CN103360997A - Adhesive composition, adhesive, and adhesive sheet - Google Patents

Adhesive composition, adhesive, and adhesive sheet Download PDF

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Publication number
CN103360997A
CN103360997A CN2013101116053A CN201310111605A CN103360997A CN 103360997 A CN103360997 A CN 103360997A CN 2013101116053 A CN2013101116053 A CN 2013101116053A CN 201310111605 A CN201310111605 A CN 201310111605A CN 103360997 A CN103360997 A CN 103360997A
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Prior art keywords
tackiness
methyl
poly
hydride compounds
agent layer
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CN2013101116053A
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CN103360997B (en
Inventor
小泽祐树
又野仁
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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/005—Diaphragms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Abstract

An adhesive composition, an adhesive, and an adhesive sheet are suitable for optical components such as a polarized sheet and have excellent stress relaxation property. The adhesive composition comprises monomer units which form a polymer, a (methyl) acrylate polymer (A) which has carboxyl-contained monomers and has weight-average molecular weight of being 500,000 to 3 million, and a reactive polyrotaxane compound (B) containing cyclic oligosaccharide having polymerized double bonds.

Description

Tackiness composition, tackiness agent and adhesive sheet
Technical field
The present invention relates to the tackiness composition, tackiness agent (tackiness composition sclerosis material) and adhesive sheet particularly, relate to the tackiness composition, tackiness agent and the adhesive sheet that are suitable for as the used for optical part of polaroid etc.
Background technology
In general, in the liquid crystal panel, polaroid and polarizer at the glass substrate of liquid crystal cells etc. then, the adhering agent layers that formed by adhesion agent composition that use more.But, the optics of polaroid and polarizer etc. can be because contractions such as heat, because the generation of the contraction of thermal distortion, its result, the adhering agent layer of this optics superimposed layer can not be followed this contraction, thereby peel off (what is called is floated, and peels off) at generation of interfaces, the optic axis of the optics that the stress the during contraction of optics causes depart from the problem that light leak (so-called hickie) can occur.
As the method that it is prevented, (1) with having suitable clinging power, and, the optics of the adhering agent layer that the mode stability is good and polaroid etc. is fitted, thereby the method that the contraction self of optics is suppressed, the method of the adhering agent layer that perhaps, the stress of (2) use when the contraction of optics is little etc.As the method for (1), the use of the adhering agent layer that the disclosed such storage elastic modulus of patent documentation 1 is high is effective.On the other hand, as the method for (2), it is effective that use can be carried out the flexibly corresponding good adhering agent layer of stress relaxation to the distortion of optics.But in the past, the occasion of the adhering agent layer that such stress relaxation is good must be established the cross-linking density in the adhering agent layer low.Thus, can make the cohesive force step-down of adhering agent layer self, the weather resistance variation.
Therefore, in patent documentation 2-4, not to establish the cross-linking density of adhering agent layer low, but with plasticizer, Liquid Paraffin, polyurethane elastomers etc. add in the acrylic acid series tackiness agent, and the adhesion agent composition that obtains thus has appropriate flexibility, give the adhering agent layer stress relaxation, obtain thus anti-light leak and weather resistance.
[look-ahead technique document]
[patent documentation]
[patent documentation 1] TOHKEMY 2006-235568 communique
[patent documentation 2] Japanese kokai publication hei 5-45517 communique
[patent documentation 3] Japanese kokai publication hei 9-137143 communique
[patent documentation 4] TOHKEMY 2005-194366 communique
But such as the adhesion agent composition that plasticizer or Liquid Paraffin added, the adhering agent layer of formation has the problem of oozing out along with time plasticizer and Liquid Paraffin.And then, thus, then weather resistance step-down, to-be-adhered object and contaminated etc. the various worries of liquid crystal cells.In addition, add the adhesion agent composition of polyurethane elastomer, keep intermiscibility, the addition of polyurethane elastomer has the upper limit.Thus, in the adhering agent layer that from then on adhesion agent composition obtains, stress relaxation be improved as insufficient and tendency.Further, for the stress relaxation raising, and strengthen the addition of polyurethane elastomer, still, the acrylic acid series tackiness agent and the intermiscibility step-down, the problem of hickie etc. can occur.So, in technology in the past, it is difficult that the stress relaxation that the adhering agent layer that adhesion agent composition forms is arranged of used for optical part is carried out basic improvement.
The present invention forms according to such actual state.Purpose of the present invention just provides a kind of optics that is suitable for polaroid etc., the tackiness composition that stress relaxation is good, tackiness agent and adhesive sheet.
Summary of the invention
Purpose of the present invention can be reached with following technical scheme:
1. tackiness composition is characterized in that comprising: as the formation monomer unit of polymkeric substance, contain monomer with carboxyl, weight average molecular weight is (methyl) acrylic ester polymer (A) of 500,000-3,000,000; With
The poly-wheel of the reactivity hydride compounds (B) that contains the cyclic oligosaccharide with the two keys of polymerizability as ring molecule.
The tackiness agent that above-mentioned 1 tackiness composition sclerosis obtains, has the three-dimensional mesh structure that the poly-wheel hydride compounds (B) of the reactivity that contains the mechanical keys that moves freely at straight chain shape molecule as ring molecule forms, insert with a plurality of (methyl) acrylic ester polymers (A), form together crosslinked configuration like the plan restrained between the polymkeric substance, because this structure can be so that the good stress relaxation of the tackiness agent that arrives performance.In addition, above-mentioned (methyl) acrylic ester polymer (A) by to contain carboxylic monomer as component unit, can insert in above-mentioned three dimensional network order structure well.
2. above-mentioned 1 described tackiness composition is characterized in that: the two keys of the polymerizability that the cyclic oligosaccharide of described reactivity poly-wheel hydride compounds (B) has are contained in by isocyanic ester and import in (methyl) acryl of described cyclic oligosaccharide.
3. above-mentioned 1,2 described tackiness compositions, it is characterized in that: described reactivity poly-wheel hydride compounds (B) be by, will contain functional group's cyclic oligosaccharide as ring-type ring molecule (b1) with contain sub stituent with above-mentioned functional group and contain compound (b1) with the two keys of the polymerizability with functional group and obtain.
The two keys of described polymerizability contain the amount of compound (b2), and the described functional group to described poly-wheel hydride compounds (b1) is 10-60mol%.
4. above-mentioned 1 described tackiness composition is characterized in that: to described (methyl) acrylic ester polymer (A) 100 mass parts, the amount of described reactivity poly-wheel hydride compounds (B) is the 5-60 mass parts.
5. above-mentioned 1 described tackiness composition is characterized in that: described (methyl) acrylic ester polymer (A), as the formation monomer unit of described polymkeric substance, contain the monomer 1-30 quality % with described carboxyl.
6. above-mentioned 1 described tackiness composition, it is characterized in that: described tackiness composition further has Photoepolymerizationinitiater initiater (C).
7. above-mentioned 6 described tackiness compositions is characterized in that: the amount of described Photoepolymerizationinitiater initiater (C) to the poly-wheel of described reactivity hydride compounds (B) 100 mass parts, is the 1-15 mass parts.
8. tackiness agent, it makes it sclerosis and forms for by shine each described tackiness composition of above-mentioned 1-7 with active energy beam.
In the foregoing invention (invention 8), the irradiation dose of described active energy ray is with 10～1000mJ/cm 2For preferably.
9. an adhesive sheet comprises base material and adhering agent layer, it is characterized in that: described adhering agent layer is made of above-mentioned 8 described tackiness agents.
10. above-mentioned 9 described adhesive sheets, it is characterized in that: described base material is optics.
11. an adhesive sheet comprises 2 pieces of stripping films and the adhering agent layer that is joined with the release surface of described 2 pieces of stripping films therefrom by described stripping film clamping, it is characterized in that: described adhering agent layer is comprised of above-mentioned 8 described tackiness agents.
