedly under the exacting terms of the inferior regulation of condition of cold condition and hot conditions, also can bring into play excellent weather resistance.
In addition, it can access the doing over again property of regulation with just suppressing to be lower value with the bounding force afterwards of being fitted by adherend on the other hand.
In addition, when constituting binder composition of the present invention, preferably the linking agent as (B) composition is the isocyanate-based linking agent, and making its content is the interior value of 0.05～5 weight part scope with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as (A) composition.
By such formation, thereby the cohesive force of binder composition be can improve, doing over again property and the weather resistance under the regulation environment improved.
In addition, when constituting binder composition of the present invention, preferably further contain static inhibitor as (D) composition.
By such formation, thereby when using as the tackiness agent of film applying usefulness in that binder composition of the present invention is solidified, even if from by under the situation of adherend stripping film, also can suppress the generation of static effectively, on the other hand, can further improve doing over again property and the weather resistance under the regulation environment.
In addition, another mode of the present invention is a kind of adhesive sheet, it is characterized in that, it is the adhesive sheet that has the binder layer that comes from binder composition at base material, described binder composition contains the linking agent as the acrylate copolymer that contains bridging property functional group of (A) composition and conduct (B) composition, and binder composition contains organosilsesquioxanes compound conduct (C) composition with reactive group.
Namely, because adhesive sheet of the present invention possesses the binder composition of regulation as binder layer, so doing over again property and the excellent in te pins of durability under the regulation environment, even and if had by adherend at liquid crystal cells etc. under the situation of the nesa coating that forms by metal evaporation etc. etc., also can stably prevent the generation of acid corrosion.
In addition, when constituting adhesive sheet of the present invention, preferred substrates is blooming, and possesses binder layer in the one side at least of this blooming.
By such formation, thereby can access following adhesive sheet with blooming, this has doing over again property and the excellent in te pins of durability under the regulation environment of the adhesive sheet of blooming, even and if have at liquid crystal cells under the situation of nesa coating, erosion resistance is also excellent.
In addition, when constituting adhesive sheet of the present invention, preferred substrates is stripping film, and on the one side opposite with this stripping film of binder layer stacked other stripping film.
By such formation, thereby can improve the operability of adhesive sheet.
Description of drawings
Fig. 1 is the figure of content and the relation that attaches the bounding force after 1 day that has the organosilsesquioxanes compound of different types of reactive group for explanation.
Fig. 2 is the figure of content and the relation that attaches the bounding force after 21 days that has the organosilsesquioxanes compound of different types of reactive group for explanation.
Fig. 3 be for explanation contain sulfydryl the organosilsesquioxanes compound content with attach after 1 day and attach the figure of the relation of the bounding force after 21 days.
Fig. 4 is the figure that contains the relation of the content of organosilsesquioxanes compound of sulfydryl and gel percentage ratio for explanation.
Fig. 5 (a)～(d) is the synoptic diagram for the manufacture method of the use-pattern of explanation binder composition etc. and adhesive sheet.
Fig. 6 is another synoptic diagram for the use-pattern of explanation binder composition etc.
Nomenclature
1: the coating layer of binder composition, 2: stripping film, 10: binder layer, 100: adhesive sheet, 101: base material, 200: by adherend
Embodiment
[the 1st embodiment]
Embodiments of the present invention are a kind of binder compositions, it is characterized in that, are to contain as the acrylate copolymer that contains bridging property functional group of (A) composition with as the binder composition of the linking agent of (B) composition; Contain organosilsesquioxanes compound conduct (C) composition with reactive group.
Below, suitably with reference to accompanying drawing, specify the 1st embodiment of the present invention.
1.(A) composition: the acrylate copolymer that contains bridging property functional group
(1) monomer component
(1)-1 monomer component (a)
The monomer component (a) of (methyl) alkyl acrylate that preferably contains the alkyl with carbonatoms 1～20 as the acrylate copolymer that contains bridging property functional group of (A) composition during as polymerization.
Its reason be if the carbonatoms of abovementioned alkyl for greater than 20 value, side chain oriented crystalline each other sometimes then, the binding property of the binder composition that obtains thus reduces.
Therefore, the carbonatoms that more preferably makes the alkyl in the acrylate copolymer that contains bridging property functional group is the value in 1～10 scope, more preferably the value in 4～8 scopes.
In addition, carbonatoms as alkyl is (methyl) alkyl acrylate of the value in 1～20 scope, for example, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate and (methyl) dodecylacrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid cetyl ester, the independent a kind of or combination more than two kinds in (methyl) vinylformic acid stearyl etc.
In addition, because (methyl) acrylate as monomer component (a) is the principal constituent of formation as the acrylate copolymer that contains bridging property functional group of (A) composition, so be preferably the above value of 50 weight % of the total monomer composition of formation (A) composition usually, the more preferably value in 60～99.5 weight % scopes, the more preferably value in 85～99 weight % scopes.
(1)-2 monomer component (b)
In addition, as the acrylate copolymer that contains bridging property functional group of (A) composition preferably contain intramolecularly have hydroxyl contain the unsaturated double-bond compound as polymerization the time monomer component (b).
Its reason is by containing above-mentioned monomer component (b), thereby this hydroxyl becomes bridging property functional group in acrylate copolymer.That is, when adding linking agent to binder composition, can carry out effectively can improving the cohesive force of the tackiness agent that obtains as each other crosslinked of the acrylate copolymer that contains functional group of (A) composition, carry out the adjustment of bounding force, storage modulus easily.
In addition, contain the unsaturated double-bond compound as what have a hydroxyl at intramolecularly, for example, preferably enumerate the hydroxyethyl vinyl ether, the hydroxybutyl vinyl ether, vinyl ether such as cyclohexyl dimethanol mono vinyl ether, vinyl carbinol, allyl group ethylene glycol, allyl etherss such as allyl group Diethylene Glycol, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester, the independent a kind of or combination more than two kinds in the monomers such as (methyl) vinylformic acid hydroxyalkyl acrylate such as (methyl) vinylformic acid 4-hydroxyl butyl ester.
In addition, if the intermiscibility of (methyl) acrylate monomer of the principal constituent of consideration and conduct formation (methyl) acrylic ester polymer, further preferred (methyl) vinylformic acid hydroxyalkyl acrylate then, any in preferred especially (methyl) vinylformic acid 2-hydroxy methacrylate and (methyl) vinylformic acid 4-hydroxyl butyl ester.
In addition, preferably making the use level of monomer component (b) is the interior value of scope of 0.5～10 weight part with respect to monomer component (a) 100 weight parts.
This reason is if the use level of monomer component (b) is the value that is lower than 0.5 weight part, and crosslinked between (A) composition becomes insufficient then sometimes, the weather resistance variation under the regulation environment.
On the other hand, if the use level of monomer component (b) is for surpassing the value of 10 weight parts, then the binding property of binder composition excessively reduces sometimes.
Therefore, more preferably making the use level of monomer component (b) is the interior value of scope of 1～5 weight part with respect to monomer component (a) 100 weight parts.
