CN102732189A

CN102732189A - Adhesive and adhesive sheet

Info

Publication number: CN102732189A
Application number: CN2012100890292A
Authority: CN
Inventors: 小泽祐树; 又野仁; 荒井隆行; 所司悟
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2011-03-31
Filing date: 2012-03-29
Publication date: 2012-10-17
Also published as: JP2012214545A; TW201245390A; TWI546363B; JP5638439B2; KR20120112020A; KR101899373B1

Abstract

The invention provides an adhesive which is suitable for polarized sheets, and other optical parts, and is excellent in anti-light leakage performance and durability, and an adhesive sheet. The adhesive contains a component which is produced by crosslinking the first (methyl) acrylate polymer (A) with the weight average molecular weight of 500 thousands to 3000 thousands and the second (methyl) acrylate polymer (B) with the weight average molecular weight of 80000 to 300 thousands. In the tensile test, after the adhesive is elongated by 900% for 300 seconds, the stress relaxation rate is above 60%, and the gel fraction is from 30 to 90%.

Description

Tackiness agent and adhesion sheet

Technical field

The present invention relates to tackiness agent and adhesion sheet, particularly relates to the used for optical part as polarized light piece etc., suitable tackiness agent and adhesion sheet.

Background technology

By and large, in the liquid crystal panel, the adhering agent layers that form by the property adhesion agent composition that polarized light piece and polarizer is bonded at glass substrate etc. that use by adhesion more.But the optics of polarized light piece and polarizer etc. the contraction that thermal distortion causes occurs because easy generation such as heat is shunk; Its result; The adhering agent layer of this optics laminated can not be followed this contraction, is created in peel off (what is called is floated, and peels off) at interface; The optic axis of optics of stress of the resulting from during contraction of optics departs from, thereby produces the problem of light leak (so-called hickie).

As the method that prevents this problem; Can give an example, (1) is high with clinging power, and; The good adhering agent layer of form stability is sticking pays the optics in polarized light piece etc.; The method that optics self is suppressed, perhaps, stress was the method for little adhering agent layer when the contraction of optics was used in (2).As the method for (1), that kind shown in patent documentation 1, it is effective using the high adhering agent layer of storage modulus.On the other hand, as the method for (2), it is effective using the flexibly corresponding good adhering agent layer of stress relaxation rate of the energy of deformation of optics.But in the past, the field boundary that form the good adhering agent layer of such stress relaxation rate closed, and was necessary that the glue in this adhering agent layer is joined density to be established low.So, just have the intensity step-down of adhering agent layer from body, durability is the problem of variation.

Thus, in the patent documentation 2 to 4, not to establish the glue couplet density of adhering agent layer low; But with plasticizer, Liquid Paraffin, ammonia ester elastomer etc. makes an addition to the acrylic acid or the like tackiness agent; Make the adhesion agent composition that obtains moderately soft thus; Give stress relaxation rate to adhering agent layer, thus, expect anti-light leak property and weather resistance.

The look-ahead technique document

[patent documentation]

[patent documentation 1] spy opens the 2006-235568 communique

[patent documentation 2] spy opens flat 5-45517 communique

[patent documentation 3] spy opens flat 9-137143 communique

[patent documentation 4] spy opens the 2005-194366 communique

The content of invention

[problem of invention]

But, the adhesion agent composition of interpolation plasticizer or Liquid Paraffin, the adhering agent layer of formation can ooze out this difficult point along with time plasticizer and Liquid Paraffin.And thus, the adhesion weather resistance is a step-down, and the liquid crystal cells of to-be-adhered object is contaminated etc., and various problems are worried by people.In addition, add the adhesion agent composition of ammonia ester elastomer, as want to keep intermiscibility, but the addition of ammonia ester elastomer has the upper limit, the improvement meeting of stress relaxation rate is insufficient.Further, for heavily stressed relaxation rate, like the addition of increase ammonia ester elastomer and the intermiscibility meeting step-down of acrylic compounds sticker, the problem of gonorrhoea etc. takes place.So, in the technology in the past, anti-light leak property and weather resistance that optics fundamentally improves the adhering agent layer that adhesion agent composition formation is arranged are difficult.

The present invention is exactly Given this to produce.The object of the invention just provides a kind of when being applicable to the optics of polarized light piece etc., tackiness agent that two sides of anti-light leak property and weather resistance are good and adhesion sheet.

[solving the means that problem solves]

In order to reach said purpose; The 1st, the present invention, provide a kind of contain weight average molecular weight be 500,000 to 3,000,000 the 1st (methyl) acrylic ester polymer (A) and; Weight average molecular weight is that 8000 to 300,000 the 2nd (methyl) acrylic ester polymer (B) glue joins the composition that forms; In stretching experiment, 900% to stretch and keep the stress relaxation rate after 300 seconds be more than 60%, and the gel ratio is 30 to 90% tackiness agent (technical scheme 1).

The tackiness agent of said invention (technical scheme 1); Be to join the three-dimensional netted structure that forms at glue by low-molecular-weight polymkeric substance (B); For the structure (supposition) that has a plurality of high molecular weight polymers (A) to insert, when big stress relaxation rate is arranged, fixed to some extent gel ratio.Thus, this tackiness agent can be brought into play suitable cohesive force and good stress relaxation rate.Use this tackiness agent, when being applicable to the optics of polarized light piece etc., can obtain all good adhesion sheet of two sides of anti-light leak property and weather resistance with good stress relaxation rate.