[effect of invention]
The tackiness agent that tackiness composition sclerosis of the present invention obtains, irradiation by active energy beam, the poly-wheel of a plurality of reactivities hydride compounds, bonding becomes three dimensional network order structure between its ring molecule, in this three-dimensional mesh structure, a plurality of (methyl) acrylic ester polymers inserts, and is restrained between the polymkeric substance, between this polymkeric substance, crosslinked configuration forms (inferring) like the plan.At this, poly-wheel hydride compounds has the mechanical keys that its ring molecule moves freely at straight chain shape molecule, and above-mentioned three-dimensional mesh is configured to contain the thing of this mechanical keys.Contain such machinery key three-dimensional mesh structure and intend like the structure that makes up of crosslinked configuration, can be so that the tackiness agent that arrives be brought into play good stress relaxation.In addition, above-mentioned (methyl) acrylic ester polymer by to contain carboxylic monomer as component unit, can insert in above-mentioned three dimensional network order structure well.
In addition, tackiness composition of the present invention is by the irradiation with active energy beam, during the firm formation of adhering agent layer, the sclerosis of tackiness agent has in fact just been finished, and described maturation just becomes not to have been needed, in addition, during the firm formation of adhering agent layer, all physical property of tackiness agent just become stable.Thus, have the dispatching from the factory and drop into to inferior operation and just can promptly carry out of parts of the adhering agent layer that is formed by this tackiness agent, this stock to middle material bears and production efficiency is very favorable.
Description of drawings
The sectional view of the adhesive sheet of the embodiment of Fig. 1 the of the present invention the 1st.
The sectional view of the adhesive sheet of the embodiment of Fig. 2 the of the present invention the 2nd.
The presentation graphs of the measurement result (FT-IR spectrum) of the fourier-transform infrared spectrophotometer of the reactivity of Fig. 3 embodiment 1 poly-wheel hydride compounds (B).
Embodiment
Below, to the explanation of embodiments of the present invention.
(tackiness composition)
The tackiness composition of present embodiment is (hereinafter referred to as " tackiness composition P ".) comprise, the weight average molecular weight (Mw) that contains the monomer (containing carboxylic monomer) with carboxyl as the component unit of polymkeric substance be (methyl) acrylic ester polymer (A) of 500,000-3,000,000 (below, the occasion that only claims " polymkeric substance (A) " is arranged.) and the poly-wheel of the reactivity hydride compounds (B) that has the cyclic oligosaccharide of the two keys of polymerizability as containing of ring molecule, preferred, further contain Photoepolymerizationinitiater initiater (C).In addition, in this specification sheets, so-called (methyl) acrylate refers to two sides of acrylate and methacrylic ester.Other similar term too.In addition, the concept that also contains " multipolymer " in " polymkeric substance ".
Above-mentioned tackiness composition P, the pre-irradiation of active energy beam (crosslinked) reaction of not hardening, so process easily, coating is good.As tackiness composition P being carried out the active energy beam irradiation, the poly-wheel of a plurality of reactivities hydride compounds (B) will form rapidly the following three-dimensional mesh structure that contains mechanical key.A plurality of (methyl) acrylic ester polymer (A) inserts this three-dimensional mesh structure, and is restrained, crosslinked configuration (inferring) like formation is intended between the polymkeric substance (A).By above-mentioned contain the three-dimensional mesh structure of mechanical keys and intend like crosslinked configuration composite construction (hereinafter referred to as " structure X "), the tackiness agent that obtains, when having sufficient cohesive force, can bring into play very good stress relaxation again, specifically, as following, both had suitable gel fraction, demonstrate again high elongation at break.In addition, above-mentioned (methyl) acrylic ester polymer (A) can insert in the above-mentioned three-dimensional mesh structure thus well by containing carboxylic monomer as component unit.
In addition, the sclerosis of the tackiness composition P that irradiation by active energy beam forms, in the firm formation of the irradiation of active energy beam, in fact just finished, so the maturation after adhering agent layer forms does not need, in addition, from the firm formation of adhering agent layer, all physical property of the clinging power of tackiness agent etc. will become stable.
(methyl) acrylic ester polymer (A) is for to contain carboxylic monomer as the polymkeric substance of necessary constituent.Polymkeric substance (A) has carboxyl, so good with the intermiscibility of following reactivity poly-wheel hydride compounds (B).
As containing carboxylic monomer, can exemplified by acrylic, methacrylic acid, β-crotonic acid, toxilic acid, methylene-succinic acid is twisted the ethene unsaturated carboxylic acid of health acid etc.They may be used alone, two or more kinds can also be used in combination.
In addition, (methyl) acrylic ester polymer (A), in order to obtain tackiness, as the unit of the formation of this polymkeric substance, the carbon number that preferably contains alkyl is (methyl) alkyl acrylate of 1-20.Carbon number as alkyl is (methyl) alkyl acrylate of 1-20, can exemplify (methyl) methyl acrylate, (methyl) vinylformic acid ethyl ester, (methyl) vinylformic acid propyl diester, (methyl) vinylformic acid n-butyl ester, (methyl) vinylformic acid n-amyl group ester, (methyl) vinylformic acid n-polyhexamethylene, (methyl) 2-ethylhexyl acrylate, (methyl) isooctyl acrylate ester, (methyl) vinylformic acid n-certain herbaceous plants with big flowers base ester, (methyl) vinylformic acid n-dodecyl ester, (methyl) vinylformic acid myristyl ester, (methyl) vinylformic acid palmityl ester, (methyl) stearyl acrylate base ester etc.Wherein, preferred take the carbon number of alkyl as (methyl) alkyl acrylate of 4-8 from the further viewpoint of degree of raising of tackiness, (methyl) vinylformic acid n-butyl ester or (methyl) 2-ethylhexyl acrylate are for particularly preferably.In addition, they may be used alone, two or more kinds can also be used in combination.
(methyl) acrylic ester polymer (A), the above-mentioned carbon number that contains carboxylic monomer and alkyl are beyond (methyl) alkyl acrylate of 1-20, only otherwise damage effect of the present invention, can be aptly with other monomer as component unit.
As above-mentioned other monomer, can be the monomer (containing the reactive functional monomer) with the reactive functional group beyond the carboxyl, also can be non-reactive monomeric.As containing the reactive functional monomer, can be the monomer (hydroxyl monomer) that molecule contains hydroxyl, also can be to have amino monomer (emulsion stability) etc. in the molecule, they can a kind of independent use, and use also can combine more than two kinds.
As the hydroxyl monomer, can exemplify (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 2-hydroxybutyl ester, (methyl) vinylformic acid 3-hydroxybutyl ester, (methyl) vinylformic acid hydroxyalkyl acrylate of (methyl) vinylformic acid 4-hydroxybutyl ester etc. etc.They may be used alone, two or more kinds can also be used in combination.
As emulsion stability, can exemplify (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid n-butyl amino-ethyl ester etc.They may be used alone, two or more kinds can also be used in combination.
As non-reacted monomer, can exemplify (methyl) vinylformic acid methoxymethyl ester, (methyl) vinylformic acid methoxy ethyl ester, (methyl) vinylformic acid ethoxyl methyl ester, (methyl) acrylate that contains alkoxyalkyl of (methyl) vinylformic acid ethoxyethyl group ester etc.; (methyl) acrylate with aliphatics ring of (methyl) vinylformic acid cyclohexyl etc. has (methyl) acrylate of the aromatic ring of (methyl) vinylformic acid phenyl etc.; Acrylic acid amides, the acrylic acid amides of the non-crosslinked of Methacrylamide etc.; (methyl) vinylformic acid N, N-dimethyl aminoethyl, (methyl) vinylformic acid N, (methyl) acrylate with tertiary amine groups of the non-crosslinked of N-dimethylaminopropyl etc.; Vinyl acetate between to for plastic base ester, vinylbenzene etc.They may be used alone, two or more kinds can also be used in combination.
As (methyl) acrylic ester polymer (A), as the unit that this polymkeric substance consists of, contain the above-mentioned carboxylic monomer 1-30 quality % that contains for preferred, particularly 3-25 quality % contains promising preferably, further contains promising preferred with 5-20 quality %.As containing carboxylic monomer in above-mentioned scope, (methyl) acrylic ester polymer (A) improves with the poly-intermiscibility of taking turns hydride compounds (B) of reactivity, can insert well in the three-dimensional mesh that reactivity poly-wheel hydride compounds (B) forms is constructed.The amount that contains carboxylic monomer as be 1 quality % less than, above-mentioned structure X can not form well, has the occasion that can not fully obtain cohesive force.On the other hand, contain the amount of carboxylic monomer as surpassing 30 quality %, the re-using property of the tackiness agent that obtains has the possibility of step-down.
