CN102373028A - Pressure Sensitive Adhesion Composition, Pressure Sensitive Adhesive And Pressure Sensitive Adhesion Sheet - Google Patents

Pressure Sensitive Adhesion Composition, Pressure Sensitive Adhesive And Pressure Sensitive Adhesion Sheet Download PDF

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Publication number
CN102373028A
CN102373028A CN2011102194953A CN201110219495A CN102373028A CN 102373028 A CN102373028 A CN 102373028A CN 2011102194953 A CN2011102194953 A CN 2011102194953A CN 201110219495 A CN201110219495 A CN 201110219495A CN 102373028 A CN102373028 A CN 102373028A
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methyl
acrylic ester
ester polymer
functional group
linking agent
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CN102373028B (en
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荒井隆行
又野仁
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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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]
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

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

Abstract

The invention provides a pressure sensitive adhesion composition, a pressure sensitive adhesive and a pressure sensitive adhesion sheet having good light leak resisting performance and durability in using for optical components. The composition has (methyl) acrylate polymer (A) in a first mass part and having a weight-average molecular weight of 0.7 million to 25 million, (methyl) acrylate polymer (B) in a second mass part and having a weight-average molecular weight of 8000-0.25 million, and a cross-linking agent (C). The polymer (B) contains a monomer having 1-50 percents by mass of functional group (b1) reacting with the cross-linking agent (C). The functional group (b1) of the polymer (B) is the functional group (b1) in essence. The polymer (A) does not contain monomer having a functional group (a1) reacting with the cross-linking agent (C). Compared with the functional group (b1), the reactivity of the functional group (a1) is lower.

Description

Pressure-sensitive-adhesive compsn, pressure sensitive adhesive and pressure sensitive adhesion sheet
Technical field
The present invention relates to pressure-sensitive-adhesive compsn, pressure-sensitive-adhesive compsn method of manufacture, pressure sensitive adhesive (make the pressure-sensitive-adhesive compsn crosslinked and material) and pressure sensitive adhesion sheet, particularly be preferably used as the pressure-sensitive-adhesive compsn of optics such as polaroid, method of manufacture, pressure sensitive adhesive and the pressure sensitive adhesion sheet of pressure-sensitive-adhesive compsn.
Background technology
Generally speaking, in liquid crystal panel, the pressure sensitive adhesive layers that formed by contact adhesive composition that use are bonded in glass substrate etc. with polaroid or phase difference film more.But; Because contractions easily such as opticses such as polaroid or phase difference film are heated; Therefore, pointed out to exist following problem: because of thermal history produces contraction, its result; The pressure sensitive adhesive layer that is laminated in this optics can not be followed its contraction, produce at the interface and peel off (so-called heave, peel off) thereby or the optic axis that optics takes place of the stress when shrinking because of optics depart from the light leak (so-called leakage is white) that causes.
As the method that prevents these problems; Can enumerate: (1) is through the pressure-sensitive optics such as polaroid that is fitted in of the pressure sensitive adhesive layer that pressure sensitive adhesion power height and morphological stability is excellent; Thereby the method that suppresses the contraction of optics itself, the method for the pressure sensitive adhesive layer that the stress when perhaps (2) use optics to shrink is little.As the method for (1), the high pressure sensitive adhesive layer of such use energy storage Young's modulus is effective shown in patent documentation 1.On the other hand, as the method for (2), the excellent pressure sensitive adhesive layer of stress retentivity that the optics distortion can be flexibly tackled in use is effective.But,, formed in desire under the situation of the excellent pressure sensitive adhesive layer of such stress retentivity in the past, cross-linking density in this pressure sensitive adhesive layer is hanged down design.Like this, the problem such as intensity reduction, weather resistance variation that has pressure sensitive adhesive layer self.
Therefore; In patent documentation 2～4; Through replacing making the cross-linking density step-down of pressure sensitive adhesive layer, in acrylic pressure-sensitive adhesive, add softening agent, whiteruss, polyurethane elastomer etc., make the moderately deliquescing and give pressure sensitive adhesive ply stress retentivity of the contact adhesive composition that obtains; Thus, obtain anti-light leak property and weather resistance.
The 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
Summary of the invention
The problem that invention will solve
But, the difficult point that the pressure sensitive adhesive layer that is formed by the contact adhesive composition that is added with softening agent or whiteruss exists softening agent or whiteruss to ooze out in time.And, can be thereupon produce various problems such as the liquid crystal cells that becomes clung body is contaminated.In addition, for the contact adhesive composition that is added with polyurethane elastomer, keep consistency, the upper limit of the addition of polyurethane elastomer is restricted, and therefore, the anterethic improvement of stress is insufficient.And then, when increasing the addition of polyurethane elastomer, produce problems such as white opacity with the consistency reduction of acrylic pressure-sensitive adhesive in order to improve the stress retentivity.Technology like this, in the past is difficult to basic anti-light leak property and the weather resistance of improving the pressure sensitive adhesive layer that is formed by the used for optical part contact adhesive composition.
The present invention accomplishes in view of such practical situation, and its purpose is, all excellent pressure-sensitive-adhesive compsn, pressure sensitive adhesive and the pressure sensitive adhesion sheet of anti-light leak property and weather resistance when being provided at opticses such as being used for polaroid.
The means that are used to deal with problems
In order to realize said purpose; The 1st aspect of the present invention provides the pressure-sensitive-adhesive compsn; It is characterized in that; Contain weight-average molecular weight and be 700,000～2,500,000 the 1st (methyl) acrylic ester polymer (A), weight-average molecular weight and be 8000～250,000 the 2nd (methyl) acrylic ester polymer (B) and linking agent (C); Said the 2nd (methyl) acrylic ester polymer (B) is 5～40 mass parts with respect to the ratio of said the 1st (methyl) acrylic ester polymers of 100 mass parts (A); Said the 2nd (methyl) acrylic ester polymer (B) comprises the monomer that has with the functional group (b1) of said linking agent (C) reaction as constituent; And then; Monomeric ratio with said functional group (b1) surpasses 1 quality % and less than 50 quality % in the 2nd (methyl) acrylic ester polymer (B); Said the 2nd (methyl) acrylic ester polymer (B) is that contain to be merely said functional group (b1) in fact with functional group said linking agent (C) reaction, said the 1st (methyl) acrylic ester polymer (A) do not comprise have with the monomer of the functional group of said linking agent (C) reaction as constituent, or comprise the have functional group monomer of (a1) as constituent (invention 1), said functional group (a 1) compares reactive low (the inventing 1) with said linking agent (C) with the said functional group (b1) of said the 2nd (methyl) acrylic ester polymer (B).
Second aspect of the present invention provides the pressure-sensitive-adhesive compsn; It is characterized in that; Contain weight-average molecular weight and be 700,000～2,500,000 the 1st (methyl) acrylic ester polymer (A), weight-average molecular weight and be 8000～250,000 the 2nd (methyl) acrylic ester polymer (B) and linking agent (C); Said the 2nd (methyl) acrylic ester polymer (B) is 5～40 mass parts with respect to the ratio of said the 1st (methyl) acrylic ester polymers of 100 mass parts (A); The reactivity that has with said linking agent (C) that comprises said the 2nd (methyl) acrylic ester polymer (B) satisfies the monomer of functional group (b1) of following formula (I) as constituent; And then; Monomeric ratio with said functional group (b1) surpasses 1 quality % and less than 50 quality % in the 2nd (methyl) acrylic ester polymer (B); And; Said the 2nd (methyl) acrylic ester polymer (B) comprises the monomer of functional group (b2) that the reactivity that has with said linking agent (C) satisfies following formula (I) as constituent with the amount below 1/5 (mass ratio) of monomeric content with said functional group (b1); Said the 1st (methyl) acrylic ester polymer (A) do not comprise have with the monomer of the functional group of said linking agent (C) reaction as constituent, or comprise the have functional group monomer of (a1) as constituent (invention 2), said functional group (a1) compares reactive low (the inventing 2) with said linking agent (C) with the said functional group (b1) of said the 2nd (methyl) acrylic ester polymer (B)
Reactivity with linking agent (C): functional group (b2)＜functional group (b1) ... (I).
The pressure-sensitive-adhesive compsn of foregoing invention (invention 1,2) is crosslinked and form in the pressure sensitive adhesive that forms by in the past the low-molecular-weight polymkeric substance (B) that is used for softening agent and carry out the crosslinked and tridimensional network that obtains of chemical.And through in said tridimensional network, inserting a plurality of high molecular weight polymers (A), constraint high molecular weight polymers (A) forms a type crosslinking structure each other between high molecular weight polymers (A).Thus, cohesive force and excellent stress retentivity that the pressure sensitive adhesive performance that obtains is suitable.Through using this to have the excellent anterethic pressure sensitive adhesive of stress, the equal pressure sensitive adhesion sheet of excellence of anti-light leak property and weather resistance in the time of can obtaining being used for optics such as polaroid.