(1)-3 monomer component (c)
In addition, preferably as the acrylate copolymer that contains functional group of (A) composition do not contain in fact intramolecularly have carboxyl contain the unsaturated double-bond compound as polymerization the time monomer component (c).
More specifically, preferably polymerization as (A) composition contain the acrylate copolymer of bridging property functional group the time, the use level of monomer component (c) is the interior value of scope of 0 weight part or 0～0.1 weight part (wherein, 0 weight part refers to not contain) with respect to above-mentioned monomer component (a) 100 weight parts.
This reason is if the use level of above-mentioned monomer component (c) is for surpassing the value of 0.1 weight part, is then had by adherend under the situation of the nesa coating that forms by metal evaporation etc. etc. at liquid crystal cells etc., then is difficult to stably prevent the generation of acid corrosion sometimes.
In addition, reason be the bounding force of binder composition sometimes to after being fitted by adherend, sharply increase the doing over again property that is difficult to play stably easily.
Therefore, under the situation that cooperates monomer component (c), more preferably making the use level of monomer component (c) is the interior value of scope of 0.0001～0.1 weight part, the more preferably value in the scope of 0.001～0.05 weight part with respect to monomer component (a) 100 weight parts.
Should illustrate, as the kind of monomer component (c), so long as the unsaturated double-bond compound that contains that has a carboxyl at intramolecularly just is not particularly limited, for example, can enumerate vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, methylene-succinic acid, citraconic acid etc.
(1)-4 other monomer component (d)
Other monomer component (d) when in addition, also the preferred acrylate copolymer that contains functional group as (A) composition contains (a) monomer that contains the non-crosslinked group in addition as polymerization.
This reason be as the acrylate copolymer that contains functional group of (A) composition by containing (a) monomer that contains the non-crosslinked group in addition, thereby adjust the binding property of binder composition sometimes easily.
Therefore, when (A) containing monomer component (d) as the formation unit in the composition, preferably making the use level of monomer component (d) usually is the following values of 49.5 weight %, the more preferably value in the scope of 5～20 weight % with respect to the total monomer that constitutes (A) composition.
In addition, as above-mentioned (a) monomer that contains the non-crosslinked group in addition, for example, can enumerate acid amides such as vinyl-acetic ester, (methyl) acrylamide, acryloyl morpholine is monomer, for example, can enumerate the N-(methyl) acryloyl-oxy methylene radical succinimide, N-(methyl) acryloyl-succinimides such as 6-oxygen hexa-methylene succinimide are monomer, for example, can enumerate vinyl monomers such as N-vinyl pyrrolidone, vinylbenzene, for example, can enumerate acrylic ester monomers such as organosilicon (methyl) acrylate, fluorine (methyl) acrylate etc.
(2) weight-average molecular weight
The weight-average molecular weight that preferably makes the acrylate copolymer that contains functional group of conduct (A) composition in addition is 1,000,000～2,200,000 the interior value of scope.
This reason is that then the doing over again property of binder composition, weather resistance become insufficient sometimes if above-mentioned weight-average molecular weight is to be lower than 1,000,000 value.On the other hand, if above-mentioned weight-average molecular weight for surpassing 2,200,000 value, then is difficult to suppress the reduction of the processing suitability that caused by the viscosity increase of binder composition etc. sometimes.
Therefore, the weight-average molecular weight that more preferably makes the acrylate copolymer that contains functional group of conduct (A) composition is 1,200,000～1,800,000 the interior value of scope, the more preferably value in 1,400,000～1,600,000 the scope.
Should illustrate that above-mentioned weight-average molecular weight can be measured by gel permeation chromatography (GPC) method based on polystyrene conversion.
2.(C) composition: the organosilsesquioxanes compound with reactive group
(1) kind
Binder composition of the present invention is characterized in that, contains the organosilsesquioxanes compound with reactive group as (C) composition, and this organosilsesquioxanes compound preferably contains the structure by following general formula (1) expression.
This reason is by containing the compound with ad hoc structure as (C) composition, thus the interaction that can average out to tackiness agent and the two performance of glass.
Therefore, do not have containing under the situation of unsaturated double-bond compound as the monomer whose composition of carboxyl even if do not contain in fact at intramolecularly as the acrylate copolymer with bridging property functional group of (A) composition, can improve the weather resistance under the regulation environment and doing over again property yet.
[RSiO 3/2] n (1)
(in the general formula (1), R is any in aryl, halogen atom or the reactive group of alkoxyl group, carbonatoms 6～20 of alkyl, the carbonatoms 1～4 of hydrogen atom, carbonatoms 1～4, a plurality of R can be identical, also can be different mutually, wherein at least one is reactive group, at least another is the alkoxyl group of hydrogen atom, carbonatoms 1～4 and any in the halogen atom in addition, and n is 2～50 integer.）
In addition, as n, be preferably 6～20 integer, more preferably 8～14 integer.
This reason is if n for surpassing 50 integer, then is difficult to adjust viscosity sometimes, perhaps with the intermiscibility variation of other resin, solvent.
Therefore, be value in the above-mentioned scope by making condensation degree, thereby organosilsesquioxanes have higher structure, the variation of occurred conformation ground obtains the molecular structure of rigidity, the interaction that can average out to tackiness agent and the two performance of glass.
In addition, reactive group refer to have endways can with (A) composition in bridging property functional group directly or be situated between and formed the group of the functional group of chemical bond (for example, covalent linkage, ionic linkage etc.) by linking agent etc.As this functional group, for example, can preferably enumerate the functional group of containing hydroxyl, epoxy group(ing), sulfydryl etc.Wherein, more preferably contain sulfydryl.
In addition, can Direct Bonding between this functional group and the Siliciumatom, also can be situated between and carry out bonding by alkyl, alkoxyl group, aryl etc.
Should illustrate, functional group by will containing sulfydryl is as reactive group, thereby as (A) even if the hydroxyl that the general silane coupling agent of bridging property functional group of the acrylate copolymer of composition is difficult to act on, for example, if use the isocyanate-based linking agent of conduct described later (B) composition, also can bring into play excellent coupling effect.
Infer that this is owing to following reason: the isocyanate group of sulfydryl and isocyanate-based linking agent forms the thioxanthamide key easily, the hydroxyl bonding of the other end of this isocyanate-based linking agent and acrylate copolymer, be somebody's turn to do (C) composition and acrylate copolymer thus and have suitable distance, and form sagging structure.
Therefore, although as the acrylate copolymer with bridging property functional group of (A) composition do not contain in fact have carboxyl at intramolecularly the unsaturated double-bond compound as the monomer whose composition, also can improve the weather resistance under the regulation environment and doing over again property.
More specifically, as shown in Figure 1, the content of organosilsesquioxanes compound with different types of reactive group and the relation that attaches the bounding force after 1 day are described.