In the said invention (technical scheme 1), the ratio to said the 2nd (methyl) acrylic ester polymer (B) of said the 1st (methyl) acrylic ester polymer (A) 100 mass parts is preferably 5 to 50 mass parts (technical scheme 2).

In the said invention (technical scheme 1,2), said the 2nd (methyl) acrylic ester polymer (B) before glue joins as constituent, preferably make the monomer that contains reactive functional group surpass 1 quality %, and 50 quality % is less than (technical scheme 3).

In the said invention (technical scheme 3), said the 2nd (methyl) acrylic ester polymer (B), the glue crosslinking agent (C) that preferably has said reactive functional group crosslinking base possible with having reaction reacts and glue couplet (technical scheme 4).

The 2nd, the present invention provides a kind of adhesion sheet with base material and adhering agent layer, and said adhering agent layer is formed by said tackiness agent (technical scheme 1 to 4) (technical scheme 5).

In the said invention (technical scheme 5), said base material preferred light optic (technical scheme 6)

The 3rd; The invention provides and a kind ofly have 2 pieces of stripping films and by the adhesion sheet of the adhering agent layer of these said 2 pieces of stripping film clampings; And said tackiness agent and said release surface are joined; This tackiness agent sheet is characterised in that said adhering agent layer, (technical scheme 7) that is formed by said tackiness agent (technical scheme 1 to 4).

[effect of invention]

In the tackiness agent of the present invention; Low-molecular-weight polymkeric substance is joined the three-dimensional netted structure of formation by the glue of chemistry; In its three-dimensional netted structure; Have a plurality of high-molecular weight polymers to insert, in bond between the high-molecular weight polymer, glue joins structure (supposition) like intending between the formation high-molecular weight polymer.Thus, this tackiness agent, when big stress relaxation rate is arranged, fixed to some extent gel ratio.Thus, this tackiness agent can be brought into play suitable cohesive force and good stress relaxation rate simultaneously.This tackiness agent with good stress relaxation rate when being applicable to the optics of polarized light piece etc., can obtain all good adhesion sheet of two sides of anti-light leak property and weather resistance.

Description of drawings

The sectional view of the adhesion sheet of [Fig. 1] the 1st embodiment of the present invention.

The sectional view of the adhesion sheet of [Fig. 2] the 2nd embodiment of the present invention.

[Fig. 3] expression has the figure in the mensuration field of the light leak property experiment in the polarized light piece of adhering agent layer.

[Fig. 4] expression has the figure of the metewand of the light leak property experiment (visual) in the mating plate of adhering agent layer.

Embodiment

Below, embodiment of the present invention is described.

(tackiness agent)

The tackiness agent of this embodiment, contain weight average molecular weight (Mw) and be 500,000 to 3,000,000 the 1st (methyl) acrylic ester polymer (A) and, weight average molecular weight is that 8000 to 300,000 the 2nd (methyl) acrylic ester polymer (B) carries out glue and joins the composition that forms.And in this specification sheets, (methyl) propenoate is meant two sides of propenoate and methacrylic ester.Other similar term too.In addition, " polymkeric substance " also contains the notion of " co-polymer ".

Described tackiness agent; Be that 500,000 to 3,000,000 the 1st (methyl) acrylic ester polymer (A), weight average molecular weight are 8000 to 300,000 the 2nd (methyl) acrylic ester polymer (B) and the tackiness compsn of glue crosslinking agent (C) preferably by containing weight average molecular weight; Preferred especially; By the tackiness compsn that further contains silane coupling agent (D), carry out glue and join and form.In the said tackiness agent, in the past, used low-molecular-weight polymkeric substance, and made it carry out chemical glue and join, and form three-dimensional netted structure as plasticizer.Three-dimensional netted structure of the present invention, supposition are that a plurality of high-molecular weight polymers are inserted, and be in bond between the high-molecular weight polymer, thereby the plan that forms between the high-molecular weight polymer joins structure like glue.Thus, the tackiness agent that obtains can be brought into play suitable cohesive force and good stress relaxation rate.Below, describe with regard to said tackiness compsn.

The 2nd (methyl) acrylic ester polymer (B),

(1) make have can with the functional group's (b1) of glue crosslinking agent (C) reaction monomer as constituent, this polymkeric substance (B) contains, the functional group with glue crosslinking agent (C) reaction is merely functional group (b1) in fact,

(2) preferably have with the reactivity of glue crosslinking agent (C) for the functional group's (b1) that satisfies following formula (I) monomer and, preferably have functional group's (b2) monomer that reactivity with glue crosslinking agent (C) satisfies following formula (I) as constituent.

Reactivity with glue crosslinking agent (C): functional group (b2)＜functional group (b1) ... (I)

That is, in the polymkeric substance (B) of preferred (2), functional group (b1) high than functional group's (b2) reactivity with glue crosslinking agent (C) with reactivity glue crosslinking agent (C).

Said (methyl) acrylic ester polymer (A) or (B); It for the carbon number of alkyl (methyl) alkyl acrylate of 1 to 20; Monomer (monomer that contains reactive functional group) with the functional group who reacts with glue crosslinking agent (C), as required, also for using other monomeric co-polymer.And the 1st (methyl) acrylic ester polymer (A) does not preferably contain the monomer with said reactive functional group yet.

As the carbon number of alkyl is (methyl) alkyl acrylate of 1 to 20, (methyl) methyl acrylate of can giving an example, (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) vinylformic acid cyclohexyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) isooctyl acrylate ester, (methyl) vinylformic acid n-certain herbaceous plants with big flowers base ester, (methyl) vinylformic acid n-Lauryl Ester, (methyl) vinylformic acid myristyl ester, (methyl) vinylformic acid cetyl ester and (methyl) stearyl acrylate base ester etc.These can a kind use separately, and use also can combine more than 2 kinds.