In foregoing invention (invention 1,2), said the 1st (methyl) acrylic ester polymer (A) does not preferably comprise the monomer that has with the functional group of said linking agent (C) reaction as constituent (invention 3).
In foregoing invention (invention 1; 3) in; Said functional group (a1) in preferred said the 1st (methyl) acrylic ester polymer (A) is a carboxyl, and the said functional group (b1) in said the 2nd (methyl) acrylic ester polymer (B) is a hydroxyl, and said linking agent (C) is isocyanate-based linking agent (invention 4).
In foregoing invention (invention 2; 3) in; Said functional group (a1) in preferred said the 1st (methyl) acrylic ester polymer (A) is a carboxyl; Said functional group (b1) in said the 2nd (methyl) acrylic ester polymer (B) is a hydroxyl, and said functional group (b2) is a carboxyl, and said linking agent (C) is isocyanate-based linking agent (invention 5).
In foregoing invention (invention 4,5), preferred said the 1st (methyl) acrylic ester polymer (A) contains 0～15 quality % and contains carboxylic monomer as the monomeric unit that constitutes this polymkeric substance (invention 6).
In foregoing invention (invention 4～6), preferred said the 2nd (methyl) acrylic ester polymer (B) contains 3～40 quality % hydroxyl monomers as the monomeric unit that constitutes this polymkeric substance (invention 7).
In foregoing invention (invention 4～7), the content of preferred said isocyanate-based linking agent is 0.1～3.5 normal amount (invention 8) for the NCO of this isocyanate-based linking agent with respect to the amount of the said functional group (b1) in said the 2nd (methyl) acrylic ester polymer (B).
The 3rd aspect of the present invention provides a kind of method of manufacture of pressure-sensitive-adhesive compsn; It is for making the method for said pressure-sensitive-adhesive compsn (invention 1～8); It is characterized in that; With said the 1st (methyl) acrylic ester polymer (A) and said the 2nd (methyl) acrylic ester polymer (B) blended while, add said linking agent (C) (invention 9) in any stage.
The 4th aspect of the present invention provides pressure sensitive adhesive, and it is to make crosslinked (invention 10) that forms of said pressure-sensitive-adhesive compsn (invention 1～8).
The 5th aspect of the present invention provides pressure sensitive adhesion sheet, and it is the pressure sensitive adhesion sheet with base material and pressure sensitive adhesive layer, it is characterized in that, above-mentioned pressure sensitive adhesive layer forms (invention 11) by above-mentioned pressure sensitive adhesive (invention 10).
In foregoing invention (invention 11), preferred above-mentioned base material is optics (invention 12).
The 6th aspect of the present invention provides pressure sensitive adhesion sheet; It possesses 2 stripping films and the mode that contacts with the release surface with said 2 stripping films by the pressure sensitive adhesive layer of above-mentioned stripping film clamping; It is characterized in that above-mentioned pressure sensitive adhesive layer forms (invention 13) by said pressure sensitive adhesive (invention 10).
The invention effect
In making the crosslinked pressure sensitive adhesive that forms of pressure-sensitive-adhesive compsn of the present invention, form by in the past the low-molecular-weight polymkeric substance that is used for softening agent and carry out the crosslinked and tridimensional network that obtains of chemical.And through in this tridimensional network, inserting a plurality of high molecular weight polymers, the constraint high molecular weight polymers forms a type crosslinking structure each other between high molecular weight polymers.Thus, cohesive force and excellent stress retentivity that the pressure sensitive adhesive performance that obtains is suitable.Through using this to have the excellent anterethic pressure sensitive adhesive of stress, the equal pressure sensitive adhesion sheet of excellence of anti-light leak property and weather resistance in the time of can obtaining being used for optics such as polaroid.
Description of drawings
Fig. 1 is the sectional view of the pressure sensitive adhesion sheet of the 1st embodiment of the present invention.
Fig. 2 is the sectional view of the pressure sensitive adhesion sheet of the 2nd embodiment of the present invention.
Fig. 3 is the figure in mensuration zone of light leak property test of the polaroid of expression band pressure sensitive adhesive layer.
Description of reference numerals
1A, the 1B... pressure sensitive adhesion sheet
11... pressure sensitive adhesive layer
12,12a, 12b... stripping film
13... base material
Embodiment
Below, embodiment of the present invention is described.
[pressure-sensitive-adhesive compsn]
It is that 700,000～2,500,000 the 1st (methyl) acrylic ester polymer (A), weight-average molecular weight are 8000～250,000 the 2nd (methyl) acrylic ester polymer (B) and linking agent (C) that the pressure-sensitive-adhesive compsn of this embodiment contains weight-average molecular weight, preferably further contains silane coupling agent (D).Need to prove, in this specification sheets, (methyl) propenoate be meant propenoate and methacrylic ester the two.Other similar terms too.In addition, " polymkeric substance " also comprises the notion of " multipolymer ".
For the 2nd (methyl) acrylic ester polymer (B),
(1) with have and the monomer of the functional group (b1) of linking agent (C) reaction as constituent, the functional group with linking agent (C) reaction that this polymkeric substance (B) contains is merely functional group (b1), perhaps in fact
(2) with have reactivity with linking agent (C) satisfy following formula (I) functional group (b1) monomer with have the monomer of functional group (b2) that reactivity with linking agent (C) satisfies following formula (I) as constituent.
Reactivity with linking agent (C): functional group (b2)＜functional group (b1) ... (I)
That is, in the polymkeric substance of (2) (B), functional group (b1) is higher with the reactivity of linking agent (C) than functional group (b2) with the reactivity of linking agent (C).
In arbitrary polymkeric substance (B) of above-mentioned (1) and (2), have the composition of monomer in polymkeric substance (B) of functional group (b1) above 1 quality % and less than 50 quality %.In addition, the polymkeric substance of above-mentioned (2) (B) with the amount below 1/5 (mass ratio) of monomeric content with above-mentioned functional group (b1) comprise have above-mentioned functional group (b2) monomer as constituent.
Need to prove that " being merely functional group (b1) in fact " in the polymkeric substance of above-mentioned (1) (B) allows other functional group so that the reactive degree that does not hinder functional group (b1) and linking agent (C) comprises and linking agent (C) reacts.Therefore, the polymkeric substance that comprises above-mentioned a small amount of functional group (b2) is also included within the polymkeric substance (B) of above-mentioned (1), and under such situation, the polymkeric substance (B) of the polymkeric substance of (1) (B) and (2) repeats.
On the other hand, the 1st (methyl) acrylic ester polymer (A) do not comprise have with the monomer of the functional group of linking agent (C) reaction as constitute the unit, or to have the monomer compared with the above-mentioned functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) with the reactive low functional group (a1) of linking agent (C) as constituent.
Above-mentioned (methyl) acrylic ester polymer (A) or (B) carbon number of the alkyl of preferred ester moiety be 1～20 (methyl) propenoate and have and the monomer (monomer that contains reactive functional groups) of the functional group of linking agent (C) reaction and other monomeric multipolymer of use as required.Need to prove that the 1st (methyl) acrylic ester polymer (A) does not also preferably comprise the above-mentioned monomer that contains reactive functional groups as constituting unitary polymkeric substance.
As the carbon number of the alkyl of ester moiety is (methyl) propenoate of 1～20, for example can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid dodecyl ester, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid stearyl etc.They can use separately, also can combination more than 2 kinds be used.
On the other hand, as the monomer that contains reactive functional groups, can preferably enumerate: intramolecularly has the monomer (hydroxyl monomer) of hydroxyl, monomer (containing carboxylic monomer), the intramolecularly that intramolecularly has carboxyl has amino monomer (containing amino monomers) etc.
As the hydroxyl monomer, for example can enumerate: (methyl) acrylic acid hydroxy alkyl esters such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 3-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester etc.They can use separately, also can combination more than 2 kinds be used.
As containing carboxylic monomer, for example can enumerate: ethylenically unsaturated carboxylic acids such as vinylformic acid, methylacrylic acid, Ba Dousuan, toxilic acid, methylene-succinic acid, citraconic acid.They can use separately, also can combination more than 2 kinds be used.
As containing amino monomers, for example can enumerate: (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid normal-butyl amino ethyl ester etc.They can use separately, also can combination more than 2 kinds be used.