Namely, in Fig. 1, show rational curve A(figure respectively ◆), rational curve B(scheme ■) and rational curve C(scheme ▲), described rational curve A(figure ◆) be to adopt content (weight part) with respect to (A) composition organosilsesquioxanes compound I 100 weight parts, that have sulfydryl (n=12) as transverse axis, adopt the bounding force (N/25mm) of attaching after 1 day of the binder composition that obtains to be depicted as the longitudinal axis; Described rational curve B(figure ■) be to adopt with respect to (A) composition organosilsesquioxanes compound I 100 weight parts, that have epoxy group(ing) I(n=10) content (weight part) as transverse axis, adopt the bounding force (N/25mm) of attaching after 1 day of the binder composition that obtains to be depicted as the longitudinal axis; Described rational curve C(figure ▲) be to adopt content (weight part) with respect to (A) composition organosilsesquioxanes compound III 100 weight parts, that have epoxy group(ing) (mixtures of n=4～6) as transverse axis, adopt the bounding force (N/25mm) of attaching after 1 day of the binder composition that obtains to be depicted as the longitudinal axis.
In addition, in Fig. 2, the content of organosilsesquioxanes compound with different types of reactive group and the relation that attaches the bounding force after 21 days are described.
Namely, in Fig. 2, show rational curve D(figure respectively ◆), rational curve E(scheme ■) and rational curve F(scheme ▲), described rational curve D(figure ◆) be to adopt content (weight part) with respect to (A) composition organosilsesquioxanes compound I 100 weight parts, that have sulfydryl (n=12) as transverse axis, adopt the bounding force (N/25mm) of attaching after 21 days of the binder composition that obtains to be depicted as the longitudinal axis; Described rational curve E(figure ■) be to adopt with respect to (A) composition organosilsesquioxanes compound I 100 weight parts, that have epoxy group(ing) I(n=10) content (weight part) as transverse axis, adopt the bounding force (N/25mm) of attaching after 21 days of the binder composition that obtains to be depicted as the longitudinal axis; Described rational curve F(figure ▲) be to adopt content (weight part) with respect to (A) composition organosilsesquioxanes compound III 100 weight parts, that have epoxy group(ing) (mixtures of n=4～6) as transverse axis, adopt the bounding force (N/25mm) of attaching after 21 days of the binder composition that obtains to be depicted as the longitudinal axis.
Should illustrate that the composition of binder composition, the condition determination of bounding force etc. are put down in writing in an embodiment.
At first, from rational curve A and D as can be known, have sulfydryl n and be 12 organosilsesquioxanes compound I along with its content increases, attaches the bounding force after 1 day and attaches bounding force after 21 days all once increasing after, minimizing.
On the other hand, thereby rational curve B and E are as can be known, have epoxy group(ing) n and be 10 organosilsesquioxanes compound I I along with its content increases, and the bounding force and the bounding force of attaching after 21 days that attach after 1 day all reduce.
In addition, from rational curve C and F as can be known, have epoxy group(ing) n and be the organosilsesquioxanes compound III of 4～6 mixture along with its content increases, attaches the bounding force after 1 day and attach all reductions significantly of bounding force after 21 days.
Therefore, as can be known in order to keep the bounding force as the lowest limit requirement of binder composition, on the other hand, for the doing over again property that obtains stipulating, preferably the reactive group of the organosilsesquioxanes compound of conduct (C) composition is the reactive group that contains sulfydryl.
(2) content
In addition, preferably making the content of the organosilsesquioxanes compound with reactive group of conduct (C) composition is the interior value of 0.001～1.50 weight part scope with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as (A) composition.
This reason is to be value in the above-mentioned scope by making content as the organosilsesquioxanes compound with reactive group of (C) composition, thus the interaction that can average out to tackiness agent and the two performance of glass.
Its result can further improve doing over again property and the weather resistance under the regulation environment.
That is, if (C) content of composition is the value that is lower than 0.001 weight part, the absolute magnitude deficiency of (C) composition is difficult to give full play to its effect then sometimes, is difficult to obtain sufficient weather resistance.On the other hand, if (C) content of composition surpasses 1.5 weight parts, then sometimes for tackiness agent and glass the two, the interaction that averages out is upset, weather resistance, doing over again property variation.
Therefore, more preferably making as the content of the organosilsesquioxanes compound with reactive group of (C) composition is value in 0.01～1.0 weight part scope with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as (A) composition, further the value in 0.1～0.5 weight part scope preferably.
Then, use Fig. 3, the content of the organosilsesquioxanes compound that contains sulfydryl and the relation that attaches after 1 day and attach the bounding force after 21 days are described.
Namely, in Fig. 3, show rational curve A(figure ◇ respectively) and rational curve D(figure ■), described rational curve A(figure ◇) is to adopt with respect to the content that contains sulfydryl organosilsesquioxanes compound I (weight part) (A) composition 100 weight parts, that general formula (1) is contained as transverse axis, adopts the bounding force (N/25mm) of attaching after 1 day of the binder composition that obtains to be depicted as the longitudinal axis; Rational curve D(schemes ■) be to adopt with respect to the content that contains sulfydryl organosilsesquioxanes compound I (weight part) (A) composition 100 weight parts, that general formula (1) is contained as transverse axis, adopt the bounding force (N/25mm) of attaching after 21 days of the binder composition that obtains to be depicted as the longitudinal axis.
Should illustrate that the composition of binder composition, the condition determination of bounding force etc. are put down in writing in an embodiment.
At first, from rational curve A and D as can be known, along with the content of organosilsesquioxanes compound I increases, attaches the bounding force after 1 day and attaches bounding force after 21 days all once increasing after, minimizing.
More specifically, as can be known in rational curve A, when the content of organosilsesquioxanes compound I is 0 weight part, the bounding force that attaches after 1 day is 3.4N/25mm, increase along with compound I, bounding force sharply increases, and when the content of compound I is 0.1 weight part, attaches the value that bounding force after 1 day is shown as 5.3N/25mm.
On the other hand, if the content of compound surpasses 0.1 weight part as can be known, the bounding force that then attaches after 1 day begins to reduce lentamente, thereafter continuous decrease always.
In addition, as can be known in rational curve D, if become attaching after 21 days, then the variation of the content of organosilsesquioxanes compound I brings very big influence to bounding force, in order to obtain the bounding force in the preferable range, preferably make the content of organosilsesquioxanes compound I be the value in the scope of regulation.
More specifically, when the content of organosilsesquioxanes compound I is 0 weight part as can be known, the bounding force that attaches after 21 days is 7.8N/25mm, increase along with compound I, bounding force sharply increases, when the content of compound I is 0.1 weight part, attach the value that bounding force after 21 days is shown as 11.4N/25mm.
On the other hand, if the content of compound is for surpassing the value of 0.1 weight part as can be known, the bounding force that then attaches after 21 days begins to reduce, thereafter continuous decrease always.
Therefore, as can be known in order to keep the bounding force as the lowest limit requirement of binder composition, on the other hand, for the doing over again property that obtains stipulating, the content that preferably makes the organosilsesquioxanes compound with reactive group of conduct (C) composition is the interior value of scope of 0.001～1.5 weight part with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as (A) composition.
Then, use Fig. 4, the content of the organosilsesquioxanes compound that contains sulfydryl and the relation of gel percentage ratio are described.