On the other hand, as the monomer that contains reactive functional group, intramolecularly has the monomer (monomer that contains hydroxyl) of hydroxyl, and intramolecularly has the monomer (monomer that contains carboxyl) of carboxyl, and intramolecularly has amino monomer (containing amino monomer) to be waited to preferably.

As the monomer that contains hydroxyl, (methyl) vinylformic acid hydroxyalkyl acrylate of (methyl) vinylformic acid 2-hydroxyethyl ester of can giving an example, (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 4-hydroxybutyl ester etc. etc.These can a kind use separately, and use also can combine more than 2 kinds.

As the monomer that contains carboxyl, can exemplified by acrylic, the ethene property unsaturated carboxylic acid of methylacrylic acid, Ba Dousuan, toxilic acid, methylene-succinic acid and citraconic acid etc.These can a kind use separately, and use also can combine more than 2 kinds.

As containing amino monomers, can give an example (methyl) acrylic-amino ethyl ester and (methyl) vinylformic acid n-butyl ester amino-ethyl ester etc.These can a kind use separately, and use also can combine more than 2 kinds.

Further; As said other monomer; Can give an example acrylic acid amides class, (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, (methyl) vinylformic acid N of non-crosslinking of (methyl) propenoate, acrylic amide and USAF RH-1 etc. that aromatic ring is arranged of (methyl) propenoate that the aliphatics ring is arranged, (methyl) phenyl acrylate etc. of (methyl) vinylformic acid cyclohexyl ester etc., (methyl) propenoate, vinyl acetate between to for plastic base ester and the vinylbenzene etc. with tertiary amine groups of the non-crosslinking of N-dimethylaminopropyl ester etc.These can a kind use separately, and use also can combine more than 2 kinds.

And; Contain the monomer of the reactive functional group (a1) that the 1st (methyl) acrylic ester polymer (A) uses and contain the monomer of the reactive functional group (b1) that the 2nd (methyl) acrylic ester polymer (B) uses and the monomeric selection that contains reactive functional group (b2)

Reactive relation according to the glue crosslinking agent (C) that uses decides.Following in detail.

At this, the 2nd (methyl) acrylic ester polymer (B) preferably contains the monomer with said reactive functional group (b1) and surpasses 1 quality %, be limited on it 50 quality % less than.Preferably, contain monomer 5 to 30 quality %, especially preferably contain 10 to 20 quality %, further preferably contain 12 to 18 quality % with said reactive functional group (b1).Have reactive functional group the monomer of (b1) is in the said scope through making to contain, the degree that the glue of the 2nd (methyl) acrylic ester polymer (B) is joined becomes good.With with the combination of the 1st (methyl) acrylic ester polymer (A), can so that the stress relaxation rate of the tackiness agent that arrives in institute more than the definite value, and, make the gel ratio in deciding scope.Its result makes weather resistance and anti-light leak property good simultaneously.In addition, the monomeric amount with reactive functional group (b1) is 1 quality % when following, and the glue of the 2nd (methyl) acrylic ester polymer (B) joins insufficient, and the gel ratio is also low than deciding scope, and the possibility that makes the weather resistance step-down is arranged thus.On the other hand; The monomeric amount that contains reactive functional group (b1) is that 50 quality % are when above; The glue of the 2nd (methyl) acrylic ester polymer (B) joins excessively, and when the gel ratio of the tackiness agent that obtains was higher than deciding scope, the stress relaxation rate had the possibility lower than institute definite value.And, make the monomeric amount that contains reactive functional group (b1) on be limited to 30 quality %, can be so that the anti-light leak property of the adhesion sheet that arrives be more good.

" having only functional group (b1) in fact " in the so-called polymkeric substance (B) described in said (1); Be meant that other functional group's the content with glue crosslinking agent (C) reaction will be the reactive degree (this field boundary closes, polymkeric substance (B) repetition of the polymkeric substance of (1) (B) and (2)) that does not hinder functional group (b1) and glue crosslinking agent (C).That is, preferred especially the 2nd (methyl) acrylic ester polymer (B) does not contain the monomer (monomer that contains reactive functional group (b2)) that has than the reactive low functional group (b2) of said functional group (b1) and glue crosslinking agent (C) as constituent.But, contain during field boundary that the monomer of reactive functional group (b2) contained as constituent closes, as mass ratio, be for containing the amount of monomeric amount below 1/5 of reactive functional group (b1), the preferred especially amount below 1/10.

The monomeric mass ratio with reactive functional group (b2) that the 2nd (methyl) acrylic ester polymer (B) contains, as surpassing 1/5 o'clock of the monomeric amount contain reactive functional group (b1), the weather resistance of the adhering agent layer that obtains just has the possibility of step-down.Reactive functional group (b2) in the 2nd (methyl) acrylic ester polymer (B) is as too much; Will be in the intravital reactive functional group of three-dimensional netted structure (b2) that forms residue in a large number, the intermiscibility of this three-dimensional netted tectosome and the 1st (methyl) acrylic ester polymer (A) will change (supposition).Its result, Hai Si (Haze) value is closed with regard to the field boundary that has rising.In addition, in a large amount of remaining three-dimensional netted tectosomes of reactive functional group (b2), insertion can be by restriction (supposition) exceedingly with the mobility of the 1st (methyl) acrylic ester polymer (A) of this three-dimensional netted tectosome.Its result, the stress relaxation rate of the tackiness agent that obtains is lower than institute's definite value, and it is that the field boundary of variation closes that weather resistance is arranged.