And then as above-mentioned other monomer, for example can enumerate: (methyl) cyclohexyl acrylate etc. has (methyl) propenoate of aliphatics ring, (methyl) propenoate that (methyl) phenyl acrylate etc. has aromatic ring; The acrylic amide of non-crosslinked such as acrylic amide, USAF RH-1 property; (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N; (methyl) propenoate of non-crosslinked property such as N-dimethylamino propyl ester with tertiary amine groups, vinyl-acetic ester, vinylbenzene etc.They can use separately, also can combination more than 2 kinds be used.
Need to prove that monomer that contains reactive functional groups (b1) that uses in middle monomer and the 2nd (methyl) acrylic ester polymer (B) that contains reactive functional groups (a1) that uses of the 1st (methyl) acrylic ester polymer (A) and the monomeric selection that contains reactive functional groups (b2) are determined by the reactive relation with the linking agent (C) that uses.This will be described in detail in the back.
At this, the 2nd (methyl) acrylic ester polymer (B) comprises the above-mentioned monomer that contains reactive functional groups (b1) that surpasses 1 quality %, and its upper limit is less than 50 quality %.Preferably comprise the above-mentioned monomer that contains reactive functional groups (b1) of 3～40 quality %, especially preferably contain 5～25 quality %.Through in above-mentioned scope, comprising the monomer that contains reactive functional groups (b1); The crosslinking degree of the 2nd (methyl) acrylic ester polymer (B) is good; With the combination of the 1st (methyl) acrylic ester polymer (A) in, the stress retentivity of the pressure sensitive adhesive that obtains is excellent.In addition, the monomeric content that contains reactive functional groups (b1) is 1 quality % when following, the 2nd (methyl) acrylic ester polymer (B) crosslinked insufficient, and weather resistance reduces thus.On the other hand, the monomeric content that contains reactive functional groups (b1) is 50 quality % when above, and the crosslinked of the 2nd (methyl) acrylic ester polymer (B) becomes excessively, thus, possibly reduce the applying flexibility of clung body.Need to prove that the upper limit of the monomeric content through will containing reactive functional groups (b1) is made as 40 quality %, the weather resistance of the pressure sensitive adhesion sheet that obtains is more excellent.
In addition; Preferred especially the 2nd (methyl) acrylic ester polymer (B) do not comprise have compare with above-mentioned functional group (b1) and the monomer (monomer that contains reactive functional groups (b2)) of the reactive low functional group (b2) of linking agent (C) as constituent; Comprise the monomer during that contains reactive functional groups (b2), preferably being to contain the amount below 1/5 of the monomeric content of reactive functional groups (b1), the particularly amount below 1/10 to contain according to mass ratio as constituent.
The 2nd (methyl) acrylic ester polymer (B) comprise by quality ratio for 1/5 the amount that surpasses the monomeric content that contains reactive functional groups (b1) contain the monomer of reactive functional groups (b2) time, the weather resistance of the pressure sensitive adhesive layer that obtains reduces.When the reactive functional groups (b2) in the 2nd (methyl) acrylic ester polymer (B) is too much; Also residual many reactive functional groups (b2) infer that the consistency of this tridimensional network body and the 1st (methyl) acrylic ester polymer (A) changes in the tridimensional network body that forms thus.Its result has the situation that haze value rises.In addition, infer that also the residual many tridimensional network cognition of reactive functional groups (b2) excessively limits the mobility of inserting the 1st (methyl) acrylic ester polymer (A) in this tridimensional network body.Its result has the situation of weather resistance variation.
And then; When the pressure-sensitive-adhesive compsn of this embodiment contains silane coupling agent (D); Silane coupling agent (D) reacts with the reactive functional groups (a1) (particularly carboxyl) of the 1st (methyl) acrylic ester polymer (A); Thereby combine with high-molecular weight the 1st (methyl) acrylic ester polymer (A); The pressure sensitive adhesive that obtains for the excellent pressure sensitive adhesive of adaptation as the glass substrate of clung body etc.; The 2nd (methyl) acrylic ester polymer (B) comprises excessive when containing the monomer of reactive functional groups (b2), the alkoxysilyl etc. of inferring silane coupling agent (D) also with reactive functional groups (b2) (particularly carboxyl) reaction of the 2nd (methyl) acrylic ester polymer (B), combine with low-molecular-weight the 2nd (methyl) acrylic ester polymer (B).Its result, pressure sensitive adhesive that obtains and adaptation variation as the glass substrate of clung body etc., thus, the weather resistance of pressure sensitive adhesive layer reduces.
At this; The carbon number of the alkyl of ester moiety is (methyl) propenoate of 1～20 and have and the polymeric species of the 2nd (methyl) acrylic ester polymer (B) that the monomer polymerization of the functional group of linking agent (C) reaction obtains can be random copolymers, also can be segmented copolymer.When particularly the 2nd (methyl) acrylic ester polymer (B) is segmented copolymer, can control the size of the mesh of tridimensional network, set out thus, preferred the 2nd (methyl) acrylic ester polymer (B) is a segmented copolymer.Particularly, for the 2nd (methyl) acrylic ester polymer (B), can also preferably enumerate: making the monomer and the carbon number that have a reactive functional groups (b1) at two ends is the form of (methyl) acrylic ester block of 1～20.
In this embodiment, above-mentioned the 2nd (methyl) acrylic ester polymer (B) can use a kind separately, also can combination more than 2 kinds be used.
The weight-average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is 8000～250,000, is preferably 20,000～150,000.That is, the 2nd (methyl) acrylic ester polymer (B) is the low-molecular weight polymer composition.Need to prove that the weight-average molecular weight in this specification sheets is the value of the polystyrene conversion that records through gel permeation chromatography (GPC) method.
Weight-average molecular weight through making the 2nd (methyl) acrylic ester polymer (B) forms distinctive tridimensional network in the pressure-sensitive-adhesive compsn of this embodiment in above-mentioned scope, help excellent stress retentivity.That is, if the weight-average molecular weight of the 2nd (methyl) acrylic ester polymer (B) then can not get good tridimensional network less than 8000.On the other hand, the weight-average molecular weight of the 2nd (methyl) acrylic ester polymer (B) surpasses at 250,000 o'clock, and consistency reduces, and the insertion of the polymkeric substance (A) in the tridimensional network body that is formed by polymkeric substance (B) is insufficient, and weather resistance and reproducibility are poor.
The 1st (methyl) acrylic ester polymer (A) do not comprise have with the monomer of the functional group of linking agent (C) reaction as constituent, or comprise have compare with the above-mentioned functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) and the monomer of the reactive low functional group (a1) of linking agent (C) as constituent; And, preferably do not comprise have compare with above-mentioned functional group (b1) and the monomer of the reactive high functional group of linking agent (C) as constituent.
The 1st (methyl) acrylic ester polymer (A) also can not comprise and has and the monomer of the functional group of linking agent (C) reaction; And comprise when having the monomer (monomer that contains reactive functional groups (a1)) of comparing reactive low reactive functional groups (a1) with the reactive functional groups (b1) of the 2nd (methyl) acrylic ester polymer (B); Promote the reaction of the 2nd (methyl) acrylic ester polymer (B) and linking agent (C); Perhaps; When using silane coupling agent (D), the reactive functional groups (a1) of the 1st (methyl) acrylic ester polymer (A) and the reactions such as alkoxysilyl of this silane coupling agent (D) can be adjusted the aggegation degree of the 1st (methyl) acrylic ester polymer (A); Can obtain desirable binding property, have preferred situation.
When the 1st (methyl) acrylic ester polymer (A) comprised the monomer that contains above-mentioned reactive functional groups (a1), its content was generally below the 20 quality %, was preferably below the 15 quality %, was preferably especially below the 10 quality %.When the monomeric content that contains reactive functional groups (a1) surpassed 20 quality %, excessively aggegation of the 1st (methyl) acrylic ester polymer (A) possibly can not get desirable stress retentivity.Need to prove, consider that from the viewpoint of giving reproducibility the monomeric content that contains reactive functional groups (a1) is preferably set to below the 15 quality %.
In addition; In the monomeric comparison that comprises reactive functional groups (b1) that contains with the 2nd (methyl) acrylic ester polymer (B), the ratio of the monomer that comprises reactive functional groups (a1) in the 1st (methyl) acrylic ester polymer (A) that the 1st (methyl) acrylic ester polymer (A) contains is preferably little than the ratio of the monomer that comprises reactive functional groups (b1) in the 2nd (methyl) acrylic ester polymer (B) that the 2nd (methyl) acrylic ester polymer (B) contains.Thus, suppress the reactive functional groups (a1) that the 1st (methyl) acrylic ester polymer (A) contains and the reaction of linking agent (C), reactive functional groups (b1) and linking agent (C) that the 2nd (methyl) acrylic ester polymer (B) is contained react reliably.