That is, in Fig. 4, adopt content (weight part) with respect to organosilsesquioxanes compound I (A) composition 100 weight parts, that general formula (1) is contained as transverse axis, the gel percentage ratio (%) of the binder composition that obtains is shown as the longitudinal axis.
Should illustrate that the condition determination of the composition of binder composition, gel percentage ratio etc. are put down in writing in an embodiment.
At first, from rational curve as can be known, the content increase along with the organosilsesquioxanes compound I after gel percentage ratio was once increasing, reduces.
More specifically, when the content of organosilsesquioxanes compound I was 0 weight part as can be known, gel percentage ratio was 79.6%, increase along with compound I, gel percentage ratio sharply increases, and when the content of compound I was 0.1 weight part, gel percentage ratio was shown as 81.6% value.
On the other hand, if the content of compound is for surpassing the value of 0.1 weight part as can be known, then gel percentage ratio begins rapid minimizing, thereafter continuous decrease always.
Therefore, as can be known in order to increase the cohesive force of binder composition, in order to improve doing over again property and the weather resistance under the regulation environment, the content that preferably makes the organosilsesquioxanes compound with reactive group of conduct (C) composition is the interior value of scope of 0.001～1.5 weight part with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as (A) composition.
(3) action effect
At this, the effect that obtains when cooperating organic silsesquioxane compound I describes.
More specifically, compare with the organoalkoxysilane compound with reactive group or the organo-siloxane oligopolymer that forms as its condenses.
Organoalkoxysilane compound with reactive group has a Siliciumatom in 1 molecule, usually, silanol base condensation with alkoxyl group and the glass surface of silicon atom bonding, condensation reaction or addition reaction take place in the organic side chain with reactive group and the bridging property functional group in the tackiness agent with silicon atom bonding in addition, glass is situated between with tackiness agent and is connected by covalent linkage by the organoalkoxysilane compound, manifests strong adhesive effect.
In addition, for the organo-siloxane oligopolymer, in glass surface and tackiness agent, each molecule is more than the organoalkoxysilane compound with respect to the number of the reaction site of bridging property functional group, so compare with the organoalkoxysilane compound, can expect to bring into play stronger effect, infer because siloxane main chain can obtain various conformations, thus obtain organic side chain each other or alkoxyl group each other at the higher structure of intramolecularly uneven distribution.For example, as an example of higher structure, can enumerate with organic side chain toward the outer side mode and siloxane main chain forms the structure of spiral.At this moment, supposition is for the organo-siloxane oligopolymer, with tackiness agent in the bridging property functional group reactions organic side chain and with the alkoxyl group of the silanol radical reaction of glass surface in the two, the one side inhomogeneous surface that is present in higher structure morely is only arranged, carry out bonding more strongly with the side in tackiness agent and the glass, adhesive effect compare with the organoalkoxysilane compound relative a little less than.
Therefore, by being added with organic siloxane oligopolymer than desirable when much higher at the adhesive effect of tackiness agent, thereby can under the situation that does not significantly hinder its adhesive effect, give doing over again property.
On the other hand, the organosilsesquioxanes compound I has the molecular configuration of rigidity, and the uneven distribution of the functional group that caused by the variation of conformation does not take place on the higher structure surface.
That is, think and compare with the organoalkoxysilane compound that per molecule has effective reaction site number more, compare with the organo-siloxane oligopolymer, the interaction that tackiness agent and the two performance of glass are averaged out.
Therefore, for the interaction that tackiness agent and the two performance of glass are averaged out, for the organosilsesquioxanes compound in adding binder composition to, reactive organo-functional group is preferably 1.5～4.0 with respect to the mol ratio of alkoxysilyl and silanol base, and more preferably 2.5～3.0.
3.(B) composition: linking agent
In addition, when constituting binder composition of the present invention, it is characterized in that, contain linking agent as (B) composition.
This reason is the linking agent that utilizes as (B) composition, is cross-linked to each other as the acrylate copolymer that contains functional group of (A) composition, can increase the cohesive force of binder composition thus, improves doing over again property and the weather resistance under the regulation environment.
(1) kind
In addition, as above-mentioned linking agent, can preferably enumerate the isocyanate-based linking agent, aziridine is that linking agent, epoxy are linking agent, metal-chelating system linking agent.
This reason is by containing these linking agents, bounding force, the storage modulus of binder composition can being adjusted to preferred scope.
Wherein, preferably use the isocyanate-based linking agent.This is owing to following reason: if the isocyanate-based linking agent, the acrylate copolymer that then contains bridging property functional group can have the hydroxyl reaction that contains the unsaturated double-bond compound of hydroxyl with the intramolecularly as monomer component (b), makes the acrylate copolymer that contains bridging property functional group carry out chemically crosslinked each other effectively.
In addition, concrete example as above-mentioned isocyanate-based linking agent, for example, can enumerate trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, the 2-trimethylene diisocyanate, 1,2-butylidene vulcabond, 2,3-butylidene vulcabond, 1,3-butylidene vulcabond, 2,4,4-or 2,2, the 4-trimethyl hexamethylene diisocyanate, 2, aliphatic diisocyanates such as 6-vulcabond methylhexanoic acid ester, for example, can enumerate 1,3-pentamethylene vulcabond, 1, the 4-cyclohexyl diisocyanate, 1, the 3-cyclohexyl diisocyanate, 3-isocyanic ester methyl-3,5,5-3-methyl cyclohexanol based isocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), methyl-2, the 4-cyclohexyl diisocyanate, methyl-2, the 6-cyclohexyl diisocyanate, 1, two (isocyanic ester methyl) hexanaphthenes of 4-, 1, alicyclic diisocyanates such as two (isocyanic ester methyl) hexanaphthenes of 3-, for example, can enumerate the metaphenylene vulcabond, to phenylene vulcabond, 4,4 '-diphenyl diisocyanate, 1, the 5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4-or 2,6-tolylene diisocyanate or its mixture, 4,4 '-Tolylamine vulcabond, the dianisidine vulcabond, 4, aromatic diisocyanates such as 4 '-diphenyl ether vulcabond, for example, can enumerate 1,3-or 1,4-eylylene diisocyanate or its mixture, ω, ω '-vulcabond-1, the 4-diethylbenzene, 1, aromatic-aliphatic vulcabond such as two (1-isocyanic ester-1-methylethyl) benzene of 3-or 1,4-or its mixture, for example, can enumerate triphenyl methane-4,4 ', 4 "-and triisocyanate; 1,3; 5-triisocyanate benzene; 2; 4,6-triisocyanate toluene; 1,3, triisocyanates such as 5-triisocyanate hexane, for example, can enumerate 4,4 '-phenylbenzene dimethylmethane-2,2 '-5, polyisocynate monomers such as 5 '-tetraisocyanate, the dimer of being derived by above-mentioned polyisocynate monomer, tripolymer, biuret, allophanate, has 2,4 a, 6-by what carbonic acid gas and above-mentioned polyisocynate monomer obtained The polyisocyanates of diazine triketone ring, for example, can enumerate ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 3,3 '-dihydroxymethyl heptane, cyclohexanedimethanol, Diethylene Glycol, triethylene glycol, dipropylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, weight-average molecular weight such as Sorbitol Powder are lower than 200 low molecular weight polyols to the affixture of above-mentioned various isocyanic ester, for example, can enumerate above-mentioned molecular weight is 200～200000 polyester polyol, polyether glycol, polyester ether polylol, the polyesteramide polyvalent alcohol, polycaprolactone polyol, poly-valerolactone polyvalent alcohol, acrylic polyol, polycarbonate polyol, poly-hydroxyl alkane, Viscotrol C, polyurethane polyols etc. are to affixture of above-mentioned various isocyanic ester etc.