Further; The field boundary that the tackiness compsn of this embodiment contains silane coupling agent (D) closes; Silane coupling agent (D) reacts with the reactive functional group (a1) (particularly carboxyl) of the 1st (methyl) acrylic ester polymer (A); Carry out bonding (supposition) with high-molecular weight the 1st (methyl) acrylic ester polymer (A), the adherence of tackiness agent that obtains thus and to-be-adhered object ground glass substrate etc. will become good.The superfluous occasion of the monomer with reactive functional group (b 2) that the 2nd (methyl) acrylic ester polymer (B) contains; The alkoxysilyl of silane coupling agent (D) etc.; Also also react, bonding (supposition) also takes place with low-molecular-weight the 2nd (methyl) acrylic ester polymer (B) with the reactive functional group (b2) (special carboxyl) of the 2nd (methyl) acrylic ester polymer (B).Its result, the adherence of the tackiness agent that obtains and the glass substrate of to-be-adhered object etc. also can variation, and thus, the weather resistance of adhering agent layer has the possibility of step-down.

At this; The carbon number of alkyl is (methyl) alkyl acrylate of 1 to 20, and has and can carry out polymerization, the polymerized form of the 2nd (methyl) acrylic ester polymer (B) that obtains with the functional group's of glue crosslinking agent (C) reaction monomer; At random co-polymer also can, block copolymer also can.

In this embodiment, described the 2nd (methyl) acrylic polymer (B) can a kind uses separately, and use also can combine more than 2 kinds.

The weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is 8000 to 300,000, preferred 10,000 to 200,000, preferred especially 50,000 to 100,000.That is, the 2nd (methyl) acrylic ester polymer (B) is the low-molecular weight polymer composition.And the weight average molecular weight in this specification sheets is the value of the polystyrene conversion of gel permeation chromatography (GPC) method mensuration.The weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is as in said scope, and the tackiness compsn of this embodiment will form distinctive three-dimensional netted structure, can contribution be arranged to good stress relaxation rate.That is, as the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) be 8000 less than, will be difficult to obtain good three-dimensional netted structure.On the other hand; The weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) was above 300,000 o'clock; With the intermiscibility of the 1st (methyl) acrylic ester polymer (A) etc. be step-down; The insertion of the polymkeric substance (A) in the three-dimensional netted tectosome that polymkeric substance (B) forms will be insufficient, and the gel ratio just has the possibility lower than deciding scope.Its result, the tackiness agent that obtains is that weather resistance and reusability close with regard to the field boundary that variation is arranged.

The 1st (methyl) acrylic ester polymer (A); Preferably; Do not contain monomer with the functional group who reacts with glue crosslinking agent (C) as constituent; Perhaps contain the low monomer with reactive functional group (a1) glue crosslinking agent (C) of the said functional group (b1) who has than the 2nd (methyl) acrylic ester polymer (B), and preferred especially, do not contain as constituent and have than monomer said functional group (b1) and reactive high functional group glue crosslinking agent (C) as constituent.

The 1st (methyl) acrylic ester polymer (A) does not contain the monomer with the functional group who reacts with glue crosslinking agent (C) and can yet.But, as contain the monomer (containing reactive functional group (a1) monomer) that has than the reactive low reactive functional group (a1) of the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B), there is further preferred field boundary to close.In the said polymkeric substance (A) as contain reactive functional group (a1); Can promote the reaction of the 2nd (methyl) acrylic ester polymer (B) and glue crosslinking agent (C); Perhaps, the field boundary that silane coupling agent (D) is used closes, the reactive functional group (a1) of the 1st (methyl) acrylic ester polymer (A) and this silane coupling agent (D) reaction; The adhesion weather resistance to the glass surface of liquid crystal cells etc. of the tackiness agent that obtains possibly further suit, and has preferred field boundary and closes.

The 1st (methyl) acrylic ester polymer (A) contains the monomeric field boundary with said reactive functional group (a1) and closes, and its amount is generally below the 20 quality %, is preferred below the 15 quality %, and is preferred for especially below the 10 quality %.As contain the monomeric amount of reactive functional group (a1) and surpass when being 20 quality %, it is too high that the glass translocation of the 1st (methyl) acrylic ester polymer (A) moves temperature (Tg), and the stress relaxation rate of the tackiness agent that obtains might be lower than institute's definite value.And from the viewpoint that the reusability of tackiness agent is given, the monomeric amount 15 quality % that contain reactive functional group (a1) are following for preferred.

In addition; The monomeric comparison of reactive functional group (b1) that contains with the 2nd (methyl) acrylic ester polymer (B); The monomeric ratio in the 1st (methyl) acrylic ester polymer (A) that the 1st (methyl) acrylic ester polymer (A) contains with reactive functional group (a1), than the 2nd (methyl) acrylic ester polymer (B) contain to have a monomeric ratio in the 2nd (methyl) acrylic ester polymer (B) of reactive functional group (b1) little of preferred.Thus; Reactive functional group (a1) that the 1st (methyl) acrylic ester polymer (A) contains and glue crosslinking agent (C) and reaction be suppressed, reactive functional group (b1) and glue crosslinking agent (C) that the 2nd (methyl) acrylic ester polymer (B) contains just possibly carry out certain reaction.The stress relaxation rate of the tackiness agent that obtains thus, and gel ratio will be in institute's definite value.