(methyl) acrylic ester polymer (A), component unit as this polymkeric substance, (methyl) alkyl acrylate 30-99 quality % take the carbon number that contains alkyl as 1-20 is as preferred, particularly to contain 50-98 quality % for preferred, further with 70-95 quality % contain promising preferably.As the amount 30 quality % of above-mentioned (methyl) alkyl acrylate less than, clinging power had low outer possibility.On the other hand, the amount of above-mentioned (methyl) alkyl acrylate is as surpassing 99 quality %, and the above-mentioned use level that contains carboxylic monomer has not enough occasion.
The polymerization state of (methyl) acrylic ester polymer (A), randomcopolymer also can, segmented copolymer also can.
The weight average molecular weight of (methyl) acrylic ester polymer (A) is 500,000-300, is preferably 600,000-2,500,000, particularly is preferably 800,000-2,000,000.In addition, the weight average molecular weight in this specification sheets is to use the value of the polystyrene conversion of gel permeation chromatography (GPC) method mensuration.
As the weight average molecular weight of (methyl) acrylic ester polymer (A) be 500,000 less than, the weather resistance of the tackiness agent that obtains and re-using property have the possibility of variation.In addition, surpass 3,000,000 such as the weight average molecular weight of (methyl) acrylic ester polymer (A), in the time of with the intermiscibility variation of reactivity poly-wheel hydride compounds (B), the stress relaxation of the tackiness agent that obtains has the possibility of step-down.
Then, tackiness composition P is to contain reactive poly-wheel hydride compounds (B) as feature.The reactivity of present embodiment is gathered rotaxane (B), irradiation by active energy beam, and the reactive poly-rotaxane of sclerosis, at least also be to have straight chain shape molecule to connect in 2 the peristome of ring molecule, and, two ends of straight chain shape molecule have END CAPPED GROUP, as ring molecule, have the cyclic oligosaccharide of the two keys of polymerizability.
In the above-mentioned reactivity poly-wheel hydride compounds (B), ring molecule is for can move freely on straight chain shape molecule, because END CAPPED GROUP, ring molecule is not for going out structure from straight chain molecule order.That is, straight chain shape molecule and ring molecule are not the chemical bonds of covalent linkage etc., but keep its structure by the key of so-called machinery.As this reactive poly-wheel hydride compounds (B) is carried out the active energy beam irradiation, a plurality of reactivities is gathered wheel hydride compounds (B), the cracking of the two keys of the polymerizability that in ring molecule, exists, and between the mutual bonding of ring molecule, three-dimensional mesh structure is formed.Reactive poly-wheel hydride compounds (B) is by having above-mentioned mechanical keys, and the three-dimensional mesh structure of formation also contains this mechanical keys, can bring into play high stress relaxation.
As the ring molecule of reactivity poly-wheel hydride compounds (B), by using cyclic oligosaccharide, can select the ring footpath aptly, thus, will obtain on the straight chain shape molecule effect that ring molecule moves.In addition, because cyclic oligosaccharide has hydroxyl, utilize this hydroxyl, or utilize the substituting group that reacts with this hydroxyl and import etc., it is easy that the importing of the two keys of polymerizability becomes.Further, also there is cyclic oligosaccharide to hold facile advantage.In addition, in this specification sheets, " ring-type " of " ring molecule " or " cyclic oligosaccharide " is the meaning of " ring-type " in fact.That is, as long as can move on straight chain shape molecule, ring molecule is not that the ring of complete closed is also passable, can exemplify to be spiral structure.
As cyclic oligosaccharide, preferred alpha-cylodextrin, beta-cyclodextrin, the cyclodextrin of γ-cyclodextrin etc., wherein, particularly alpha-cylodextrin is preferred.The ring molecule of reactive poly-wheel hydride compounds (B) mixes more than 2 kinds in reactivity poly-wheel hydride compounds (B) or in the adhesion agent composition and also can.
The poly-wheel of the reactivity hydride compounds (B) that has the two keys of polymerizability in the ring molecule, the poly-wheel hydride compounds (b1) that contains the cyclic oligosaccharide with functional group as ring molecule reacts with the substituent polymerizability double bond compound (b2) that contains that has with above-mentioned functional group's reaction, can be obtained well.Above-mentioned poly-wheel hydride compounds (b1) can obtain with known method (can exemplify the described method of TOHKEMY 2005-154675) in the past.
As the functional group with cyclic oligosaccharide, can exemplify hydroxyl, carboxyl, amino, substituted-amino, epoxy group(ing) etc. are wherein take hydroxyl as preferred.Hydroxyl, the hydroxyl that cyclic oligosaccharide initial (state before modifying) contains is also passable, as substituting group be imported in the cyclic oligosaccharide hydroxyl also passable.Functional group beyond the hydroxyl, the reaction that can be undertaken by the hydroxyl that initially has with cyclic oligosaccharide imports in the cyclic oligosaccharide.
In addition, above-mentioned functional group is, in cyclic oligosaccharide, between substituting group exist also can, further, between the hydroxyl that initially has of cyclic oligosaccharide, the substituting group bonding that 2 different kinds are above has a functional group also passable in the substituting group of wherein any.
As above-mentioned substituting group, can exemplify ethanoyl, alkyl, trityl, p-toluenesulfonyl, TMS, phenyl etc.In addition, can exemplify polyester chain, oxyethylene chain, alkyl chain, ether chain, ester chain, acrylate chains etc.Substituent molecular weight (perhaps number-average molecular weight), with 100-10,000 is preferred, particularly with 400-2,000 is preferred.Above-mentioned substituent importing rate (substitution value) to the hydroxyl of cyclic oligosaccharide is, take 10-90% as preferred, particularly take 30-70% for preferably.
On the other hand, have the substituting group that contains polymerizability double bond compound (b2), the functional group's that can have according to the ring molecule of poly-wheel hydride compounds (b1) kind suits to select.For example the functional group is hydroxyl, the occasion of amino or substituted-amino, and as substituting group, isocyanate group or epoxy group(ing) are preferred; Be the occasion of carboxyl the functional group, with '-aziridino, epoxy group(ing) or azoles quinoline base are preferred as substituting group; The functional group is the occasion of epoxy group(ing), and as amino, carboxyl or '-aziridino are preferred as substituting group.Such substituting group is to contain in per 1 molecule of polymerizability double bond compound (b2) and contain one.
Contain in addition in the polymerizability double bond compound (b2), the two keys (carbon-to-carbon double bond) of polymerizability are that per 1 molecule contains 1-5 usually, preferably contains 1-2.As such polymerizability double bond compound (b2) that contains, can exemplify methylacryoyloxyethyl isocyanic ester, methyl isopropyl thiazolinyl alpha, alpha-dimethylbenzyl isocyanic ester, methacryloyl based isocyanate, allyl group isocyanic ester; Diisocyanate cpd or polyisocyanate compounds and, the acryl monoisocyanates compound that further obtains in the reaction of hydroxyethyl (methyl) acrylate; The acryl monoisocyanates compound that the reaction of diisocyanate cpd or polyisocyanate compounds and polyalcohols compound and hydroxyethyl (methyl) acrylate obtains; Diepoxy glycerine (methyl) acrylate; (methyl) vinylformic acid, the 2-(1-aziridine) ethyl (methyl) acrylate, 2-vinyl 2-azoles quinoline, 2-pseudoallyl 2-azoles quinoline etc.
As containing polymerizability double bond compound (b2); among above-mentioned; has isocyanate group as substituting group; as the base that contains the two keys of polymerizability; the base that preferably contains the two keys of ethene, particularly take compound with (methyl) acryl for preferably, specifically; with (methyl) acrylyl oxy-ethyl isocyanic ester, particularly take the methylacryoyloxyethyl isocyanic ester as preferred.
Contain polymerizability double bond compound (b2), to the above-mentioned functional group of poly-wheel hydride compounds (b1), with 10-60mol%, particularly with 15-50mol%, further use as preferred take the amount of 20-40mol%.
In addition, contain polymerizability double bond compound (b2) and be, cyclic oligosaccharide 1 molecule to poly-wheel hydride compounds (b1) consists of is preferably the 0.01-10 molecule, 0.05-5 molecule more preferably, and the amount that is particularly preferably the 0.5-2 molecule is carried out addition.