The 1st (methyl) acrylic ester polymer (A) is not included in preferably that intramolecularly has and the monomer of the functional group of the reactivity of linking agent (C) more than the reactive functional groups (b1) of the 2nd (methyl) acrylic ester polymer (B) is equal; When supposing to contain said monomer; The monomeric content that intramolecularly has this functional group preferably is below the 1 quality %, to be preferably especially below the 0.5 quality % in polymkeric substance (A).When this monomeric content surpasses 1 quality %, may hinder the 2nd (methyl) acrylic ester polymer (B) of answering preferential reaction and the reaction of linking agent (C).
At this, the polymeric species of the carbon number that makes the alkyl of ester moiety the 1st (methyl) acrylic ester polymer (A) that to be (methyl) propenoate of 1～20 obtain with the monomer polymerization that contains reactive functional groups can be random copolymers, also can be segmented copolymer.
In this embodiment, above-mentioned the 1st (methyl) acrylic ester polymer (A) can use a kind separately, also can combination more than 2 kinds be used.
The weight-average molecular weight of the 1st (methyl) acrylic ester polymer (A) is 700,000～2,500,000, is preferably 1,000,000～2,000,000.That is, the 1st (methyl) acrylic ester polymer (A) becomes the high-molecular weight polymer composition.
Weight-average molecular weight through making the 1st (methyl) acrylic ester polymer (A) is in above-mentioned scope; Deduction is inserted the 1st (methyl) acrylic ester polymer (A) well in the tridimensional network that the 2nd (methyl) acrylic ester polymer (B) forms; Through the class crosslinking structure that this polymkeric substance (A) more than 2 molecules forms, polymkeric substance (A) is restrained with the state with degree of freedom to a certain degree.Thus, the pressure sensitive adhesive of formation has suitable cohesive force and excellent stress retentivity simultaneously, its result, and anti-light leak property is excellent, and in addition, the adhesion durability under high temperature, the wet heat condition becomes fully, can prevent to heave and peel off etc.
At this, the weight-average molecular weight of the 1st (methyl) acrylic ester polymer (A) was less than 700,000 o'clock, and (A) cohesive force of composition reduces, weather resistance and reproducibility possible deviation.In addition, the weight-average molecular weight of the 1st (methyl) acrylic ester polymer (A) surpasses at 2,500,000 o'clock, and with the consistency variation that the 2nd (methyl) acrylic ester polymer (B) waits, the haze value rising possibly can not get desirable stress retentivity.
The 2nd (methyl) acrylic ester polymer (B) is 5～40 mass parts with respect to the ratio of 100 mass parts the 1st (methyl) acrylic ester polymers (A), is preferably 10～30 mass parts.
For the pressure sensitive adhesive that obtains by the pressure-sensitive-adhesive compsn that contains the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) with aforementioned proportion; Infer; The 2nd (methyl) acrylic ester polymer (B) (low-molecular weight polymer) forms tridimensional network via linking agent (C); Be utilized in the structure that is inserted with above the 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) of 2 molecules in this tridimensional network, form polymkeric substance (A) each other to have the to a certain degree restrained class crosslinking structure of state of degree of freedom.Thus, the pressure sensitive adhesive that obtains is brought into play excellent stress retentivity when having suitable cohesive force.The weather resistance of the pressure sensitive adhesive that therefore, obtains and anti-light leak property are excellent.
As linking agent (C), can preferably enumerate: isocyanate-based linking agent, epoxy are that linking agent, Soluol XC 100 are linking agent, metal-chelating system linking agent etc.
The isocyanate-based linking agent comprises polyisocyanate compound at least.As polyisocyanate compound, for example can enumerate: ester ring type POLYMETHYLENE POLYPHENYLISOCYANATE such as aliphatic polyisocyantes such as aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethanediisocyanate, XDI, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate etc., and they biuret body, isocyanuric acid ester body and with reactant that terepthaloyl moietie, Ucar 35, NSC 6366, TriMethylolPropane(TMP), castor-oil plant wet goods contain the low molecular compound of active hydrogen be adducts etc.
As epoxy is linking agent; For example can enumerate: 1, two (N, the N '-diglycidyl amino methyl) hexanaphthenes of 3-, N; N; N ', N '-four glycidyl group-m-xylene diamine, ethylene glycol bisthioglycolate glycidyl ether, 1,6-pinakon diglycidyl ether, TriMethylolPropane(TMP) diglycidyl ether, diglycidylaniline, diglycidyl amine etc.
As Soluol XC 100 is linking agent; For example can enumerate: ditan-4; 4 '-two (1-Soluol XC 100 methane amides), trimethylolpropane tris-β-'-aziridino propionic ester, tetramethylol methane three-β-'-aziridino propionic ester, Toluene-2,4-diisocyanate, 4-two (1-Soluol XC 100 methane amide), triethylene trimeric cyanamides, two isophthaloyl-1-(2-methylaziridine), three-1-(2-methylaziridine) phosphine, trimethylolpropane tris-β-(2-methylaziridine) propionic ester etc.
It is the chelate compound of aluminium, zirconium, titanium, zinc, iron, tin etc. that metal-chelating system linking agent has atoms metal, considers from aspect of performance, preferred aluminium chelate compound.As the aluminium chelate compound, for example can enumerate: diisopropoxy aluminium list oil base acetylacetic ester, the two oil base acetylacetic esters of single aluminum isopropoxide, single aluminum isopropoxide monoleate list ethyl acetoacetic ester, diisopropoxy aluminium list lauryl acetylacetic ester, diisopropoxy aluminium list stearyl acetylacetic ester, diisopropoxy aluminium list iso stearyl acetylacetic ester etc.
Content for linking agent (C); For the crosslinkable groups (for example NCO) of this linking agent (C) becomes 0.05～5 normal amount usually with respect to the amount of the reactive functional groups (b1) (for example hydroxyl) of the 2nd (methyl) acrylic ester polymer (B); Being preferably becomes 0.1～3.5 normal amount, and being preferably especially becomes 0.2～1.8 normal amount.If the amount of above-mentioned crosslinkable groups is more than 0.1 equivalent, the gel per-cent of the pressure sensitive adhesive that then obtains is more than 40%, can bring into play sufficient cohesive force, is 0.2 equivalent when above, can be so that the weather resistance of the pressure sensitive adhesive that arrives excellence more.On the other hand, the amount of above-mentioned crosslinkable groups is 3.5 equivalents when following, can be so that the reproducibility of the pressure sensitive adhesive that arrives be excellent, and then, if below 1.8 equivalents, then can the haze value of the pressure sensitive adhesive that obtains be suppressed at lower.
In addition, in this embodiment, as linking agent (C), and if the two the linking agent of kind of reactive relationship consistency of reactive functional groups (b1) and reactive functional groups (a1), then also can and use multiple linking agent.From can easily controlling the viewpoint of the tridimensional network that is formed by the 2nd (methyl) acrylic ester polymer (B), preference only uses a kind linking agent as as only using the isocyanate-based linking agent, and then, especially preferably only use 1 linking agent.
On the other hand; As other form; As linking agent (C); The linking agent of preferred a kind, preferred especially 1 linking agent, simultaneously, can in and the mass ratio of linking agent (C) is preferably below 1/20, the amount below 1/30 of being preferably is especially used and the two reactive relation other linking agent (CR) opposite with linking agent (C) of reactive functional groups (b1) and reactive functional groups (a 1).For example can preferably enumerate linking agent (C) is made as the isocyanate-based linking agent, using a small amount of epoxy is the form of linking agent as other linking agent (CR).The making an addition to of other linking agent like this do not inserted enough polymkeric substance (A) and is effective under the insufficient situation of cohesive force in the tridimensional network that polymkeric substance (B) constitutes.Need to prove that above-mentioned other linking agent (CR) is not included in the linking agent (C), it is excluded outside linking agent (C) in the relation of above-mentioned amount.
At this; As linking agent (C) and (methyl) acrylic ester polymer (A) and (B) separately the monomeric combination that contains reactive functional groups; At linking agent (C) is under the situation of isocyanate-based linking agent, and the monomer that contains reactive functional groups (a1) as polymkeric substance (A) preferably contains carboxylic monomer; The monomer that contains reactive functional groups (b1) as polymkeric substance (B); Preferred hydroxyl monomer or contain amino monomers, the monomer that contains reactive functional groups (b2) as polymkeric substance (B) preferably contains carboxylic monomer.