(2) content
In addition, preferably making the content of the linking agent of conduct (B) composition is the interior value of scope of 0.05～5 weight part with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as (A) composition.
This reason is if the content of above-mentioned linking agent is the value that is lower than 0.05 weight part, then under the situation that cohesive force reduces by the additive with particular configuration that adds conduct (C) composition, is difficult to obtain sufficient adhesive, storage modulus sometimes.On the other hand, if the content of above-mentioned linking agent is for surpassing the value of 5 weight parts, then sometimes as the acrylate copolymer that contains bridging property functional group of (A) composition each other crosslinked excessively, on the contrary, bounding force reduces easily.
Therefore, more preferably making the content of the linking agent of conduct (B) composition is the interior value of scope of 0.05～3 weight part, the more preferably value in the scope of 0.1～1 weight part with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as (A) composition.
4. diluting solvent
Consider from the dispersiveness of improving each composition or the viewpoint that to coating adhesive compositions such as stripping films the time, is adjusted to suitable viscosity, can in binder composition of the present invention, use solvent.
As above-mentioned solvent, for example, aliphatic hydrocarbons such as preferred hexane, heptane, aromatic hydrocarbons such as toluene, dimethylbenzene, halohydrocarbon such as methylene dichloride, ethylene dichloride, alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, ketone such as acetone, methylethylketone, 2 pentanone, isophorone, pimelinketone, ester such as ethyl acetate, butylacetate, cellosolve series solvents such as ethyl cellosolve, glycol ethers series solvents such as propylene glycol monomethyl ether etc., the concentration of the binder composition when adding solvent are preferably the interior value of scope of 10～40 weight %.
5. additive
As other additive, preferably in binder composition, contain tackifier, antioxidant, UV light absorber, photostabilizer, tenderizer, weighting agent, high refractive index agent, diffusant, static inhibitor etc.
In addition, at this moment, even if depend on the kind of additive, also preferably making its content is the interior value of scope of 0.1～20 weight part with respect to acrylate copolymer 100 weight parts as (A) composition.
［ the 2nd embodiment ］
The 2nd embodiment of the present invention is a kind of adhesive sheet, it is characterized in that, it is the adhesive sheet that has the binder layer that comes from binder composition at base material, described binder composition contains the linking agent as the acrylate copolymer that contains bridging property functional group of (A) composition and conduct (B) composition, and binder composition contains organosilsesquioxanes compound conduct (C) composition with reactive group.
Below, with reference to Fig. 5, centered by the point different with the 1st embodiment, the 2nd embodiment of the present invention is specifically described.
1. binder layer
Binder composition can become the binder layer with predetermined characteristic via following operation (1)～(3).
(1) prepares to contain (A), (B) and (C) operation of the binder composition of the regulation of composition
(2) binder composition is applied on the stripping film, forms the operation of coating layer
(3) make binder composition cross-links, make coating layer become the operation of binder layer
Below, suitably with reference to accompanying drawing, to being specifically described until the operation that constitutes binder layer.
(1) operation (1) (preparatory process of binder composition)
Operation (1) is to prepare to contain (A), (B) and (C) operation of the binder composition of the regulation of composition.
More specifically, preferably (A) composition is diluted with diluting solvents such as for example ethyl acetate according to demand, stir and add (C) composition down, make uniform mixed solution.
In addition, preferably meanwhile, in mixed solution, add (B) composition, further add other additive according to demand after, the limit is stirred to evenly, the limit further adds diluting solvent as required until the viscosity that becomes demand, obtains the solution of binder composition thus.
Should illustrate that the detail of each composition and cooperation ratio are described like the 1st embodiment, therefore omit.
(2) operation (2) (painting process of binder composition)
Shown in Fig. 5 (a), operation (2) is that binder composition is applied to the operation that forms coating layer 1 on the stripping film 2.
As stripping film, for example, can enumerate the stripping film that film coating stripper is arranged peel ply, described film is polyester films such as polyethylene terephthalate, polybutylene terephthalate, PEN, polyolefin film such as polypropylene, polyethylene, described stripper are silicone resin, fluoro-resin, Synolac etc.
Should illustrate that the thickness of above-mentioned stripping film is preferably the value in 20～150 mu m ranges usually.
In addition, as coating adhesive method for compositions on stripping film, for example, preferred use rod is coated with method, scraper is coated with the binder composition that coatings such as method, rolling method, scraper plate coating method, mould coating method, intaglio plate coating method have added solvent, after forming coating layer (filming), make its drying.
At this moment, benchmark during according to drying, the thickness that preferably makes coating layer are the interior value of scope of 5～100 μ m, the more preferably value in the scope of 10～50 μ m, the more preferably value in the scope of 15～30 μ m.
This reason is if the thickness of coating layer is thin excessively, then can not get abundant adhesion characteristic sometimes, if opposite blocked up, then residual solvent becomes problem sometimes.
In addition, as drying conditions, usually, preferably at 50～120 ℃, in the scope of 10 second～10 minute.
(3) operation (3) (the crosslinked operation of coating layer)
Operation (3) is to make the coating layer of binder composition crosslinked, makes coating layer become the operation of binder layer.
That is, shown in Fig. 5 (b), preferably make base material 101 such as blooming be layered in the surface of the coating layer 1 of drying regime on the stripping film 2, make coating layer 1 crosslinked with this state, form binder layer 10.
Perhaps, also can make the coating layer of the binder composition that is coated with at stripping film crosslinked in advance, form binder layer after, stacked with base material such as blooming.
In addition, also preferred substrates is stripping film, and to the mode of exposing folded another stripping film of surface layer of binder layer.
Namely, as shown in Figure 6, also be preferably as follows the adhesive sheet 100b of formation, namely, to stripping film 2 coating adhesive compositions and make its drying, form coating layer 1 after, another stripping film 2 is layered on the coating layer 1, carry out crosslinkedly, the peel ply side with 2 stripping films 2 forms with the mode clamping that binder layer 10 joins respectively thus.
In addition, the adhesive sheet 100b of aforesaid way also can be the adhesive sheet that forms in the following way, namely, stripping film 2 is formed the coating layer 1 of binder composition, after making it dry and crosslinked, another stripping film 2 is layered on the binder composition that becomes binder layer 10, is formed by 2 stripping film 2 clampings thus.
In addition, the peeling force of the side in preferred 2 stripping films is different with the opposing party's peeling force.
This reason is by the peeling force difference, thereby when using the adhesive sheet obtain, can peel off a side stripping film with not damaging binder layer.