Poly-wheel hydride compounds (b1) and contain the reaction of polymerizability double bond compound (b2) is generally normal pressure, and reactive atmosphere does not enclose under the gas, in room temperature or 40-70 ℃ heat, carries out 12-48 hour degree in the organic solvent of acetic acid ethyl etc.During reaction, catalyst and polymerization can be forbidden the uses that suit such as agent.For example, the functional group that ring molecule has for the poly-wheel hydride compounds (b1) of hydroxyl and, substituting group is the occasion of the reaction that contains polymerizability double bond compound (b2) of isocyanate group, the catalyst that the organotin of dibutyl tin lauryl etc. is is preferred.In addition, according to functional group and substituent combination, the temperature of reaction, pressure, solvent, the time, the having or not of catalyst, the kind of catalyst can suit to select.Thus, the functional group who exists in the ring molecule of poly-wheel hydride compounds (b1) and the substituting group that contains in the polymerizability double bond compound (b2) react, and the reactivity poly-wheel hydride compounds (B) that the two keys of polymerizability are imported in the ring molecule can be obtained.Functional group and substituent reactivity in this reaction be, and be common more than 70%, is preferably more than 80%, and unreacted functional group is remaining also passable in the ring molecule of reactivity poly-wheel hydride compounds (B).
The straight chain shape molecule of reactive poly-wheel hydride compounds (B), as being encircled in the cyclic oligosaccharide of ring molecule, not by the chemical bond of covalent linkage etc., but with the integrated molecule of mechanical keys or material, so long as the thing of straight chain shape, just there is no particular limitation.In addition, in this specification sheets, " straight chain " of " straight chain shape molecule " be, in fact the meaning of " straight chain ".That is, as long as ring molecule can move on straight chain shape molecule, straight chain shape molecule also can have branched chain.
Straight chain shape molecule as reactivity poly-wheel hydride compounds (B) can preferably exemplify polyoxyethylene glycol, polypropylene glycol, polyisoprene, polyisobutene, polyhutadiene, polytetrahydrofuran, polyacrylic ester, polydimethylsiloxane, polyethylene, polypropylene etc., these straight chain shape molecules are to mix more than 2 kinds in adhesion agent composition and also can.
The number-average molecular weight of the straight chain shape molecule of reactive poly-wheel hydride compounds (B) is, with 3,000-300,000 be preferred, and particularly with 10,000-200,000 is that preferably further with 20,000-100,000 is preferred.Number-average molecular weight as 3,000 less than, the amount of movement of ring molecule on straight chain shape molecule is little, the stress relaxation of tackiness agent has inadequate possibility.In addition, number-average molecular weight is as surpassing 300,000, to the solvability of the solvent of reactivity poly-wheel hydride compounds (B) and with the intermiscibility of following (methyl) acrylic ester polymer (A) bad possibility arranged.
The END CAPPED GROUP of reactive poly-wheel hydride compounds (B), as long as can keep ring molecule to be conspired to create the mode of shape by straight chain shape molecule, there is no particular limitation.As such base, can exemplify macoradical, ionic base etc.
Specifically, the END CAPPED GROUP of reactive poly-wheel hydride compounds (B) is two nitrated phenyl classes, cyclodextrin, Buddha's warrior attendant base class, trityl class, fluoresceins, pyrene class, anthracene class etc., perhaps, number-average molecular weight 1,000-1,000,000 high molecular main chain or side chain etc. are preferred, and these END CAPPED GROUP are, in the reactive poly-wheel hydride compounds (B) or in the adhesion agent composition, mix more than 2 kinds and also can.
As above-mentioned number-average molecular weight 1,000-1,000,000 polymer can exemplify, polymeric amide, imide, urethane, polydimethylsiloxane, polyacrylic ester etc.
Straight chain shape molecule by the ring molecule more than 2 with the maximum amount of encircling of the ring molecule of string thorn-like when encircling as 100% occasion, the amount of encircling of ring molecule is, is preferably 0.1-60%, particularly is preferably 1-50%, more preferably 5-40%.
In addition, the maximum amount of encircling of ring molecule comes Decision fixed by the length of straight chain shape molecule and the thickness of ring molecule.For example, straight chain shape molecule is polyoxyethylene glycol, and ring molecule is the occasion of alpha-cylodextrin molecule, and the maximum amount of encircling is, with ask (Macromolecules1993,26, the 5698-5703 reference) of experiment.
Reactivity described above is gathered rotaxane (B), among the tackiness composition P, a kind of independent use also can, 2 kinds combine to use and also can.
The amount of the poly-wheel hydride compounds of the reactivity in the adhesion agent composition of present embodiment (B) is, to (methyl) acrylic ester polymer (A) 100 mass parts, take the coating of 5-60 mass parts as preferred, particularly take the 7-45 mass parts as preferred, further take the 10-30 mass parts as preferred.The tackiness agent that the tackiness composition P of (methyl) acrylic ester polymer (A) and reactive poly-wheel hydride compounds (B) obtains from contain above-mentioned amount can form the thing (inferring) with above-mentioned structure X well.
In addition, the amount of reactive poly-wheel hydride compounds (B) as be 5 mass parts less than the time, the growing amount of the structure X that this reactivity poly-wheel hydride compounds (B) obtains is very few, having gel fraction is step-down, the inadequate possibility of cohesive force.On the other hand, when the amount of reactive poly-wheel hydride compounds (B) surpasses 60 mass parts, the relative amount mistake of (methyl) acrylic ester polymer (A), the possibility of cohesively step-down.
At this, tackiness composition P irradiation active energy beam is being used in the ultraviolet occasion, tackiness composition P is further to contain Photoepolymerizationinitiater initiater (C) as preferred.So contain Photoepolymerizationinitiater initiater (C), reactive poly-wheel hydride compounds (B) can efficient harden well, and the irradiation dose of polymerization setting time and active energy beam can reduce in addition.
As such Photoepolymerizationinitiater initiater (C), specifically, can exemplify benzophenone, methyl phenyl ketone, benzoin, benzoin methyl ether, the benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, the benzoin M-nitro benzoic acid, benzoin M-nitro benzoic acid methyl, benzoin dimethyl ketal, 2,4-diethyl thioxanthone, the 1-hydroxycyclohexylphenylketone, the benzyl diphenyl sulfide, tetra methylthiuram list sulfide, azobis isobutyronitrile, benzyl, dibenzyl, diacetyl, β-chloroanthraquinone, (2,4,6-trimethyl benzyl phenylbenzene) phosphine oxide, 2-[4-morpholinodithio N, N-diethyldithiocarbamate etc.They may be used alone, two or more kinds can also be used in combination.
The amount of Photoepolymerizationinitiater initiater (C) is to the poly-wheel of reactivity hydride compounds (B) 100 mass parts, to be preferably the 1-15 mass parts, particularly preferred 2-10 mass parts.
Tackiness composition P further can contain silane coupling agent (D).As containing this silane coupling agent (D), the tackiness agent that obtains can degree of being improved to the adherence in the glass substrate.For example, (methyl) acrylic ester polymer (A) has the occasion of carboxyl as reactive functional group, the carboxyl reaction of the organic reaction base of silane coupling agent (D) etc. and (methyl) acrylic ester polymer (A), on the other hand, alkoxysilyl of silane coupling agent (D) etc. acts on the surface of the to-be-adhered object of glass substrate etc.Thus, such as the occasion that polaroid and liquid-crystalline glasses etc. are fitted, tackiness agent and liquid-crystalline glasses and between adherence can be further good.In addition, the reactive functional group of polymkeric substance (A) is, in the occasion beyond the carboxyl, the silane coupling agent (D) that has with the organic reaction base of this reactive functional group effect can be suitable the selection.
Be in molecule as silane coupling agent (D), have the silicoorganic compound of 1 alkoxysilyl at least, good with the intermiscibility of tackiness agent composition, and for the thing of photopermeability is arranged, for example transparent in fact thing is for suitable.The use level of such silane coupling agent (D) is to (methyl) acrylic ester polymer (A) 100 mass parts, for the 0.01-1.0 mass parts is preferred, particularly take the 0.05-0.5 mass parts as preferred.