On the other hand; Linking agent (C) is that linking agent, Soluol XC 100 are under the situation of linking agent or metal-chelating system linking agent for epoxy, as the monomer that contains reactive functional groups (a1) of polymkeric substance (A), and preferred hydroxyl monomer; The monomer that contains reactive functional groups (b1) as polymkeric substance (B); Preferably contain carboxylic monomer, as the monomer that contains reactive functional groups (b2) of polymkeric substance (B), preferred hydroxyl monomer.
From to the flexibility of the key that forms between linking agent (C) and the polymkeric substance (B), and the stability of crosslinking reaction and reactive group aspect consideration favourable of polymkeric substance (A) with silane coupling agent (D) appropriate reaction to the cohesive force that improves polymkeric substance (A); Especially preferably linking agent (C) is made as the isocyanate-based linking agent; The monomer that contains reactive functional groups (a1) of polymkeric substance (A) is made as contains carboxylic monomer; The monomer that contains reactive functional groups (b1) of polymkeric substance (B) is made as the hydroxyl monomer, the monomer that contains reactive functional groups (b2) of polymkeric substance (B) is made as contains carboxylic monomer.
The pressure-sensitive-adhesive compsn of this embodiment preferably further contains silane coupling agent (D).When containing this silane coupling agent (D); Have under the situation of carboxyl at the 1st (methyl) acrylic ester polymer (A); The carboxyl reaction of organic reaction property group of silane coupling agent (D) etc. and the 1st (methyl) acrylic ester polymer (A); On the other hand, alkoxysilyl of silane coupling agent (D) etc. acts on clung body faces such as glass substrate.Therefore, when for example polaroid being fitted in liquid-crystalline glasses unit etc., the adaptation between pressure sensitive adhesive and the liquid-crystalline glasses unit is better.
As this silane coupling agent (D), be preferably at intramolecularly and have the silicoorganic compound of at least 1 alkoxysilyl and and the consistency of pressure sensitive adhesive composition is good and coupling agent with light transmission, for example transparent in fact coupling agent.The addition of such silane coupling agent (D) is 0.01～0.5 mass parts with respect to 100 mass parts the 1st (methyl) acrylic ester polymers (A) preferably, is preferably 0.05～0.3 mass parts especially.
Concrete example as silane coupling agent (D); Can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane etc. contain the silicon compound of polymerizability unsaturated group; 3-glycidoxypropyltrimewasxysilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane etc. has the silicon compound of epoxy construction; 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane etc. contain amino silicon compound, 3-r-chloropropyl trimethoxyl silane, 3-isocyanic ester propyl-triethoxysilicane etc.They can use a kind separately, also can combination more than 2 kinds be used.
In the above-mentioned pressure-sensitive-adhesive compsn; Can add normally used various additives in the acrylic pressure-sensitive adhesive as required, for example tackifier, inhibitor, UV light absorber, photostabilizer, tenderizer, weighting agent, static inhibitor, specific refractory power regulator etc.
[method of manufacture of pressure-sensitive-adhesive compsn]
Above-mentioned pressure-sensitive-adhesive compsn can add the silane coupling agent (D) of linking agent (C) and interpolation as required and make through with the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) blended while in any stage.
As preferred concrete example, utilize common radical polymerization preparation (methyl) acrylic ester polymer (A) to reach (B) respectively.(methyl) acrylic ester polymer (A) and (B) polymerization can be used polymerization starter as required, utilize solution polymerization process etc. to carry out.As polymer solvent, for example can enumerate: ETHYLE ACETATE, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone etc., can be also with more than 2 kinds.
As polymerization starter, can enumerate azo based compound, organo-peroxide etc., can be also with more than 2 kinds.As the azo based compound, for example can enumerate: 2,2 '-Diisopropyl azodicarboxylate, 2; 2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene 1-formonitrile HCN), 2,2 '-azo two (2; 2,2 the 4-methyl pentane nitrile), '-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-methylol propionitrile), 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] etc.
As organo-peroxide; For example can enumerate: Lucidol, peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (2-ethoxy ethyl ester), new peroxide tert-butyl caprate, the peroxo-PIVALIC ACID CRUDE (25) tert-butyl ester, peroxo-(3; 5,5-trimethyl acetyl), dipropyonyl peroxide, diacetyl peroxide etc.
Then, polymkeric substance that obtains (A) and solution (B) are mixed, add diluting solvent.Thereafter, add linking agent (C) and silane coupling agent as required (mixing D), thorough mixing thus, obtains the pressure-sensitive-adhesive compsn of crossing with solvent cut (coating solution).
The diluting solvent that forms coating solution as being used to dilute the pressure-sensitive-adhesive compsn; For example can use aliphatic hydrocarbons such as hexane, heptane, hexanaphthene; Halons such as aromatic hydrocarbons such as toluene, YLENE, methylene dichloride, vinylchlorid, methyl alcohol, ethanol, propyl alcohol, butanols, 1-methoxyl group-alcohol such as 2-propyl alcohol, ketone such as acetone, methyl ethyl ketone, 2 pentanone, isophorone, pimelinketone; Ester such as ETHYLE ACETATE, butylacetate, cellosolve series solvents such as ethyl cellosolve etc.
Concentration viscosity as the coating solution for preparing thus gets final product in the scope that can be coated with, and not special the qualification can according to circumstances suitably do not selected.For example, be that the mode of 10～40 quality % is diluted with the concentration of pressure-sensitive-adhesive compsn.Need to prove that when obtaining coating solution, the interpolation of diluting solvent etc. is not a prerequisite, the pressure-sensitive-adhesive compsn gets final product for the viscosity that can be coated with etc., also can not add diluting solvent.Under this situation, the pressure-sensitive-adhesive compsn is directly as coating solution.
[pressure sensitive adhesive]
The pressure sensitive adhesive of this embodiment is that above-mentioned pressure-sensitive-adhesive compsn is crosslinked and obtain.The crosslinked of above-mentioned pressure-sensitive-adhesive compsn can carry out through heat treated.Need to prove the drying treatment when this heat treated also can double as makes the volatilizations such as diluting solvent of pressure-sensitive-adhesive compsn.
When carrying out heat treated, Heating temperature is preferably 50～150 ℃, is preferably 70～120 ℃ especially.In addition, be preferably 30 seconds heat-up time～3 minutes, be preferably 50 seconds especially～2 minutes.And then, after the heat treated, preferably set at the curing time of normal temperature (for example 23 ℃, 50%RH) about following 1～2 week especially.
Infer that through above-mentioned heat treated (and maintenance) utilize linking agent (C), the 2nd (methyl) acrylic ester polymer (B) is crosslinked, forms fine and close tridimensional network.And, in this tridimensional network, do not following direct chemically bonded or following under the considerably less chemically bonded, insert above the 1st (methyl) Yodo Sol GH 28 (A) of 2 molecules, thus, (A) is restrained for this polymkeric substance, forms a type crosslinking structure.In addition, the 1st (methyl) acrylic ester polymer (A) is when having carboxyl, and the 1st (methyl) acrylic ester polymer (A) reacts with silane coupling agent (D), the degree of aggegation regulation.
More than the pressure sensitive adhesive of explanation can be preferably used as optics, for example, is preferred for bonding or polaroid (polarizing coating) or phase difference film (phase retardation film) and glass substrate bonding of polaroid and phase difference film.Utilize the stress retentivity of the pressure sensitive adhesive layer that above-mentioned pressure sensitive adhesive forms very excellent, therefore, even under the big situation of the dimensional change of clung body; Also can absorb, relax the stress that produces because of this dimensional change through pressure sensitive adhesive layer; Therefore, peel off from clung body through also being difficult for for a long time, simultaneously; When being used for aforesaid optics, can prevent light leak property effectively.That is, the pressure sensitive adhesive of this embodiment has been realized taking into account of anti-light leak property and weather resistance.
[pressure sensitive adhesion sheet]
As shown in Figure 1, the pressure sensitive adhesion sheet 1A of the 1st embodiment is made up of stripping film 12, the pressure sensitive adhesive layer 11 that is laminated in the release surface of stripping film 12, the base material 13 that is laminated in pressure sensitive adhesive layer 11 from following beginning successively.
In addition, as shown in Figure 2, the pressure sensitive adhesion sheet 1B of the 2nd embodiment is made up of 2 stripping film 12a, 12b and the pressure sensitive adhesive layer 11 that is clamped between these 2 stripping film 12a, the 12b with the mode that the release surface with these 2 stripping film 12a, 12b contacts.Need to prove that the release surface of the stripping film in this specification sheets is meant the face that has separability in the stripping film, even also comprise the face of having implemented lift-off processing and do not implement in the face that lift-off processing also shows separability any.