In addition, the adhesive sheet of aforesaid way can be by fitting on the base materials such as blooming with peeling off a side stripping film, make the binder layer driving fit of exposing, and obtaining with blooming etc. thus is the adhesive sheet of base material.
At this moment, according to demand, in order to improve the adaptation with base material, can carry out surface treatments such as corona treatment, Cement Composite Treated by Plasma and saponification processing to the tackiness agent aspect.
Aforesaid way is because the use of the manufacturing of binder layer and above-mentioned binder layer is to carry out etc. in different places, becomes necessary for the situation that must only carry binder layer etc.
In addition, as other mode, also can not be situated between by stripping film, directly form the coating layer of binder composition at base materials such as bloomings, obtain adhesive sheet thus.
At this moment, the face side of exposing of the coating layer of binder composition is protected when using by stacked stripping film after drying.
Should illustrate that crosslinked in the coating layer of binder composition undertaken by above-mentioned drying process and air-dry (seasoning) operation.
As the condition of above-mentioned air-dry operation, never coating layer, the base material to binder composition causes damage and makes the coating layer of binder composition carry out crosslinked equably viewpoint consideration, preferably is made as 20～50 ℃, more preferably is made as 23～30 ℃.
In addition, as humidity, preferably be made as 30～75%RH, more preferably be made as 45～65%RH.
And, as during, preferably be made as 3～20 days, more preferably be made as 5～14 days.
(4) bounding force
In addition, be the polaroid of the band binder layer of polaroid about base material, preferably make being attached bounding force after 1 day by adherend (glass surface) for greater than 1N/25mm and smaller or equal to the value in the scope of 10N/mm.
This reason is that then the weather resistance under prescribed condition becomes insufficient sometimes if above-mentioned bounding force is the following value of 1N/25mm.On the other hand, if above-mentioned bounding force is for surpassing the value of 10N/25mm, then releasable excessively reduces sometimes.
Therefore, more preferably making the bounding force of the polaroid of band binder layer is greater than 2.5N/25mm and smaller or equal to the value in the scope of 8N/25mm, more preferably greater than 3.5N/25mm and smaller or equal to the value in the scope of 5.5N/25mm.
In addition, from same reason, preferably make being attached bounding force after 21 days by adherend for greater than 3N/25mm and smaller or equal to the value in the scope of 30N/25mm, more preferably greater than 4N/25mm and smaller or equal to the value in the scope of 20N/25mm, more preferably greater than 5N/25mm and smaller or equal to the value in the scope of 15N/25mm.
Should illustrate that the measuring method record of bounding force in an embodiment.
2. base material
In the present invention, preferably possessing above-mentioned binder layer and form adhesive sheet in the one side at least of base material.
As shown in Figure 5, as the base material 101 in the adhesive sheet 100 of the present invention, be not particularly limited, for example, preferably enumerate overlays such as polyvinyl alcohol, polyethylene terephthalate, triacetyl cellulose, polycarbonate, liquid crystalline polymers, cycloolefin, polyimide, polymeric amide, polyamidoimide, polyphenylene oxide, polyetherketone, polyether-ether-ketone, polysulfones, polyethersulfone, polyphenylene sulfide, polyarylester, acrylic resin, the polymkeric substance that contains the ester ring type structure, aromatic series based polymer.
In addition, if illustrate from the aspect of purposes, then preferably enumerate the blooming that uses in polaroid, polarizing layer protective membrane, field angle expansion film, antiglare film, polarizer etc., the liquid-crystal display etc.
For example, according to the present invention, even if base material is under the situation of polaroid, also can access the advantage that can suppress the generation of light leak effectively.
In addition, according to the present invention, because also can be to driving fits well such as polarizers, so will be as the containing that the iodine polyvinyl alcohol resin extends of the raw material of polaroid and the polarizer itself made also can become the base material 101 in the adhesive sheet 100 of the present invention.And the polarizer that the single face of polarizer is covered by protective membranes such as triacetyl cellulose, polyethylene terephthalates etc. becomes object too.
Should illustrate that the adhesive sheet when base material is polaroid is called the polaroid of being with binder layer.
In addition, be not particularly limited as the thickness of base material, be preferably the value in the scope of 1～1000 μ m usually.
This reason is that then physical strength, operability excessively reduce sometimes if the thickness of above-mentioned base material is lower than 1 μ m, perhaps is difficult to form uniform thickness.On the other hand, if the thickness of above-mentioned base material surpasses 1000 μ m, then operability excessively reduces sometimes, and is unfavorable to economy.
Therefore, the thickness that more preferably makes base material is the interior value of scope of 5～500 μ m, the more preferably value in the scope of 10～200 μ m.
Should illustrate that base material is under the situation of stripping film, be preferably the interior value of scope of 20～150 μ m usually.
In addition, consider from improving with the viewpoint of the adaptation of binder layer, preferably the face side of the formation coating layer of base material 101 is implemented surface treatment.
As this surface treatment, for example, can enumerate linging processing, corona treatment, flame treating, saponification processing etc., preferred especially linging is handled.
This reason is the base material that has formed this undercoat by use, and base material ground improves and the adaptation of binder layer thereby can not damage.
Should illustrate, as the material that constitutes this undercoat, can enumerate cellulose ester (for example, rhodia, cellulose acetate-propionate, cellulose acetate butyrate (CAB), nitrocellulose and their combination), polyacrylic acid, urethane, polyvinyl alcohol, polyvinyl ester, polyvinylacetal, polyvinyl ether, polyethylene ketone, polyvinyl carbazole, polyvinyl butyral acetal and their combination.
In addition, the thickness of undercoat also is not particularly limited, and usually, is preferably the interior value of scope of 0.05 μ m～10 μ m.
Should illustrate, fit in by the method for adherend as the adhesive sheet that will finally obtain, preferably shown in Fig. 5 (c)～(d), at first, peel ply is stacked in the stripping film 2 on the binder layer 10, then, the surface of the binder layer 10 that exposes is sealed at by adherend 200 fits.
Embodiment
Below, with reference to embodiment, further describe the present invention.
［ embodiment 1 ］
1. the preparation of binder composition
The binder composition that preparation is made of as the organosilsesquioxanes compound of (C) composition as the linking agent of (B) composition and 0.20 weight part as the acrylate copolymer with bridging property functional group of (A) composition, 0.15 weight part following 100 weight parts.
Should illustrate that the value that solids component converts has been carried out in the numeric representation in the table 1.
In addition, in the table 1, the weight part the when use level of monomer component refers to monomer component integral body as 100 weight parts.
In addition as the linking agent of (B) composition with the weight part when referring to (A) composition as 100 weight parts as the content of the organosilsesquioxanes compound of (C) composition.
(1) about (A) composition
Under nitrogen environment, in container, take in 99.0 weight parts as the n-butyl acrylate (BA) of monomer component (a), 1.0 weight parts as the vinylformic acid 4-hydroxyl butyl ester (4HBA) of monomer component (b), 0.3 weight part Diisopropyl azodicarboxylate and the 150 weight part ethyl acetate as polymerization starter.