As the concrete example of silane coupling agent (D), can the exemplified by vinyl Trimethoxy silane, vinyltriethoxysilane, the silicon compound that contains the polymerizability unsaturated group of methacryloyl propyl trimethoxy silicane etc.; The 3-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) silicon compound with epoxy structure of ethyl trimethoxy silane etc., the 3-TSL 8330, the N-(2-amino-ethyl)-the 3-TSL 8330, the N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane etc. contain amino silicon compound; The silicon compound that contains sulfydryl of 3-sulfydryl propyl trimethoxy silicane etc.; The haloalkyl containing silicon compound of 3-r-chloropropyl trimethoxyl silane etc.; The silane compound that contains isocyanate group of 3-isocyanic ester propyl-triethoxysilicane etc.; The hydrolyzate of above-mentioned silane compound; The cohydrolysis thing of the tetraalkoxysilane of above-mentioned silane compound and tetraethoxysilane etc. etc.They can use separately, also can 2 kinds of uses that combine.
Tackiness composition P is, preferably do not contain the linking agent that adhering agent layer forms the heat cross-linking system of after ripen necessity, and for example isocyanate-based linking agent and epoxy are linking agent for they.On the other hand, after preferred adhering agent layer forms, the linking agent that maturation is unnecessary, for example aziridine is linking agent.
Among the above-mentioned tackiness composition P, as required, can add the normally used various additives of acrylic acid series tackiness agent, for example adhesion invests agent, charged preventor, antioxidant, UV light absorber, light stabilizer, tenderizer, filling agent, specific refractory power adjusting agent etc.
(manufacture method of tackiness composition)
Tackiness composition P is fabricated to, with the respectively manufacturing of (methyl) acrylic ester polymer (A) and reactive poly-wheel hydride compounds (B), and when their are mixed, as required, the stage is added Photoepolymerizationinitiater initiater (C) etc. arbitrarily.
(methyl) acrylic ester polymer (A) is to make by common radical polymerization.Being polymerized to of (methyl) acrylic ester polymer (A) used polymerization starter as required, carries out with solution polymerization process etc.As the polymerization solvent, can exemplify, the acetic acid ethyl ester, acetic acid n-butyl ester, the acetic acid isobutyl, toluene, acetone, hexane, methyl ethyl ketones etc. are more than 2 kinds and with also can.
As polymerization starter, can exemplify the azo based compound, organo-peroxides etc. are more than 2 kinds and with also can.As the azo based compound, can exemplify 2, the 2'-azobis isobutyronitrile, 2,2'-azo two (2-methylbutyronitrile), 1,1'-azo two (hexanaphthene 1-nitrile), 2,2'-azo two (2, the 4-methyl pentane nitrile), 2,2'-azo two (2,4-dimethyl 4-methoxyl group valeronitrile), dimethyl 2,2'-azo two (2 Methylpropionic acid ester), 4,4'-azo two (4-cyanopentanoic acid), 2,2'-azo two (2-hydroxymethyl propionitrile), 2,2'-azo two ［ 2-(2-tetrahydroglyoxaline 2-yls) propane ］ etc.
As organo-peroxide, can exemplify benzoyl peroxide, t-butyl peroxybenzoic acid, hydrogen peroxide isopropyl dimethylbenzene sec.-propyl peroxide two carbonic ethers, two n-propyl group peroxides, two carbonic ethers, two (2-ethoxyethyl group) peroxide, two carbonic ethers, t-butyl peroxy neodecanoic acid, t-butyl peroxy trimethylacetic acid, (3,5, the 5-trimethyl acetyl) superoxide, two propionyl superoxide, diacetyl superoxide etc.
In addition, in the above-mentioned polymerization process, can come by the chain-transfer agent that cooperates 2 mercapto ethanol etc. the weight average molecular weight of the polymkeric substance that obtains is regulated.
On the other hand, reactive poly-wheel hydride compounds (B) is as above-mentioned, for the poly-wheel hydride compounds (b1) that contains the cyclic oligosaccharide with functional group as ring molecule with contain that polymerizability double bond compound (b2) reacts to make.
After obtaining (methyl) acrylic ester polymer (A) and reactive poly-wheel hydride compounds (B), polymkeric substance (A) and the reactive solution that gathers wheel hydride compounds (B) are mixed, as required, will dilute solvent and add., as required, with interpolations such as Photoepolymerizationinitiater initiaters (C), fully mix, obtain the tackiness composition (coating solution) of solvent dilution thereafter.
As the dilution of tackiness composition is obtained the used diluting solvent of coating solution, can exemplify hexane, heptane, the aliphatic hydrocarbon of hexanaphthene etc.; Toluene, the aromatic hydrocarbons of dimethylbenzene etc., methylene dichloride, vinylchlorid etc. be halohydrocarbon; Methyl alcohol, ethanol, propyl alcohol, butanols, the alcohol of 1-methoxyl group 2-propyl alcohol etc.; Acetone, methyl ethyl ketone, 2 pentanone, different fluorine that ketone, the ketone of pimelinketone etc.; The acetic acid ethyl ester, the ester of acetic acid butyl ester etc.; The cellosolve series solvent of ethyl cellosolve etc. etc.
So the concentration viscosity of the coating solution of modulation as long as in the possible scope of coating, just have no particular limits, can according to circumstances suit selected.For example, can be with the concentration dilution of tackiness composition 10-40 quality %.In addition, when obtaining coating solution, the interpolation of diluting solvent etc. is not prerequisite, as long as the tackiness composition is the possible viscosity of coating, diluting solvent does not add passable yet.This occasion, the tackiness composition uses as coating solution for remaining untouched.
(tackiness agent)
The tackiness agent of present embodiment is preferably, and tackiness composition P is dry in needed object coating, with the irradiation tackiness composition P of active energy beam, makes it sclerosis, just can obtain.
The drying of tackiness composition P is, can be air-dry, but be generally heat treated (preferred, warm air drying).Carry out the occasion of heat treated, Heating temperature is, take 50-150 ℃ as preferred, particularly 70-120 ℃ is preferred.In addition, be divided into preferably in 10 seconds-10 heat-up time, particularly be divided into preferred in 50 seconds-2.
As active energy beam, usually, use ultraviolet ray, electric wire etc.The irradiation dose of active energy beam is, according to the kind of energy line and difference, and ultraviolet occasion for example, light quantity is with 50-1000mJ/cm 2For preferably, particularly with 100-500mJ/cm 2For preferably.In addition, the occasion of electric wire is take the 10-1000krad degree as preferred.
As tackiness composition P being carried out above-mentioned active energy beam irradiation, will form the thing (inferring) with above-mentioned structure X.So with the tackiness agent that obtains after the tackiness composition P sclerosis, be considered to by above-mentioned structure X, existing sufficient cohesive force can be brought into play again and has good stress relaxation.In addition, the sclerosis of the tackiness composition P of the irradiation of active energy beam can be carried out rapidly, so maturation is unnecessary, just stabilize in the early stage by the stage for all physical property of the clinging power of the tackiness agent that obtains etc.Thus, have the adhering agent layer that is formed by this tackiness agent parts dispatch from the factory and inferior operation drops into and can promptly carry out, be very favorable to stock's burden of reducing intermediate materials and the face of production efficiency.
The tackiness agent of present embodiment is, what adhering agent layer was firm when forming (considers the hysteresis of the time of mensuration, what is called in this specification sheets " during the firm formation of adhering agent layer ", in finger shines about half day from active energy beam) gel fraction as G1, be formed on 23 ℃ from adhering agent layer, carry out 7 days gel fractions after the keeping under the environment of 50%RH as G2, with following formula
The gel fraction rate of change (%)=| (G2-G1)/G2| * 100
The gel fraction rate of change of calculating is, 10% take interior as preferred.The measuring method of gel fraction is that test example described as follows is described.Above-mentioned such gel fraction rate of change is in 10%, and when just meaning from the firm formation of adhering agent layer, the sclerosis of tackiness agent in fact just is over.
Gel fraction G2 after gel fraction G1 during the firm formation of adhering agent layer and the keeping in above-mentioned 7 days is that 20-90% is preferred respectively, particularly take 30-70% as preferred.Be 20% not enough less than the cohesive force of, tackiness agent such as gel fraction, weather resistance and re-using property have the occasion of step-down.In addition, surpass 90% such as gel fraction, because the stress relaxation step-down of tackiness agent, it is the occasion of step-down that elongation at break is arranged.