The 1st (methyl) acrylic ester polymer (A), the monomer that does not contain identical or the functional group more than it of reactive functional group (b1) with reactivity and the 2nd (methyl) acrylic ester polymer (B) of glue crosslinking agent (C) at its intramolecularly is for preferred.But if the field boundary that contains closes, the monomer with this functional group is to be preferred below the 1 quality % in polymkeric substance (A) at intramolecular amount, is preferred below the special 0.5 quality %.Like this monomeric amount as surpassing 1 quality %, the 2nd (methyl) acrylic ester polymer (B) that should preferentially carry out and glue crosslinking agent (C) and reaction hindered possible arranged.Its result, will can not get fixed stress relaxation rate.

At this, the carbon number of alkyl is (methyl) alkyl acrylate of 1 to 20, the polymerized form of the 1st (methyl) acrylic ester polymer (A) that obtains with the monomer polymerization that contains reactive functional group, at random co-polymer also can, block copolymer also can.

In this embodiment, described the 1st (methyl) acrylic ester polymer (A) can a kind uses separately, and use also can combine more than 2 kinds.

The weight average molecular weight 500,000 to 3,000,000 of the 1st (methyl) acrylic ester polymer (A) is preferably 700,000 to 2,500,000, is preferably 1,000,000 to 2,000,000 especially.That is, the 1st (methyl) acrylic ester polymer (A) is the high molecular weight polymers composition.The weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is in said scope the time; The insertion meeting of the 1st (methyl) acrylic ester polymer (A) of the three-dimensional netted structure that forms to the 2nd (methyl) acrylic ester polymer (B) is good; Glue joins structure like the plan more than 2 molecules of this polymkeric substance (A); Polymkeric substance (A) is with the state with degree of freedom to a certain degree (supposition) in bond.In addition, polymkeric substance (A) as said, has the big molecular weight of comparison, between the three-dimensional netted tectosome that polymkeric substance (B) forms, keeps glue couplet state like the plan on one side, Yi Bian as molecular chain high degree of freedom is arranged also.Thus, the tackiness agent of formation, have fixed stress relaxation rate and gel ratio, have suitable cohesive force and good stress relaxation rate simultaneously.Its result, this tackiness agent, anti-light leak property is good, and in addition, the adhesion weather resistance under the hot conditions is also abundant, can prevent to float and peel off etc.

At this, the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) be 500,000 less than the time, the gel ratio of the tackiness agent that obtains is a step-down, weather resistance and reusability have the possibility of variation.In addition, the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) surpasses at 3,000,000 o'clock, and with the intermiscibility variation that the 2nd (methyl) acrylic ester polymer (B) waits, the stress relaxation rate of the tackiness agent that obtains has than low possible of institute definite value.

To the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of the 2nd (methyl) acrylic ester polymer (B), 5 to 50 mass parts are preferred, and 5 to 40 mass parts are further preferred, and 10 to 30 mass parts are preferred for especially.

With said ratio; From the tackiness agent that the tackiness compsn that contains the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) obtains; The 2nd (methyl) acrylic ester polymer (B) (low-molecular weight polymer) is between glue crosslinking agent (C); Form three-dimensional netted structure; To this three-dimensional netted structure, the above structure that forms that inserts of 2 molecules of the 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) is for joining structure (supposition) with glue like the bound plan of the state that degree of freedom is to a certain degree arranged between the polymer (A).Thus, the tackiness agent that obtains, have simultaneously fixed stress relaxation rate and gel ratio.Thus, the tackiness agent weather resistance and the anti-light leak property that obtain are good.

As glue crosslinking agent (C), can preferably enumerate the isocyanates glue crosslinking agent, epoxies glue crosslinking agent, ethylenimine class glue crosslinking agent, metal-chelating class glue crosslinking agent etc.

The isocyanates glue crosslinking agent contains polyisocyanate compounds at least.As the aliphatic polymeric isocyanate of the aromatic poly-isocyanate of polyisocyanate compounds, the benzyl of can giving an example support vulcabond, methyl diphenylene diisocyanate, p-Xylol group diisocyanate etc., cyclohexylidene vulcabond etc., different fluorine and the ester lopps polymeric polyisocyanate of ketone vulcabond and hydrogenation methyl diphenylene diisocyanate etc. etc.; And the biuret body of compound; Isocyanuric acid ester; Further, the affixture of the compound that contains low molecular activity hydrogen of terepthaloyl moietie, Ucar 35, NSC 6366, TriMethylolPropane(TMP) and castor-oil plant wet goods etc.

As the epoxies glue crosslinking agent; Can give an example 1, two (N, the N '-diglycidyl amino methyl) hexanaphthenes of 3-, N; N; N ', N '-four glycidyl group m-p-Xylol base diamines, ethylene glycol bisthioglycolate glycidyl ether, 1,6-pinakon diglycidyl ether, TriMethylolPropane(TMP) diglycidyl ether, diglycidylaniline and diglycidyl amine etc.

As ethylenimine class glue crosslinking agent; The diphenyl methyl-4 of can giving an example; 4 '-two (1-azacyclopropane methane amides), trimethylolpropane tris β-ethylenimine propionic ester, tetramethylol methane three β-ethylenimine propionic ester, toluene 2,4-two (1-azacyclopropane methane amide), triethylene melamines, two different xylylene 1-(2-methyl ethylenimine), three 1-(2-methyl ethylenimine) phosphine, trimethylolpropane tris β-(2-methyl ethylenimine) propionic ester etc.