Then, under 60 ℃, 8 hours condition, carry out polymerization, obtain the ethyl acetate solution as the acrylate copolymer of the weight-average molecular weight 1,500,000 of (A) composition.Should illustrate that the weight-average molecular weight of acrylate copolymer is to utilize gel permeation chromatography (below, abbreviate the GPC method as) to measure.
That is, at first, use polystyrene to make calibration curve.Below, weight-average molecular weight is with the polystyrene conversion value representation.Then, the concentration of determination objects such as preparation acrylate copolymer is tetrahydrofuran (THF) (THF) solution of 1 weight %, utilizes the GEL PER processed MEATION CHROMATOGRAPH HLC-8020(of TOSOH Co., Ltd. by TSK GELGMH XL, TSK GELGMH XL, TSK GELG2000 HXL3 columnss in series that constitute) measure weight-average molecular weight with the condition of 40 ℃, THF solvent, 1ml/ minute.And, use the TSK GUARD processed COLUMN of TOSOH Co., Ltd. as guard column.
(2) about (B) composition
Adding in the acrylic acid polymer solution with bridging property functional group of conduct (A) composition of solids component 100 weight parts that obtain converts with solids component counts isocyanate-based linking agent (TD-75) (Soken Chemical ﹠ Engineering Co., Ltd.'s system as (B) composition of 0.15 weight part, solids component 75 weight %, ethyl acetate solution).
(3) about (C) composition
Then, in the acrylic acid polymer solution with bridging property functional group of conduct (A) composition of solids component 100 weight parts, add when adding above-mentioned (B) composition conduct (C) composition of 0.20 weight part the organosilsesquioxanes compound I (HBSQ-105-7) that contains sulfydryl (Arakawa Chemical Industries, Ltd.'s system, n=12).
Then, evenly mix, become 20 weight % with the ethyl acetate dilution until solid component concentration, obtain binder composition solution.
2. the coating of binder composition solution
Then, to polyethylene terephthalate stripping film processed (the LINTEC Co., Ltd. system as the thickness 38 μ m of stripping film, SP-PET3811) lift-off processing face, be the binder composition solution that the mode of 25 μ m uses the coating of scraper type coating machine to obtain with dried thickness, form coating layer.
Then, to the coating layer that obtains 90 ℃ implement 1 minute drying treatment after, fit with the polaroid of thickness 180 μ m, with autoclave pressurization 20 minutes under 23 ℃, the condition of 0.5MPa, obtain the duplexer that coating layer and polaroid by binder composition constitute.
3. binder composition is air-dry
Then, the duplexer that obtains is placed 7 days (air-dry) under 23 ℃, the condition of 50%RH, make binder composition full cross-linked, obtain the polaroid of the band binder layer of embodiment 1.
4. estimate
(1) evaluation of bounding force
Measure respectively from fitted beginning by adherend after 1 day and the bounding force of the polaroid of the band binder layer after 21 days.
That is, use cutting device (wild Co., Ltd. of institute system, the SUPER CUTTER of making of reed), the polaroid severing of the band binder layer that obtains is become the size of width 25mm * length 100mm, make the mensuration sample.
Then, peel off stripping film from the mensuration sample that obtains after, be fitted in non-alkali glass (Corning Co., Ltd. system, EAGLE XG).
Then, the non-alkali glass of having measured sample with having fitted is put into autoclave (tremble Co., Ltd. of former makings institute system), and after pressurizeing 20 minutes under 0.5MPa, 50 ℃ the condition, placement is 1 day under 23 ℃, the condition of 50%RH.
Then, (ORIENTEC Co., Ltd. system TENSILON), is measured bounding force with following condition to measuring sample, estimates according to following benchmark to use tensile testing machine.With the table 1 that the results are shown in that obtains.
Peeling rate: 300mm/ minute
Peel angle: 180 °
◎: the value of bounding force is greater than 3.5 and smaller or equal to the value of 5.5N/25mm.
Zero: the value of bounding force is greater than 2.5 and smaller or equal to the value of 3.5N/25mm, perhaps is greater than 5.5 and smaller or equal to the value of 8.0N/25mm.
△: the value of bounding force is greater than 1.0 and smaller or equal to the value of 2.5N/25mm, perhaps is greater than 8.0 and smaller or equal to the value of 10.0N/25mm.
*: the value of bounding force is the following value of 1.0N/25mm, perhaps is the value greater than 10.0N/25mm.
In addition, after similarly will measuring sample and fitting in non-alkali glass, under 23 ℃, the condition of 50%RH, place 21 days (504 hours), measure the bounding force of this situation, estimate according to following benchmark.With the table 1 that the results are shown in that obtains.
◎: the value of bounding force is the value of 5.0～20N/25mm.
Zero: the value of bounding force is more than 3.0 and is lower than the value of 5.0N/25mm.
*: the value of bounding force is the value that is lower than 3.0N/25mm, perhaps is the value greater than 20N/25mm.
(2) Evaluation of Durability
The weather resistance of the polaroid of the band binder layer of evaluation under prescribed condition.
That is, use cutting device (wild Co., Ltd. of institute system, the SUPER CUTTER of making of reed), the polaroid severing of the band binder layer that obtains is become the size of 233mm * 309mm, make the mensuration sample.
Then, peel off stripping film from the mensuration sample that obtains after, fit in non-alkali glass (Corning Co., Ltd. system, EAGLE XG).
Then, the non-alkali glass of having measured sample with having fitted is put in the autoclave (tremble Co., Ltd. of former making institute system), in pressurization under 0.5MPa, 50 ℃ the condition after 20 minutes, after under drying, dropping under each durable condition of 80 ℃, 60 ℃/90%RH and thermal shocking (HS) condition (1 cycle is-35 ℃ (30 minutes)/70 ℃ (30 minutes)), placed 100 hours.
Then, use 10 times of magnifying glasses that the state of measuring sample is observed, according to following benchmark, estimate weather resistance.With the table 1 that the results are shown in that obtains.
◎: do not have the peeling of polaroid to peel off fully.
Zero: apart from having peeling to peel off below the 0.5mm of end.(be starting point with the end, do not have peeling to peel off in the position that surpasses 0.5mm)
△: apart from having peeling to peel off below the 1.0mm of end.(be starting point with the end, do not have peeling to peel off in the position that surpasses 1.0mm)
*: surpassing 1.0mm apart from the end has peeling to peel off.
In addition, after similarly will measuring sample and fitting in non-alkali glass, put in the autoclave (tremble Co., Ltd. of former making institute system), in pressurization under 0.5MPa, 50 ℃ the condition after 20 minutes, after under drying, dropping under each durable condition of 80 ℃, 60 ℃/90%RH and thermal shocking (HS) condition (1 cycle is-35 ℃ (30 minutes)/70 ℃ (30 minutes)), placed 500 hours.
Then, use 10 times of magnifying glasses that the state of measuring sample is observed, according to following benchmark, estimate weather resistance.With the table 1 that the results are shown in that obtains.
◎: do not have the peeling of polaroid to peel off fully.
Zero: apart from having peeling to peel off below the 0.5mm of end.