The tackiness agent of present embodiment, clinging power during the firm formation of adhering agent layer and adhering agent layer form rear at 23 ℃, carrying out 7 days differences of clinging power after the keeping under the environment of 50%RH is, with ± 3.0N/25mm take interior for preferred, particularly with ± 2.5N/25mm take interior as preferably.In addition, in this said clinging power, refer to by JISZ0237,180 ° of peel adhesion (peeling rate is 300mm/min) namely attach 0.5MPa at to-be-adhered object, after the pressurization in 20 minutes, 23 ℃, carry out placing in 24 hours the afterwards value of mensuration under the condition of 50%RH in 50 ℃.Clinging power is poor as described above is ± 3.0N/25mm in, adhering agent layer is firm can bring into play unchangeably clinging power once forming.
In addition, the clinging power of the tackiness agent of present embodiment is, the occasion that no matter adhering agent layer is firm when forming and or keeping in 7 days after occasion, for example take polaroid as base material, to the clinging power of non-alkali glass take 0.1-50N/25mm as preferred, particularly take 0.5-30N/25mm for preferably., can obtain from the floating and peel off etc. when can be prevented from of glass substrate in above-mentioned scope such as clinging power, re-using property is good adhesive sheet also.
The haze value of the tackiness agent of present embodiment (value of measuring according to JISK7105) is, take 10% below for preferred, particularly take below 7% as preferably, further take below 4% as preferably.Be below 10% such as haze value, the transparency is high, and is suitable as optical applications.
The elongation at break of the tension test of the tackiness agent of present embodiment is, take more than 2000% as preferred, particularly take 3000% or more for preferred, further think more than 4000% to be preferably.The value of elongation at break as being, tackiness agent demonstrate has good stress relaxation.
In addition, above-mentioned tension test is to obtain width 10mm with lamination etc., length 20mm, and the tackiness agent sheet of thickness 500 μ m (the independent adhering agent layer that does not have base material etc.).The speed of being divided with 200mm/ by tension test makes its elongation.
The tackiness agent of present embodiment is, preferred as used for optical part, such as following between the optics that can be used for polaroid (polarizing film) and polarizer (phase-contrast film) etc., perhaps polaroid (polarizing film) and polarizer (phase-contrast film) and glass substrate follows.
(adhesive sheet)
As shown in Figure 1, the adhesive sheet 1A of the 1st embodiment is, under, be stripping film 12 Hes, adhering agent layer 11 Hes of the release surface superimposed layer of stripping film 12, consist of at the base material 13 of adhering agent layer 11 superimposed layers.
In addition, as representing among Fig. 2, the adhesive sheet 1B of the 2nd embodiment is, 2 pieces stripping film 12a, 12b and, by these 2 pieces of stripping film 12a, the 12b clamping, thereby with this stripping film 12a, the adhering agent layer 11 that the release surface of 12b is joined consists of.In addition, the release surface of the stripping film in so-called this specification sheets, for the face of separability is arranged in the stripping film, though implement the face of lift-off processing and do not carried out lift-off processing, demonstrate face any of separability.
The adhesive sheet 1A of any, among the 1B, adhering agent layer 11 is all formed by the tackiness agent that forms after the above-mentioned tackiness composition sclerosis.
The thickness of adhering agent layer 11, according to adhesive sheet 1A, the application target of 1B and Shi Yi Decision are fixed, be generally 5-100 μ m, be preferably the scope of 10-60 μ m, for example as used for optical part, the occasion that the adhering agent layer of particularly using as polaroid uses, with 10-50 μ m, particularly take 15-30 μ m as preferred.
As base material 13, have no particular limits, as the substrate sheets of common adhesive sheet use thing all can use.For example, except desired optics, can example as by artificial silk, vinylformic acid, the woven that the fiber of polyester etc. obtains or non-woven fabrics; Synthetic paper; Upper matter paper, Ge Laxin paper, impregnation paper, the stationery of White Board etc.; Aluminium, the tinsel of copper etc.; Polyurethane foaming body, the foam of foam polyethylene etc.; Polyethylene terephthalate, poly terephthalic acid fourth glycol ester, the polyester film of poly-ethylnaphthalene dicarboxylic acid esters etc., polyurethane film, polyethylene film, polypropylene film, the cellulosefilm of triacetyl cellulose etc., polyvinyl chloride base film, polyvinylidene chloride film, the polyvinyl alcohol film, ethylene vinyl acetate copolymers film, polystyrene film, polycarbonate film, the acrylic resin film, norbornene resin film, the plastics film of cyclic olefin resins film etc.; These multilayer body more than 2 kinds etc.Plastics film is that an axle extends or the thing of two axle extensions can.
As optics, can exemplify, polaroid (polarizing film), polarisation, polarizer (phase-contrast film), angle of visibility are mended the reward film, and briliancy improves film, and contrast gradient improves film, liquid crystal polymer film, diffusion film, semi-penetration film etc.
The thickness of base material 13 is that difference for example in the occasion of optics, is generally 10 μ m-500 μ m according to its kind is different, is preferably 50 μ m-300 μ m.
As stripping film 12,12a, 12b, can exemplify polyethylene film, polypropylene film, the polybutene film, polyhutadiene film, poly-methyl pentene film, the polyvinyl chloride base film, the chlorovinyl copolymer film, pet film, poly-ethylnaphthalene dicarboxylic acid esters film, poly terephthalic acid fourth glycol ester film, polyurethane film, the ethylene-vinyl acetate base film is from the polyimide precursor resin film, ethene (methyl) acrylic copolymer film, ethene (methyl) acrylate copolymer film, polystyrene film, polycarbonate film, imide membrane, fluorine resin film etc.In addition, their crosslinked film also can use.Further, their laminate film also can use.In addition, stripping film 12,12a, 12b be, take the thing of active energy beam perviousness as preferred.
The release surface of above-mentioned stripping film (face that particularly joins with adhering agent layer 11) is to have implemented lift-off processing as preferred.As the stripper that uses in the lift-off processing, can exemplify alkyd system, polysiloxane series, fluorine system, unsaturated polyester system, polyolefin, the stripper of wax system etc.
To stripping film 12,12a, the thickness of 12b has no particular limits, and is generally 20-150 μ m degree.
In the manufacturing of above-mentioned adhesive sheet 1A, on the release surface of stripping film 12, the solution (coating solution) that will contain tackiness composition P is coated with drying, form the film layer of adhesion agent composition P after, on its film layer with base material 13 laminations.And then, see through stripping film 12, above-mentioned film layer is shone with active energy beam, adhering agent layer 11 forms.After the active energy beam irradiation, maturation does not need.In addition, about the condition of active energy beam, as above-mentioned.
In addition, in the manufacturing of above-mentioned adhesive sheet 1B, stripping film 12a(or 12b a side) release surface on, the coating solution that will contain above-mentioned tackiness composition is coated with drying, after the film layer of tackiness composition P forms, on its film layer, with another stripping film 12b(or 12a) carry out lamination.And then, see through stripping film 12a(or 12b) above-mentioned film layer is shone with active energy beam, obtain adhering agent layer 11.
In addition, adhering agent layer 11 formation after the irradiation of the above-mentioned active energy beam that sees through like that stripping film are replaced, on stripping film, the film layer of tackiness composition P is formed, at the state that film layer is exposed, intactly, adhering agent layer 11 is formed, on this adhering agent layer 11, base material and stripping film lamination also can thereafter.Further, on base material, the film layer of tackiness composition P is formed, after this film layer is shone with active energy beam, adhering agent layer 11 is formed also passable.
As the coating process of above-mentioned coating solution, can exemplify the barcode method, scraper for coating method, roller coating method, scraper for coating method, mould coating method, notch board coating method etc.
At this, for example, in the manufacturing of the liquid crystal display device that liquid crystal cells and polaroid consist of, use polaroids as the base material 13 of adhesive sheet 1A, after the stripping film 12 of this adhesive sheet 1A was peeled off, the adhering agent layer 11 that exposes was fitted with liquid crystal cells and is got final product.