At arbitrary pressure sensitive adhesion sheet 1A, among the 1B, pressure sensitive adhesive layer 11 constitutes by the crosslinked pressure sensitive adhesive that forms of above-mentioned pressure-sensitive-adhesive compsn.
The thickness of pressure sensitive adhesive layer 11 comes suitably decision according to the application target of pressure sensitive adhesion sheet 1A, 1B; Common scope at 5～100 μ m, preferred 10～60 μ m; For example; When the pressure sensitive adhesive layer of using as optics, particularly polaroid uses, be preferably 10～50 μ m, be preferably 10～30 μ m especially.
As base material 13, not special the qualification, the base material of the common substrate sheets that is used as pressure sensitive adhesion sheet all can use.For example, except the optics of wanting, can enumerate: use weaving cotton cloth or non-woven fabrics of fibers such as regenerated fiber, acrylic, polyester; Stationeries such as the paper of wood-free, zellglas, impregnated paper, White Board; Tinsel such as aluminium, copper; Foam such as polyurethane foaming body, foam polyethylene; Plastic films such as polyester films such as polyethylene terephthalate, polybutylene terephthalate, PEN, polyurethane film, polyethylene film, polypropylene screen, polychloroethylene film, polyvinylidene chlorida film, polyvinyl alcohol film, vinyl-vinyl acetate copolymer film, Polystyrene Film, polycarbonate membrane, acrylic resin film, norbornene resin film, cycloolefin resin film; Laminate of these films etc. more than 2 kinds.Plastic film can carry out uniaxial extension or biaxial stretch-formed.
As optics, for example can enumerate: polaroid (polarizing coating), polariscope, phase difference film (phase retardation film), compensation film for angular field of view, brightness improve film, contrast gradient improves film, liquid crystalline polymer film etc.Wherein, polaroid (polarizing coating) is prone to shrink, and dimensional change is big, considers from the viewpoint of anti-light leak property, and preferably conduct forms the object of the pressure sensitive adhesive (above-mentioned pressure sensitive adhesive layer 11) of this embodiment.
The thickness of base material 13 is generally 10 μ m～500 μ m according to its kind and difference for example is under the situation of optics, is preferably 50 μ m～300 μ m.
As stripping film 12; 12a; 12b for example can use polyethylene film, polypropylene screen, polybutylenes film, polyhutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, poly (ethylene naphthalate) film, polybutylene terephthalate film, polyurethane film, ethane-acetic acid ethyenyl ester film, ionomer resin film, ethene (methyl) PEMULEN TR2 film, ethene (methyl) Yodo Sol GH 28 film, Polystyrene Film, polycarbonate membrane, polyimide film, fluororesin film etc.In addition, also can use the cross linking membrane of these films.And then, also can be the laminate film of these films.
Preferably the release surface (face that particularly contacts with pressure sensitive adhesive layer 11) of above-mentioned stripping film is implemented lift-off processing.As the stripper that uses in the lift-off processing, for example can enumerate: alkyd system, silicon-type, fluorine system, unsaturated polyester system, polyolefin, wax series stripping agent.
The thickness of stripping film 12,12a, 12b is not special to be limited, and is generally about 20～150 μ m.
When making above-mentioned pressure sensitive adhesion sheet 1A, comprise the solution (coating solution) of above-mentioned pressure-sensitive-adhesive compsn, carry out heat treated in the release surface coating of stripping film 12, form pressure sensitive adhesive layer 11 after, layered base 13 on this pressure sensitive adhesive layer 11.
Need to prove that the condition of heat treated as stated.
In addition; When making above-mentioned pressure sensitive adhesion sheet 1B; The coating solution that comprises above-mentioned pressure-sensitive-adhesive compsn in the release surface coating of a stripping film 12a (or 12b); Carry out heat treated, behind the formation pressure sensitive adhesive layer 11, in the release surface of this pressure sensitive adhesive layer 11 superimposed another stripping film 12b (or 12a).
As the method for the above-mentioned coating solution of coating, for example can utilize rod to be coated with method, scraper coating method, rolling method, scraper plate coating method, mould and be coated with method, gravure roll coating method etc.
At this, for example, when making the liquid crystal watch showing device that constitutes by liquid crystal cells and polaroid, use the base material 13 of polaroid as pressure sensitive adhesion sheet 1A, peel off the stripping film 12 of this pressure sensitive adhesion sheet 1A, the pressure sensitive adhesive layer 11 that will expose is fitted with liquid crystal cells and is got final product.
In addition, for example, when being manufactured on the liquid crystal indicator that disposes phase difference film between liquid crystal cells and the polaroid; The stripping film 12a (or 12b) of releasing pressure sensitive adhesive sheet 1B; The pressure sensitive adhesive layer 11 that will expose is fitted with liquid crystal cells, then, peels off another stripping film 12b (or 12a); The pressure sensitive adhesive layer 11 that will expose is fitted with phase difference film; And then, there is polaroid to peel off use as the stripping film 12 of the pressure sensitive adhesion sheet 1A of base material 13, the pressure sensitive adhesive layer 11 that will expose is fitted with phase difference film and is got final product.
Utilize above pressure sensitive adhesion sheet 1A, 1B; The stress retentivity of pressure sensitive adhesive layer 11 is very excellent; Therefore when for example promptly being used in polaroid bonding; Can absorb through pressure sensitive adhesive layer 11, relax stress because of the distortion generation of polaroid, thus, anti-light leak property and high-durability that performance is excellent.
More than the embodiment of explanation is put down in writing in order to understand the present invention easily, is not to put down in writing for limiting the present invention.Therefore, disclosed respectively being characterized as also comprises the whole design alterations that belong to technical scope of the present invention and the purport of equivalent in the above-mentioned embodiment.
For example, the stripping film 12 of pressure sensitive adhesion sheet 1A can omit, and the stripping film 12a among the pressure sensitive adhesion sheet 1B, any among the 12b also can be omitted.
Embodiment
Below, through embodiment etc. the present invention is explained more specifically, but scope of the present invention is not limited to these embodiment etc.
[embodiment 1]
1. the preparation of polymkeric substance (A)
In the reaction vessel that possesses stirrer, TM, reflux exchanger, Dropping feeder and nitrogen ingress pipe, add n-butyl acrylate 95.0 mass parts, vinylformic acid 5.0 mass parts, ETHYLE ACETATE 200 mass parts, reach 2; 2 '-Diisopropyl azodicarboxylate 0.08 mass parts, the air displacement in the above-mentioned reaction vessel is become nitrogen.Under this nitrogen atmosphere, stir, simultaneously, reaction soln is warming up to 60 ℃, react after 16 hours, be cooled to room temperature.At this, with after the method stated the part of the solution that obtains carried out GPC measure, confirm to generate weight-average molecular weight and be 1,500,000 polymkeric substance (A).
2. the preparation of polymkeric substance (B)
In the reaction vessel that possesses stirrer, TM, reflux exchanger, Dropping feeder and nitrogen ingress pipe, add n-butyl acrylate 85.0 mass parts, vinylformic acid 2-hydroxyl ethyl ester 15.0 mass parts, ETHYLE ACETATE 200 mass parts, 2; 2 '-Diisopropyl azodicarboxylate 0.16 mass parts, and 2 mercapto ethanol 0.3 mass parts, the air displacement in the above-mentioned reaction vessel is become nitrogen.Under this nitrogen atmosphere, stir, simultaneously, reaction soln is warming up to 70 ℃, react after 6 hours, be cooled to room temperature.At this, with after the method stated the part of the solution that obtains carried out GPC measure, confirm to generate weight-average molecular weight and be 50,000 polymkeric substance (B).
3. pressure-sensitive-adhesive preparation of compositions
After 20 mass parts (solids component scaled value) polymkeric substance (B) mixing that obtains in 100 mass parts that obtain in the above-mentioned operation (1) (solids component scaled value) polymkeric substance (A) and the above-mentioned operation (2); As linking agent (C); Add tolylene diisocyanate (TDI system) affixture (Japanese Port リ ウ レ タ Application society system, trade(brand)name " コ ロ ネ one ト L ") of the TriMethylolPropane(TMP) of the hydroxyl 0.8 normal amount be equivalent to polymkeric substance (B).At last,, add 3-glycidoxypropyltrimewasxysilane (chemical company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ") 0.2 mass parts, fully stir, thus, obtain the diluting soln of pressure-sensitive-adhesive compsn as silane coupling agent (D).
Here, the proportioning with this pressure-sensitive-adhesive compsn is shown in table 1.Need to prove that the details of the abbreviation that table 1 is put down in writing etc. is described below.