In the metal-chelating class glue crosslinking agent, it is the chelate compound of aluminium, zirconium, titanium, zinc, iron and tin etc. that atoms metal is arranged,, be preferred from performance aluminium chelate compound.As the aluminium chelate compound, the diisopropoxy aluminium list oleyl alcohol acetylacetate of can giving an example, the two oleyl alcohol acetylacetates of single aluminum isopropoxide, single aluminum isopropoxide list oleic acid list ethyl acetoacetic acid salt, diisopropoxy aluminium list bay acetylacetate, diisopropoxy aluminium list stearyl acetylacetate and diisopropoxy aluminium list iso stearyl acetylacetate etc.

The amount of glue crosslinking agent (C); For the crosslinking base of this glue crosslinking agent (C) (for example; NCO) with the amount of the reactive functional group (b1) (for example, hydroxyl) of the 2nd (methyl) acrylic ester polymer (B), is generally 0.05 to 5 normal amount; Preferred 0.1 to 3.5 normal amount, preferred especially 0.3 to 1.0 normal amount.The amount of said crosslinking base be 0.05 equivalent less than field boundary close, the gel ratio of the tackiness agent that obtains be 30% less than, the possibility that can not bring into play sufficient cohesive force is arranged.In addition, the amount of said crosslinking base is more than 0.1 equivalent, and when particularly 0.3 equivalent was above, the weather resistance of the tackiness agent that obtains can be further good.On the other hand, the amount of said crosslinking base is 3.5 equivalents when following, and the reusability of the tackiness agent that obtains is good.Further, the amount of said crosslinking base is 1.0 equivalents when following, and glue crosslinking agent (C) can prevent preferentially that to the contribution that is formed with of the three-dimensional netted structure of polymkeric substance (B) glue of polymkeric substance (A) from joining (supposition).Its result, the tackiness agent stress relaxation rate that obtains is good.

In addition, in this embodiment,, be the glue crosslinking agent of consistent kind with reactive relation of two sides of reactive functional group (b1) and reactive functional group (a1) as glue crosslinking agent (C), multiple type also can and use.The viewpoint that is easy to control of the three-dimensional netted structure that forms from the 2nd (methyl) acrylic ester polymer (B); For example as only with the isocyanates glue crosslinking agent; As the functional group; The preferred glue crosslinking agent that only uses a kind further preferably as compound, only uses 1 glue crosslinking agent preferred for especially.

At this; As glue crosslinking agent (C) and (methyl) acrylic ester polymer (A) and the monomeric combination that contains reactive functional group (B); Close for the field boundary of isocyanates glue crosslinking agent at glue crosslinking agent (C); Monomer as the reactive functional group that contains polymkeric substance (A) (a1) serves as preferred with the monomer that contains carboxyl, as the monomer of the reactive functional group that contains polymkeric substance (B) (b1), serves as preferred with monomer that contains hydroxyl or the monomer that contains amino.

On the other hand; Glue crosslinking agent (C) closes for the field boundary of epoxies glue crosslinking agent or ethylenimine class glue crosslinking agent or metal-chelating class glue crosslinking agent; Monomer as the reactive functional group that contains polymkeric substance (A) (a1); With the monomer that contains hydroxyl serves as preferred, as the monomer of the reactive functional group that contains polymkeric substance (B) (b1), serves as preferred with the monomer that contains carboxyl.

Flexibility from the key of formation between glue crosslinking agent (C) and the polymkeric substance (B); And glue joins the stability of reaction; Further, the reactive base of polymkeric substance (A) carries out practical reaction with silane coupling agent (D), the high contributive viewpoint of the adhesion weather resistance of the tackiness agent that obtains thus; Glue crosslinking agent (C) serves as preferred with the isocyanates glue crosslinking agent; The monomer that contains the reactive functional group (a1) of polymkeric substance (A) serves as preferred with the monomer that contains carboxyl, and reactive functional group (b1) monomer that contains polymkeric substance (B) serves as preferred with the monomer that contains hydroxyl, and does not use the monomer that contains reactive functional group (b2) preferred for especially.

The tackiness compsn of this embodiment, preferred, further contain silane coupling agent (D).As contain this silane coupling agent (D); The 1st (methyl) acrylic ester polymer (A) closes for the field boundary that contains carboxylic and have; The carboxyl reaction of organic reaction property base 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 the surface of the to-be-adhered object of glass substrate etc.Thus, the field boundary that for example polarized light piece is fitted in liquid-crystalline glasses unit etc. closes, and the adherence between tackiness agent and the liquid-crystalline glasses unit can be more good

As this silane coupling agent (D), for intramolecularly has the silicoorganic compound of an alkoxysilyl at least,, and photopermeability is arranged with good with the intermiscibility of tackiness agent composition, for example in fact transparency for suitable.The addition of such silane coupling agent (D), to the 1st (methyl) acrylic ester polymer (A) 100 mass parts, 0.01 to 0.5 mass parts is preferred, particularly 0.05 to 0.3 mass parts is preferred.

As silane coupling agent (D) can the exemplified by vinyl Trimethoxy silane, vinyltriethoxysilane, methyl allyl acyloxypropyl trimethoxysilane etc. contain the silicon compound of polymerizability unsaturated group; The silicon compound that the epoxy structure is arranged of 3-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.; The 3-TSL 8330, the silicon compound that contains amino of N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane etc.; 3-r-chloropropyl trimethoxyl silane, 3-isocyanic ester propyl-triethoxysilicane etc.These can a kind use separately, and use also can combine more than 2 kinds.