In addition, for example, in the manufacturing of the liquid crystal display device of the polarizer configuration between liquid crystal cells and the polaroid, as an example, at first, with the side's of adhesive sheet 1B stripping film 12a(or 12b) peel off after, the adhering agent layer that exposes 11 of adhesive sheet 1B and polarizer are fitted.Then, use the stripping film 12 of the adhesive sheet 1A of polaroids to peel off as base material 13 after, fit at the adhering agent layer that exposes 11 and the above-mentioned polarizer of adhesive sheet 1A.Further, from the adhering agent layer 11 of above-mentioned adhesive sheet B stripping film 12b(or the 12a with another) peel off after, adhering agent layer 11 and liquid crystal cells that adhesive sheet B is exposed are fitted.
Above adhesive sheet 1A, 1B, the stress relaxation of adhering agent layer 11 is good, for example polaroid then in the applicable occasion, weather resistance is high, then floats in the interface and peel off to be difficult to occur.
Embodiment described above is, makes for the present invention is more readily understood, and the present invention is not limited to them.But each key element that game clock is shown in the above-mentioned embodiment all is a part of the present invention at design alteration and the equivalent of the scope that belongs to technology of the present invention.
For example, the stripping film 12 of adhesive sheet 1A can omit, the stripping film 12a among the adhesive sheet 1B, and the opposing party that appoints of 12b also can omit.
[embodiment]
Below, with embodiment etc. the present invention is further specified, but scope of the present invention is not restricted among these embodiment.
(embodiment 1)
1.(the methyl) modulation of acrylic ester polymer
To having stirrer, thermometer, the circulation water cooler, in the reaction vessel of dripping device and nitrogen ingress pipe, with vinylformic acid n-butyl ester 95 mass parts, vinylformic acid 5 mass parts, acetic acid ethyl ester 200 mass parts, and the adding of 2,2'-azobis isobutyronitrile, 0.08 mass parts, the air in the above-mentioned reaction vessel is replaced with nitrogen.This nitrogen atmosphere gas bottom stirs, and the limit is warming up to 60 ℃ with reaction soln, after the reaction in 16 hours, is cooled to room temperature.At this, an one of the solution that obtains carries out molecular weight determination with following method, and the generation of (methyl) acrylic ester polymer of weight average molecular weight (Mw) 2,000,000 (polymkeric substance (A)) is identified.
2. the modulation of reactive poly-wheel hydride compounds (B)
Straight chain shape molecule is polyoxyethylene glycol, and ring molecule has hydroxypropyl and caprolactone chain, and the end of this caprolactone chain is the alpha-cylodextrin that hydroxyl is arranged, and END CAPPED GROUP is the poly-wheel hydride compounds (b1 of adamantyl; Advanced Softmaterials company system, the super polymer A 1000 of Selm, weight average molecular weight 600,000, hydroxyl valency 72mgKOH/g, solid component concentration 100 quality %) be diluted to solid component concentration 20 quality % in the toluene.
In the solution of above-mentioned poly-wheel hydride compounds (b1), will be as the methylacryoyloxyethyl isocyanic ester that contains polymerizability double bond compound (b2) (MOI: clear and electrician company system, CallensMO I), MOI is added, making the amount of this MOI is 20mol% for the hydroxyl to poly-wheel hydride compounds (b1), simultaneously, as catalyst, the dibutyl tin lauryl is added, making it is 10 quality % to MOI, under the nitrogen atmosphere gas, in 23 ℃, carry out reaction in 24 hours, obtain containing as ring molecule the poly-wheel of the reactivity hydride compounds (B) of the alpha-cylodextrin with the methacryloxy that contains the two keys of polymerizability.The generation of this reactive poly-wheel hydride compounds (B), can be from the mensuration of fourier-transform infrared spectrophotometer (FT-IR), the peak (3350cm of the urethane bonds origin that the reaction of the hydroxyl of the isocyanate group of MOI and poly-wheel hydride compounds (b1) forms -1Near, 1650cm -1, and 1500cm -1) be identified (spectrum of FT-IR shown in Fig. 3 with reference to), and the rising of the gel fraction during from following tackiness composition middle-ultraviolet lamp irradiation is identified.
3. the modulation of tackiness composition
To (methyl) acrylic ester polymer (polymkeric substance (A)) 100 mass parts (solids component scaled value) that obtain in the above-mentioned operation (1), after the poly-wheel of reactivity hydride compounds (B) the 20 mass parts mixing that obtains in the above-mentioned operation (2), as Photoepolymerizationinitiater initiater (C), with benzophenone and 1-hydroxycyclohexylphenylketone thing (the Ciba Specialty Chemicals company system with the mass ratio mixing of 1:1, IRGACURE500) 0.5 mass parts is added, fully stir, obtain the coating solution of tackiness composition.
At this, the cooperation of this tackiness composition is as shown in table 1.In addition, described contracted notation of table 1 etc. following shown in.
[polymkeric substance (A)]
BA: vinylformic acid n-butyl ester
AA: vinylformic acid
HEA: vinylformic acid 2-hydroxyethyl ester
[isocyanate-based linking agent]
CORONATEL: the tolylene diisocyanate affixture of TriMethylolPropane(TMP) (Japanese polyurethane company system, trade(brand)name " CORONATEL ")
TAKENATED-110N: the Xylene Diisocyanate affixture of TriMethylolPropane(TMP) (Mitsui Chemicals urethane company system, trade(brand)name " TAKENATED-110N ")
[epoxy is linking agent]
TETRAD-X:N, N, N', N'-four diepoxy glycerine m-xylylene amines (gas chemical company of Mitsubishi system, trade(brand)name " TETRAD-X ")
[plasticizer]
ADEKASIZERC-8: trimellitate is plasticizer (tri trimellitate (2 ethylhexyl) ester) (Asahi Electro-Chemical Co. Ltd's system, trade(brand)name " ADEKASIZERC-8 ")
4. the manufacturing that has the polaroid of adhering agent layer
Coating solution with the tackiness composition that obtains, with polysiloxane series stripping agent to a face of pet film carried out lift-off processing stripping film (Lin Deke company system, SP-PET3811, thickness: be coated with knife coater on the lift-off processing face 38 μ m), 90 ℃, 1 minute heat treated, the film layer of tackiness composition forms.
Then, will be formed with the liquid crystal layer polarizing film by discoid, polarizing film and angle of visibility enlarge the integrated polaroid of film fits, and the exposing surface of above-mentioned film layer and the surface of discoid liquid crystal layer joined.Thereafter, see through stripping film and carry out uviolizing with following condition, as adhering agent layer, the polaroid with adhering agent layer is obtained with above-mentioned film layer.The thickness of adhering agent layer is 25 μ m.
＜uviolizing condition＞
Fusion company electrodeless lamp processed uses the H bulb
Illumination 600mW/cm 2, light quantity 150mJ/cm 2
UV illumination quantorecorder uses EYEGRAPHICS company system " UVPF-36 "
(embodiment 2-5, comparative example 1-2)
The kind that respectively consists of monomer and the amount of (methyl) acrylic ester polymer, and the use level of reactive poly-wheel hydride compounds (B) and Photoepolymerizationinitiater initiater (C) is listed in table 1, go out beyond this, similarly to Example 1, the polaroid that will have adhering agent layer is made.
(comparative example 3-4)
Except with the kind that respectively consists of monomer of (methyl) acrylic ester polymer and quantitative change more, make it as shown in table 1, do not use reactive poly-wheel hydride compounds (B) and Photoepolymerizationinitiater initiater (C), such linking agent or plasticizer of using shown in the use table 1, do not use ultraviolet ray, in addition, similarly to Example 1, the polaroid with adhering agent layer must be made.
At this, above-mentioned weight average molecular weight (Mw) is to measure the weight average molecular weight of the polystyrene conversion of (GPC mensuration) under following condition with gel permeation chromatography (GPC).