△: apart from having peeling to peel off below the 1.0mm of end.
*: surpassing 1.0mm apart from the end has peeling to peel off.
(3) evaluation of gel percentage ratio
Estimate the gel percentage ratio of binder composition.
Namely, operation according to above-mentioned " the 2. coating of binder composition solution ", coating adhesive composition on the peel ply of stripping film, 90 ℃ implement 1 minute heat treated after, replace polaroid and will (LINTEC Co., Ltd. system, SP-PET3801) mode of joining with its peel ply fits in coating layer as the polyethylene terephthalate stripping film processed of the thickness 38 μ m of another stripping film.
Then, the polaroid of band binder layer is placed 12 days (air-dry) and obtained adhesive sheet under 23 ℃, the condition of 50%RH.
Then, peel off the stripping film on the two sides of the adhesive sheet that obtains, the binder composition that takes out about 0.1g wraps into TETORON screen cloth (#200), employing with the ethyl acetate be solvent based on Soxhlet extraction element (Tokyo glass apparatus Co., Ltd. system, the fat extraction device) backflow, extract the non-gel component of binder composition, utilize and calculate gel percentage ratio with the ratio of initial mass.With the table 1 that the results are shown in that obtains.
(4) evaluation of haze value
Estimate the haze value of binder layer.
Namely, operation according to above-mentioned " the 2. coating of binder composition solution ", coating adhesive composition on the peel ply of stripping film, 90 ℃ implement 1 minute heat treated after, replace polaroid and will (LINTEC Co., Ltd. system, SP-PET3801) mode of joining with its peel ply fits in coating layer as the polyethylene terephthalate stripping film processed of the thickness 38 μ m of another stripping film.
Then, air-dry by carrying out under the condition same with the polaroid that obtains with binder layer the time, obtain adhesive sheet.
Then, peel off the stripping film on the two sides of the adhesive sheet that obtains, make the mensuration sample, use integrating sphere type light transmittance determinator (Japanese electric look Industrial Co., Ltd system, NDH-2000), based on JIS K7105, the mensuration sample that obtains is measured diffused transmission rate (Td%) and full light transmittance (Tt%), calculate haze value with following formula (3).With the table 1 that the results are shown in that obtains.
Haze value=(Td/Tt) * 100 (3)
［ embodiment 2～4 ］
In embodiment 2～4, make the content of the organosilsesquioxanes compound that contains sulfydryl of conduct (C) composition be respectively 0.1 weight part, 0.3 weight part and 1.0 weight parts with respect to 100 weight parts of the acrylate copolymer with bridging property functional group as (A) composition, in addition, make the polaroid of band binder layer similarly to Example 1, estimate.With the table 1 that the results are shown in that obtains.
［ embodiment 5～7 ］
In embodiment 5～7, to change to the organosilsesquioxanes compound I I(SQ-506(Arakawa Chemical Industries, Ltd. system that contains epoxy group(ing) as the organosilsesquioxanes compound that contains sulfydryl of (C) composition, n=10), and making addition separately is 0.10 weight part, 0.30 weight part and 1.00 weight parts with respect to 100 weight parts of the acrylate copolymer with bridging property functional group as (A) composition, in addition, make the polaroid of band binder layer similarly to Example 1, estimate.With the table 1 that the results are shown in that obtains.
［ comparative example 1 ］
In comparative example 1, do not add the organosilsesquioxanes compound that contains sulfydryl as (C) composition, in addition, make the polaroid of band binder layer similarly to Example 1, estimate.With the table 1 that the results are shown in that obtains.
［ comparative example 2 ］
In comparative example 2, to change to the organoalkoxysilane compound IV (KBM-803(Shin-Etsu Chemial Co., Ltd system) by formula (4) expression as the organosilsesquioxanes compound that contains sulfydryl of (C) composition), in addition, make the polaroid of band binder layer respectively similarly to Example 1, estimate.With the table 1 that the results are shown in that obtains.
Figure BDA00002674090100311
［ comparative example 3 ］
In comparative example 3, to change to the linear siloxanes oligomer compounds V(X-41-1805(Shin-Etsu Chemial Co., Ltd system as the condenses of the organoalkoxysilane compound of being represented by above-mentioned formula (4) as the organosilsesquioxanes compound that contains sulfydryl of (C) composition)), in addition, make the polaroid of band binder layer respectively similarly to Example 1, estimate.With the table 1 that the results are shown in that obtains.
Table 1
Figure BDA00002674090100321
Utilizability on the industry
More than, as describing in detail, according to the present invention, by in the acrylate copolymer that contains bridging property functional group, containing linking agent and have the organosilsesquioxanes compound of ad hoc structure with the regulation ratio, thereby obtain doing over again property and the excellent in te pins of durability under the regulation environment and to the binder composition of the excellent corrosion resistance of metal.
Therefore, can expect that it is high-qualityization of the various films of representative that binder composition of the present invention etc. obviously helps the blooming with liquid crystal indicator, plasm display device, Organnic electroluminescent device, inorganic EL device etc.

Claims (9)

1. a binder composition is characterized in that, be to contain as the acrylate copolymer that contains bridging property functional group of A composition with as the binder composition of the linking agent of B composition,
Contain have reactive group the organosilsesquioxanes compound as the C composition.
2. binder composition according to claim 1 is characterized in that, is the organosilsesquioxanes compound that contains sulfydryl as the organosilsesquioxanes compound with reactive group of described C composition.
3. binder composition according to claim 1, it is characterized in that the content that makes described organosilsesquioxanes compound is value in 0.001～1.5 weight part scope with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as described A composition.
4. binder composition according to claim 1 is characterized in that, as the acrylate copolymer that contains bridging property functional group of described A composition for from the polymkeric substance as following (a)～(c) composition of monomer component,
(a) have (methyl) alkyl acrylate that carbonatoms is 1～20 alkyl: 100 weight parts,
What (b) intramolecularly had a hydroxyl contains the unsaturated double-bond compound: 0.5～10 weight part,
What (c) intramolecularly had a carboxyl contains the unsaturated double-bond compound: 0 weight part or 0～0.1 weight part, wherein, 0 weight part refers to not contain.
5. binder composition according to claim 1, it is characterized in that, linking agent as described B composition is the isocyanate-based linking agent, and making its content is value in 0.05～5 weight part scope with respect to the acrylate copolymer that contains bridging property functional group 100 weight parts as the A composition.
6. binder composition according to claim 1 is characterized in that, further contains static inhibitor as the D composition.
7. an adhesive sheet is characterized in that, is the adhesive sheet that has the binder layer that comes from binder composition at base material, and described binder composition contains as the acrylate copolymer that contains bridging property functional group of A composition with as the linking agent of B composition,
Described binder composition contain have reactive group the organosilsesquioxanes compound as the C composition.
8. adhesive sheet according to claim 7 is characterized in that, described base material is blooming, and is equipped with described binder layer at least one mask of this blooming.
9. adhesive sheet according to claim 7 is characterized in that, described base material is stripping film, and at stacked other stripping film of the one side opposite with this stripping film of described binder layer.
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