In the said tackiness compsn; As required; Can add the normally used various additives of acrylic acid or the like tackiness agent, for example tackiness imparting agent, antioxidant, UV light absorber, light stabilizer, softening agent, filling agent, charged preventor and specific refractory power adjustment agent etc.

Said adherence composition when the 1st (methyl) acrylate polymer (A) and the 2nd (methyl) acrylate polymer (B) mix, can add glue crosslinking agent (C) and silane coupler as required (D) on section rank arbitrarily.

As preferred concrete example, (methyl) acrylic ester polymer (A) and (B), they be respectively by common radical polymerization come synthetic.(methyl) acrylic ester polymer (A) and polymerization (B) can be used polymerization starter as required, make with solution polymerization process etc.As the polymerization solvent, the acetic acid ethyl ester of can giving an example, acetic acid n-butyl ester, acetic acid isobutyl, toluene, acetone, hexane, methyl ethyl ketone etc. also can more than 2 kinds and be used.

As polymerization starter, the azo compound of can giving an example, organo-peroxides etc. also can more than 2 kinds and be used.As azo compound, can give an example 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1; 1 '-azo two (hexanaphthene 1-nitrile), 2,2 '-azo two (2,4-dimethyl-nitrile), 2; 2 '-azo two (2,4-dimethyl-4-methoxyl group nitrile), dimethyl-2,2 '-azo two (2 Methylpropionic acid), 4; 4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-hydroxymethyl propionitrile), 2,2 '-azo two [2-(2-tetrahydroglyoxaline 2-yl) propane] etc.

As organo-peroxide; The card acid t-butyl ester (t-Block チ Le パ one オキシネオデカノエ one ト) that the benzoyl peroxide, peroxo-phenylformic acid t-butyl ester, hydrogen phosphide cumene, peroxide two dimethyl isopropyl esters, peroxide two carbonic acid two n-propyl diesters, peroxide two carbonic acid two (2-ethoxyethyl group) ester, peroxide of can giving an example is new, peroxide are than crust sour t-butyl ester (t-Block チ Le パ one オキシ PVC バレ one ト), (3; 5,5-trimethylammonium ketopentamethylene base) superoxide, two propionyl superoxide and diacetyl superoxide etc.

Then, polymkeric substance that obtains (A) and solution (B) mix, and add the dilution solvent.Thereafter, add glue crosslinking agent (C) and silane coupling agent as required (D), thorough mixing just can obtain the tackiness compsn (coating solution) with the solvent dilution.

The dilution of tackiness compsn is processed the diluting solvent that coating solution is used, the aliphatic hydrocarbon of can give an example hexane, heptane, hexanaphthene etc.; The halohydrocarbon of the aromatic hydrocarbons of toluene, YLENE etc., methylene dichloride and ethylene dichloride etc., the alcohol of methyl alcohol, ethanol, propyl alcohol, butanols, 1-methoxyl group 2-propyl alcohol etc.; The ketone of acetone, methyl ethyl ketone, 2-amylalcohol, different fluorine and ketone, ketopentamethylene etc.; The ester of acetic acid ethyl ester, acetic acid butyl ester etc.; The cellosolve kind solvent of ethyl cellosolve etc. etc.

As the concentration viscosity of synthetic coating solution like this, as long as in the possible scope of coating, have no particular limits, it is selected according to circumstances to suit.For example, the concentration of tackiness compsn can be 10 to 40 quality %.And when obtaining coating solution, the interpolation of diluting solvent etc. is not a prerequisite, and the tackiness compsn just can not add diluting solvent for being coated with possible viscosity etc.This field boundary closes, and the tackiness compsn remains untouched and just can be used as coating solution

Described tackiness agent forms for said tackiness compsn glue joins.The glue of said tackiness compsn joins, and carries out through heat treated.And, this heat treated, can double as drying treatment during by the volatilizations such as dilution solvent of tackiness compsn carry out.

The field boundary that carries out heat treated closes, Heating temperature, and preferred 50 to 150 ℃, particularly 70 to 120 ℃ for more preferably.In addition, do heat-up time, served as preferred with 30 seconds to 3 minutes, and special 50 seconds to 2 minutes is preferred.Further, after the heat treated, it is (for example, 23 ℃, preferred for especially during the maturation about 1 to 2 week 50%RH) to be arranged on normal temperature.

Described heat treated (and maturation) joins the 2nd (methyl) acrylic ester polymer (B) glue by glue crosslinking agent (C), thereby forms three-dimensional netted structure (supposition).And; It is not direct chemical bond that above the 1st (methyl) acrylic polymer (A) of 2 molecules is arranged in its three-dimensional netted structure; Perhaps only have and only follow few chemical bond to insert to form, (A) is in bond for this polymkeric substance, thus form intend like glue join structure (supposition).In addition, the 1st (methyl) acrylic ester polymer (A) closes for the field boundary that contains carboxyl, the 1st (methyl) acrylic ester polymer (A) and silane coupling agent (D) reaction, and the adhesion weather resistance to the glass surface of liquid crystal cells etc. of the tackiness agent that obtains can further improve.

Carrying out 900% in the stretching experiment of the tackiness agent of this embodiment and stretch, keep the stress relaxation rate after 300 seconds, is more than 60%, preferred more than 62%.And this stretching experiment is not have base material etc., but only carry out with adhering agent layer.The tackiness agent that forms from described material has said big stress relaxation rate, and this tackiness agent demonstrates good stress relaxation rate, and two sides of anti-light leak property and weather resistance are good.