＜condition determination＞
GPC determinator: Tosoh company system, HLC-8020
GPC post (following order is passed through): Tosoh company system
ＴＳＫ?ｇｕａｒｄ?ｃｏｌｕｍｎ?ＨＸＬ－Ｈ
ＴＳＫ?ｇｅｌ?ＧＭＨＸＬ（×2）
ＴＳＫ?ｇｅｌ?Ｇ2000ＨＸＬ
Measure solvent: tetrahydrofuran (THF)
Measure temperature: 40 ℃
(test example 1) (mensuration of gel fraction)
Replace having the polaroid that uses in the making of polaroid of adhering agent layer in embodiment or the comparative example, a face of use pet film has carried out having carried out with polysiloxane series stripping agent stripping film (the Lin Deke company system of lift-off processing, SP-PET3801, thickness: 38 μ m), carry out adhesive sheet and make.Specifically, on the basic film layer that is exposed by the constituting body of the film layer of the stripping film that in the manufacturing processed of embodiment or comparative example, obtains/tackiness composition, above-mentioned stripping film is carried out lamination, lift-off processing face side is joined, see through stripping film, with with in above-mentioned same condition, carry out uviolizing.Thus, the adhesive sheet that is made of stripping film/adhering agent layer/stripping film is produced.In addition, the thickness of adhering agent layer is 25 μ m.
With above-mentioned such adhesive sheet of making, (after the uviolizing, passed through front on 1st) immediately after the making, after the size sampling of 80mm * 80mm, its adhering agent layer wraps with in the polyester net (net size 200), only with the quality of tackiness agent precision balance weighing.In addition, with above-mentioned such adhesive sheet of making, at 23 ℃, the keeping of lower 7 days of the condition of 50%RH, thereafter, use with above-mentioned same in, only the quality of tackiness agent is carried out weighing.With these quality as M1.
Then, with the tackiness agent that has wrapped in the above-mentioned polyester net, at room temperature (23 ℃) carry out 24 hours dippings in the acetic acid ethyl ester.Tackiness agent taken out thereafter, 23 ℃ of temperature, under the environment of relative humidity 50%, 24 hours are air-dry, further carry out 12 hours dryings in 80 ℃ of baking boxs.Only with the quality of dried tackiness agent, use the precision balance weighing.The quality of this moment is as M2.
From M1 and the M2 that obtains, with following formula
Gel fraction (%)=(M2/M1) * 100
Calculate adhesive sheet make firm form after the gel fraction G1(% of when forming (adhering agent layer is firm)), and make (adhering agent layer formation) from adhesive sheet and will at 23 ℃, carry out 7 days gel fraction G2(% after the keeping under the environment of 50%RH) calculate.
In addition, from G1 and the G2 that obtains, with following formula
The gel fraction rate of change (%)=| (G2-G1)/G2| * 100
Calculate the gel fraction rate of change (%).The results are shown in table 2.
(test example 2) (mensuration of clinging power)
The polaroid with adhering agent layer that will obtain in embodiment or comparative example blocks, and makes the 25mm width, the sample that 100mm is long.As sample, polaroid with adhering agent layer is made firm finishing (during the firm formation of adhering agent layer, namely from uviolizing degree on the half) thing and, polaroid with adhering agent layer is made (adhering agent layer formation) at 23 ℃, carries out 7 days rear things of keeping under the environment of 50%RH and prepares.From these samples stripping film is peeled off, between the adhering agent layer that exposes, after on the non-alkali glass (Corning Incorporated's system, hawk XG) this sample being attached, in the former making company of institute of chestnut autoclave processed, with 0.5MPa, 50 ℃, pressurizeed in 20 minutes.Thereafter, at 23 ℃, after carrying out under the condition of 50%RH placing in 24 hours, with tensile testing machine (ORIENTEC company system, smooth Thelen), with peeling rate 300mm/min, the condition that peel angle is 180 °, the clinging power (S1:N/25mm) during with the firm formation of adhering agent layer and the clinging power (S2:N/25mm) after the keeping in 7 days are measured.In addition, the clinging power (S2) after the keeping in 7 days deducts the clinging power (S1) when adhering agent layer is firm to be formed, and clinging power poor (Δ S) is calculated.The results are shown in table 2.
(test example 3) (mensuration of haze value)
As working sample, the same adhesive sheet (keeping in 7 days is complete) of the adhesive sheet of using in the mensuration with gel fraction is prepared.To the adhering agent layer of this adhesive sheet, (Japanese electric look industrial system NDH2000), is pressed JISK7105, and (%) measures to haze value with haze meter.The results are shown in table 2.
(test example 4) (tension test)
Same with the adhesive sheet of in the mensuration of above-mentioned gel fraction, making, make the adhesive sheet of the structure with stripping film/adhering agent layer/stripping film.
With a plurality of layer laminate, the aggregate thickness that makes the adhering agent layer of described adhesive sheet is 500 μ m with described adhering agent layer, and only the stripping film on the top layer of multilayer body is stayed.Thereafter (comparative example 3,4 are, 23 ℃, carrying out for 2 weeks under the atmosphere gas of 50%RH places), cut out the long sample of 10mm width * 75mm from the adhesive sheet of a plurality of layer laminate of above-mentioned adhering agent layer, the stripping film of the top layer superimposed layer of multilayer body is peeled off, sample is set up, making the sample determination position is 10mm width * 20mm long (prolonging direction), 23 ℃, (ORIENTEC company system Tan Xilun) is divided with draw speed 200mm/ and is made its elongation, measures elongation at break (%) with tensile testing machine under the environment of 50%RH.The results are shown in table 2.
[table 1]
Figure BDA00002998725200231
[table 2]
Can learn from table, the tackiness agent of the adhering agent layer that obtains among the embodiment has very high elongation at break, in addition, adhering agent layer is firm when forming and keeping in 7 days after in gel fraction and the change of clinging power small.
[utilizing on the industry possibility]
Tackiness composition of the present invention and tackiness agent, at optics, for example following of polaroid and polarizer is suitable, and in addition, adhesive sheet of the present invention uses as the adhesive sheet of the used for optical part of polaroid and polarizer etc., and is suitable.In addition, the poly-rotaxane of reactivity of the present invention preferably uses as a composition of above-mentioned tackiness composition.
[explanation of symbol]
1A, 1B ... adhesive sheet
11 ... adhering agent layer
12,12a, 12b ... stripping film
13 ... base material

Claims (11)

1. tackiness composition is characterized in that comprising: as the formation monomer unit of polymkeric substance, contain monomer with carboxyl, weight average molecular weight is (methyl) acrylic ester polymer (A) of 500,000-3,000,000; With
The poly-wheel of the reactivity hydride compounds (B) that contains the cyclic oligosaccharide with the two keys of polymerizability as ring molecule.
2. tackiness composition claimed in claim 1 is characterized in that: the two keys of the polymerizability that the cyclic oligosaccharide of described reactivity poly-wheel hydride compounds (B) has are contained in by isocyanic ester and import in (methyl) acryl of described cyclic oligosaccharide.
3. tackiness composition claimed in claim 1, it is characterized in that: described reactivity poly-wheel hydride compounds (B) be by, the poly-wheel hydride compounds (b1) that contains the cyclic oligosaccharide with functional group as ring molecule and substituent compound (b2) reaction that contains the two keys of polymerizability that has with described functional group's reaction are obtained
The two keys of described polymerizability contain the amount of compound (b2), and the described functional group to described poly-wheel hydride compounds (b1) is 10-60mol%.
4. tackiness composition claimed in claim 1 is characterized in that: to described (methyl) acrylic ester polymer (A) 100 mass parts, the amount of described reactivity poly-wheel hydride compounds (B) is the 5-60 mass parts.
5. tackiness composition claimed in claim 1 is characterized in that: described (methyl) acrylic ester polymer (A), as the formation monomer unit of described polymkeric substance, contain the monomer 1-30 quality % with described carboxyl.
6. tackiness composition claimed in claim 1, it is characterized in that: described tackiness composition further has Photoepolymerizationinitiater initiater (C).
7. tackiness composition claimed in claim 6 is characterized in that: the amount of described Photoepolymerizationinitiater initiater (C) to the poly-wheel of described reactivity hydride compounds (B) 100 mass parts, is the 1-15 mass parts.
8. tackiness agent, it makes it sclerosis and forms for by each the described tackiness composition with active energy beam irradiation claim 1-7.
9. an adhesive sheet comprises base material and adhering agent layer, it is characterized in that: described adhering agent layer is made of tackiness agent claimed in claim 8.
10. adhesive sheet claimed in claim 9, it is characterized in that: described base material is optics.
11. an adhesive sheet comprises 2 pieces of stripping films and the adhering agent layer that is joined with the release surface of described 2 pieces of stripping films therefrom by described stripping film clamping, it is characterized in that: described adhering agent layer is comprised of tackiness agent claimed in claim 8.
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