[polymkeric substance (A) reaches (B)]
BA: n-butyl acrylate
AA: vinylformic acid
HEA: vinylformic acid 2-hydroxyl ethyl ester
HBA: vinylformic acid 4-hydroxy butyl ester
HEMA: methylacrylic acid 2-hydroxyl ethyl ester
[linking agent (C)]
The isocyanate-based linking agent
TDI system: the tolylene diisocyanate affixture of TriMethylolPropane(TMP) (Japanese Port リ ウ レ タ Application society system, trade(brand)name " コ ロ ネ one ト L ")
Isocyanuric acid ester system: the isocyanuric acid ester thing of hexamethylene diisocyanate (Japanese Port リ ウ レ タ Application Industrial Co., Ltd system, trade(brand)name " コ ロ ネ one ト HXR ")
Other linking agent (epoxy is a linking agent)
N, N, N ', N '-four glycidyl group m-xylene diamine (gas chemical company of Mitsubishi system, trade(brand)name " TETRAD-X ")
[silane coupling agent (D)]
KBM403:3-glycidoxypropyltrimewasxysilane (chemical company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ")
KBE9007:3-isocyanic ester propyl-triethoxysilicane (chemical company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBE9007 ")
KBE403:3-glycidoxypropyl triethoxyl silane (chemical company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBE403 ")
Utilize knife coater, be that the mode of 25 μ m is coated on stripping film (the リ Application テ ッ Network society system of a face of polyethylene terephthalate film being carried out lift-off processing with the silicon-type stripper with the diluting soln of the pressure-sensitive-adhesive compsn that obtains with dried thickness; SP-PET3811; Thickness: lift-off processing face 38 μ m); Then, 90 ℃ of following heat treated 1 minute, form pressure sensitive adhesive layer.
Then; The polarizing coating that will be made up of the polarizing coating of tep reel shape liquid crystal layer enlarges the mode pressure sensitive adhesion that the integrated polaroid that forms of film contacts with the discotic mesogenic layer with pressure sensitive adhesive layer with the visual angle; Maintenance is 7 days under 23 ℃, 50%RH, obtains the polaroid with pressure sensitive adhesive layer thus.
[embodiment 2～32, comparative example 1～7]
With each the monomeric kind and the kind of ratio, linking agent and silane coupling agent and as shown in table 1 change of proportioning of addition and polymkeric substance (A) and polymkeric substance (B) that constitute the pressure-sensitive-adhesive compsn; In addition, likewise make the polaroid of band pressure sensitive adhesive layer with embodiment 1.
[Test Example 1] (evaluation of pressure sensitive adhesion power mensuration-reproducibility)
The polaroid of the band pressure sensitive adhesive layer that from embodiment or comparative example, obtains cuts the sample that 25mm is wide, 100mm is long; Peel stripping film; Pressure sensitive adhesive layer through exposing sticks on non-alkali glass (コ one ニ Application グ society system with it; イ one グ Le XG) after, the autoclave made from society of the former making of chestnut institute is in 0.5MPa, 50 ℃ pressurization 20 minutes down., 23 ℃, the condition held of 50%RH 24 hour, then, use tensile testing machine (オ リ エ Application テ ッ Network corporate system, テ Application シ ロ Application), under the condition of 300mm/min peeling rate, 180 degree peel angle, measure pressure sensitive adhesion power (N/25mm) thereafter.Condition beyond the condition of record is measured based on JIS Z0237:2009 here.
Again 23 ℃, the condition held of 50%RH 14 days, then, (paste the pressure sensitive adhesion power after 14 days with the above-mentioned pressure sensitive adhesion power of likewise measuring; N/25mm).Need to prove that the scope of preferred pressure sensitive adhesion power is more than the 0.1N/25mm and less than 25N/25mm.
Based on the pressure sensitive adhesion power of above-mentioned stickup after 14 days, the benchmark below utilizing carries out the evaluation of reproducibility.The result is shown in table 2.
The pressure sensitive adhesion power of pasting after 14 days is below the 20N/25mm: ◎
The pressure sensitive adhesion power after 14 days of pasting is for surpassing 20N/25mm and less than 25N/25mm: zero
The pressure sensitive adhesion power of pasting after 14 days is more than the 25N/25mm: *
[Test Example 2] (mensuration of gel per-cent)
In embodiment or comparative example; The polaroid that uses in the making of the polaroid of replacement band pressure sensitive adhesive layer; Use with the silicon-type stripper face of polyethylene terephthalate film is carried out stripping film (the リ Application テ ッ Network society system that lift-off processing is crossed; SP-PET 3801, thickness: 38 μ m), make pressure sensitive adhesion sheet.Particularly; In the manufacturing processed of embodiment or comparative example, obtain by stripping film/pressure sensitive adhesive layer (thickness: on the pressure sensitive adhesive layer that exposes of the constituting body that 25 μ m) forms; Close with the mode layer of contact lift-off processing face side and to state stripping film; Thus, make the pressure sensitive adhesion sheet that forms by constituting of stripping film/pressure sensitive adhesive layer/stripping film.
With the pressure sensitive adhesion sheet that obtains maintenance 7 days under 23 ℃, the condition of 50%RH., get this pressure sensitive adhesion sheet of 80mm * 80mm size, said pressure sensitive adhesive layer is wrapped in the polyester sieve (size of mesh 200), the quality of pressure sensitive adhesive is only arranged with the precision balance weighing thereafter.The quality of this moment is made as M1.
Use Soxhlet, the sample of pressure sensitive adhesive is immersed in the ethyl acetate solvent, carry out refluxing in 16 hours., take out pressure sensitive adhesive,, in 80 ℃ baking oven, make its dry 12 hours again the environment air dried of 23 ℃ of temperature, 50% relative humidity 24 hours thereafter.With the dried quality that pressure sensitive adhesive is only arranged of precision balance weighing.The quality of this moment is made as M2.Gel per-cent (%) is with (M2/M1) * 100 expression.The result is shown in table 2.
[Test Example 3] (mensuration of optical property)
As working sample, the identical pressure sensitive adhesion sheet (maintenance got final product in 7 days) of pressure sensitive adhesion sheet that uses in the mensuration of preparation and gel per-cent.To the pressure sensitive adhesive layer of this pressure sensitive adhesion sheet, (Japanese electric look industrial society system NDH2000), is measured haze value (%) based on JIS K7105 to use haze meter.The result is shown in table 2.Need to prove that the scope of preferred haze value is 0～5%.
[Test Example 4] (durability evaluation)
(the wild system ス one パ one カ ッ タ one of society of institute that makes of reed PN1-600) is adjusted into 233mm * 309mm size with cutting means with the polaroid of the band pressure sensitive adhesive layer that obtains in embodiment or the comparative example.Peel stripping film, be fitted in after non-alkali glass (コ one ニ Application グ society system, イ one グ Le XG) goes up through the pressure sensitive adhesive layer that exposes, with the autoclave of the former making manufacturing of chestnut in 0.5MPa, 50 ℃ pressurization 20 minutes down.
, drop into the environment of following each durable condition under, after 500 hours, use 10 times of reading lenses to observe thereafter.The benchmark of cosmetic variation is following.The result is shown in table 2.
◎: immaculate on 4 limits
Zero: on 4 limits, immaculate apart from the position more than the peripheral end 0.6mm
*: at least 1 limit of 4 conditions, exist apart from the position more than the peripheral end 0.6mm heave, peel off, the unusual shortcomings of pressure sensitive adhesive outward appearance more than the 0.1mm such as foaming, striped
< durable condition >
60 ℃, relative humidity 90%
80 ℃ of dryings
[Test Example 5] (test of light leak property)
(the wild system ス one パ one カ ッ タ one of society of institute that makes of reed PN1-600) is adjusted into 233mm * 309mm size with cutting means with the polaroid of the band pressure sensitive adhesive layer that obtains in embodiment or the comparative example.Peel stripping film, stick on non-alkali glass (コ one ニ Application グ society system, イ one グ Le XG) through the pressure sensitive adhesive layer that exposes after, with the autoclave of the former making manufacturing of chestnut in 0.5MPa, 50 ℃ pressurization 20 minutes down.Need to prove that above-mentioned applying is table, the back side at non-alkali glass, is the fit polaroid of band pressure sensitive adhesive layer of the mode of cross Nicols state (45 ° of polarization axle: ∠, 135 ° of ∠) with the polarization axle.Under this state, after 500 hours, estimate light leak property with the method shown in following 80 ℃ of dry environment held.The result is shown in table 2.
< evaluation of light leak property >
The MCPD-2000 that Shi Yong Da mound electronics society makes measures each the regional brightness shown in Fig. 3, obtains luminance difference Δ L with following formula *:
ΔL *＝[(b+c+d+e)/4]-a
(wherein, a, b, c, d and e are respectively the brightness of a-quadrant, B zone, C is regional, D is regional and E is regional predefined measuring point (each regional central part 1 place).), as light leak property.Δ L *Value more little, the expression light leak property few more.
Here, above-mentioned weight-average molecular weight is measured the weight-average molecular weight of the polystyrene conversion that (GPC mensuration) obtain for using gel permeation chromatography (GPC) under following condition.
< condition determination >
GPC determinator: eastern ソ one corporate system, HLC-8020
GPC chromatographic column (passing through): eastern ソ one corporate system according to following order
TSK guard column (guard column) HXL-H
TSK gel (gel column) GMHXL (* 2)
TSK gel (gel column) G2000HXL
Measure solvent: THF
Measure temperature: 40 ℃
[table 1]
Figure BSA00000549152800261
[table 2]
Figure BSA00000549152800271
Can be known that by table 2 weather resistance of the polaroid of the band pressure sensitive adhesive layer that obtains among the embodiment is no problem, anti-light leak property is also excellent.Need to prove that more more than preferred amount about the carboxyl-content in embodiment 30, the 1 (methyl) acrylic ester polymer (A), therefore, reproducibility is poor.In addition, about embodiment 31 and embodiment 32, the content of isocyanate-based linking agent is more more than preferred amount, and therefore, reproducibility is poor.
Content about the hydroxyl in comparative example 1, the 2 (methyl) acrylic ester polymer (B) is too much, therefore, and poor durability.Weight-average molecular weight about comparative example 2, the 1 (methyl) acrylic ester polymer (A) is too small, and therefore, weather resistance and reproducibility are poor.Content about the hydroxyl in comparative example 3, the 2 (methyl) acrylic ester polymer (B) is very few, and therefore, gel per-cent (crosslinking degree) is low, poor durability.Weight-average molecular weight about comparative example 4, the 2 (methyl) acrylic ester polymer (B) is too small, so poor durability.Weight-average molecular weight about comparative example 5, the 2 (methyl) acrylic ester polymer (B) is excessive, so weather resistance and reproducibility are poor.Content about comparative example 6, the 2 (methyl) acrylic ester polymer (B) is too much, so poor durability.Content about comparative example 7, the 2 (methyl) acrylic ester polymer (B) is very few, and gel per-cent (crosslinking degree) is low, poor durability.
Utilizability in the industry
Pressure-sensitive-adhesive compsn of the present invention and pressure sensitive adhesive are suitable for the bonding of optics, for example polaroid and phase difference film, and in addition, pressure sensitive adhesion sheet of the present invention is suitable as the pressure sensitive adhesion sheet of used for optical part such as polaroid and phase difference film.

Claims (13)

1. the pressure-sensitive-adhesive compsn is characterized in that,
Contain weight-average molecular weight and be 700,000～2,500,000 the 1st (methyl) acrylic ester polymer (A),
Weight-average molecular weight be 8000～250,000 the 2nd (methyl) acrylic ester polymer (B) and
Linking agent (C),
Said the 2nd (methyl) acrylic ester polymer (B) is 5～40 mass parts with respect to the ratio of said the 1st (methyl) acrylic ester polymers of 100 mass parts (A),
Said the 2nd (methyl) acrylic ester polymer (B) comprises the monomer that has with the functional group (b1) of said linking agent (C) reaction as constituent; And then; Monomeric ratio with said functional group (b1) surpasses 1 quality % and less than 50 quality % in the 2nd (methyl) acrylic ester polymer (B)
The functional group with said linking agent (C) reaction that said the 2nd (methyl) acrylic ester polymer (B) contains is merely said functional group (b1) in fact,
Said the 1st (methyl) acrylic ester polymer (A) do not comprise have with the monomer of the functional group of said linking agent (C) reaction as constituent, or comprise the have functional group monomer of (a1) as constituent, said functional group (a1) compares reactive low with said linking agent (C) with the said functional group (b1) of said the 2nd (methyl) acrylic ester polymer (B).
2. the pressure-sensitive-adhesive compsn is characterized in that,
Contain weight-average molecular weight and be 700,000～2,500,000 the 1st (methyl) acrylic ester polymer (A),
Weight-average molecular weight be 8000～250,000 the 2nd (methyl) acrylic ester polymer (B) and
Linking agent (C),
Said the 2nd (methyl) acrylic ester polymer (B) is 5～40 mass parts with respect to the ratio of said the 1st (methyl) acrylic ester polymers of 100 mass parts (A),
The reactivity that has with said linking agent (C) that comprises said the 2nd (methyl) acrylic ester polymer (B) satisfies the monomer of functional group (b1) of following formula (I) as constituent; And then; Monomeric ratio with said functional group (b1) surpasses 1 quality % and less than 50 quality % in the 2nd (methyl) acrylic ester polymer (B)
And; Said the 2nd (methyl) acrylic ester polymer (B) comprises the monomer of functional group (b2) that the reactivity that has with said linking agent (C) satisfies following formula (I) as constituent with the amount below 1/5 (mass ratio) of monomeric content with said functional group (b1)
Said the 1st (methyl) acrylic ester polymer (A) do not comprise have with the monomer of the functional group of said linking agent (C) reaction as constituent, or comprise the have functional group monomer of (a1) as constituent; Said functional group (a1) compares reactive low with said linking agent (C) with the said functional group (b1) of said the 2nd (methyl) acrylic ester polymer (B)
And the reactivity of linking agent (C): functional group (b2)＜functional group (b1) ... (I).
3. according to claim 1 or claim 2 pressure-sensitive-adhesive compsn is characterized in that, said the 1st (methyl) acrylic ester polymer (A) does not comprise the monomer that has with the functional group of said linking agent (C) reaction as constituent.
4. like claim 1 or 3 described pressure-sensitive-adhesive compsns; It is characterized in that; Said functional group (a1) in said the 1st (methyl) acrylic ester polymer (A) is a carboxyl; Said functional group (b1) in said the 2nd (methyl) acrylic ester polymer (B) is a hydroxyl, and said linking agent (C) is the isocyanate-based linking agent.
5. like claim 2 or 3 described pressure-sensitive-adhesive compsns; It is characterized in that; Said functional group (a1) in said the 1st (methyl) acrylic ester polymer (A) is a carboxyl; Said functional group (b1) in said the 2nd (methyl) acrylic ester polymer (B) is a hydroxyl, and said functional group (b2) is a carboxyl
Said linking agent (C) is the isocyanate-based linking agent.
6. like claim 4 or 5 described pressure-sensitive-adhesive compsns, it is characterized in that said the 1st (methyl) acrylic ester polymer (A) contains 0～15 quality % and contains carboxylic monomer as the monomeric unit that constitutes this polymkeric substance.
7. like arbitrary described pressure-sensitive-adhesive compsn in the claim 4～6, it is characterized in that said the 2nd (methyl) acrylic ester polymer (B) contains 3～40 quality % hydroxyl monomers as the monomeric unit that constitutes this polymkeric substance.
8. like each described pressure-sensitive-adhesive compsn in the claim 4～7; It is characterized in that the content of said isocyanate-based linking agent is 0.1～3.5 normal amount for the NCO of this isocyanate-based linking agent with respect to the amount of the said functional group (b1) in said the 2nd (methyl) acrylic ester polymer (B).
9. pressure-sensitive-adhesive preparation of compositions method; It is each described pressure-sensitive-adhesive method for compositions in the preparation claim 1～8; It is characterized in that; With said the 1st (methyl) acrylic ester polymer (A) and said the 2nd (methyl) acrylic ester polymer (B) blended while, add said linking agent (C) in any stage.
10. pressure sensitive adhesive, it is with crosslinked the forming of each described pressure-sensitive-adhesive compsn in the claim 1～8.
11. pressure sensitive adhesion sheet, it is the pressure sensitive adhesion sheet with base material and pressure sensitive adhesive layer,
It is characterized in that said pressure sensitive adhesive layer is formed by the described pressure sensitive adhesive of claim 10.
12. pressure sensitive adhesion sheet as claimed in claim 11 is characterized in that, said base material is an optics.
13. pressure sensitive adhesion sheet, it has:
2 stripping films with
The mode that contacts with the release surface with said 2 stripping films is by the pressure sensitive adhesive layer of said stripping film clamping,
It is characterized in that said pressure sensitive adhesive layer is formed by the described pressure sensitive adhesive of claim 10.
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