In addition, the tackiness agent of this embodiment carries out 900% and stretches in stretching experiment, keep the stress relaxation rate after 100 seconds, is preferred more than 50%, and special is preferred more than 52%.

Said stretching experiment specifically, is thickness 500 μ m, wide 10mm, and the shaping tackiness agent of long 75mm (measurement range wherein is 20mm), at 23 ℃, under the environment of 50%RH, with the speed that 200mm/ divides, 900% stretches carries out.In addition, said stress relaxation rate is calculated with following formula.

Stress relaxation rate (%)={ stress after (stress after second maintenance of the stress-300 after 900% stretching is straight)/900% stretches directly } * 100

In addition, the tackiness agent of this embodiment, when stretching with the condition identical with said stretching experiment, until fracture, elongation serves as preferred with elongation more than 3000% particularly for preferred more than 1500%.

Further, according to the stress after 900% stretching directly of said stretching experiment, is preferred below the 10N, preferred below the 1.5N for especially.Stress after the 900% stretching constraint just is more little, and the stress that takes place during to-be-adhered object (for example, polarized light piece) distortion will be more little, and thus, anti-light leak property is just high more, thereby is preferred.On the other hand, the lower value 0.2N of the stress after the 900% stretching constraint just is above preferred for especially, and particularly 0.5N is above is preferred.Maximum stress was that low field boundary closes, and it is possible of variation that weather resistance is arranged.

The gel ratio of the tackiness agent of this embodiment is 30 to 90%, preferred 40 to 80%, preferred especially 45 to 75%.The gel ratio, when promptly the degree that joins of glue was this scope, the three-dimensional netted structure that the glue of the 2nd (methyl) acrylic ester polymer (B) joins can form well, and tackiness agent is that two sides of anti-light leak property and weather resistance are good.And, the gel ratio of tackiness agent, the value of (between aging time through after) during for sticking paying.Specifically, be that the tackiness compsn is applied and stripping film, after the heat treated, 23 ℃, carry out 7 days gel ratios after the keeping under the environment of 50%R H.The gel ratio of tackiness agent, before the process, its value changes between aging time.From such viewpoint, whether close through unclear field boundary between aging time, can be again, at 23 ℃, carry out keeping in 7 days under the environment of 50%RH after, the gel ratio gets final product when becoming said scope.

More than the tackiness agent of explanation be preferably as used for optical part, for example, be used for polarized light piece and polarizer and adhesion, perhaps the adhesion of polarized light piece (polarized light film) and polarizer (phase-contrast film) and glass substrate suits.The adhering agent layer that said tackiness agent forms; Stress relaxation rate is very good; The field boundary that the dimensional change of to-be-adhered object is big closes; The stress that its dimensional change produces can be absorbed loose by adhering agent layer, so be difficult to when to-be-adhered object is peeled off for a long time, the light leak when in described optics, using just can effectively be prevented.That is, the tackiness agent of this embodiment, when being used for optics, the two can reach anti-light leak property and weather resistance.

(adhesion sheet)

That kind shown in Figure 1, the adhesion sheet 1A of the 1st embodiment with order from bottom to top, is stripping film 12, the base material 13 of the adhering agent layer 11 of the release surface laminated of stripping film 12 and adhering agent layer 11 laminated and constituting.

In addition, that kind as shown in Figure 2, the adhesion sheet 1B of the 2nd embodiment, 2

pieces stripping film

12a, 12b, by this stripping film 12a of 2 pieces, the adhering agent layer 11 that 12b seizes on both sides by the arms constitutes, this adhering agent layer and this stripping film of 2 layers release surface join.And the release surface of the stripping film in this specification sheets is meant the face that separability is arranged in the stripping film, has implemented the face of lift-off processing and even without carrying out lift-off processing, but demonstrates the face of separability.

Adhesion sheet 1A, the adhering agent layer 11 of any of 1B join the tackiness agent that forms by described tackiness compsn glue to constitute.

Adhering agent layer 11 thickness, according to adhesion sheet 1A, the application target of 1B determines, is generally 5 to 100 μ m; The scope of preferred 10 to 60 μ m, for example, optics; The field boundary of the adhering agent layer of particularly using as polarized light piece closes, and with 10 to 50 μ m, serves as preferred with 10 to 30 μ m particularly.

Base material 13 has no particular limits, and the thing of the substrate sheets use of the adhesion sheet that can be used as usually can use.Can exemplify except that the optics that needs, use the woven or the nonwoven of the fiber of artificial silk, acrylic acid, polyester etc.; The stationery of last matter paper, glassine paper, impregnation paper and coated paper etc.; The metal forming of aluminium and copper etc.; The foaming body of ammonia ester foaming body and foam polyethylene etc.; PETG; Polybutylene terephthalate (PBT); The polyester film that gathers naphthoic acid ethanol ester etc.; The cellophane of triacetyl cellulose etc.; Polyurethane film; Polyethylene film; Polypropylene film; Polychlorostyrene is for vinyl film; The inclined to one side vinyl film of polychlorostyreneization; The polyvinyl alcohol film; Ethylene-vinyl acetate base ester co-polymer film; Polystyrene film; Polycarbonate film; The acrylic resin film; Gather the bornylene based resin film; The plastic sheeting of cyclic olefin resins film etc.; These the duplexer more than 2 kinds etc. can.Plastics film, an axial compression prolong or two axial compressions are prolonged and can be used.

As the optical component may, for example the polarizing plate (polarizing film), a polarizer, a retardation plate (phase difference film), viewing angle compensation films, brightness enhancement films, improved contrast liquid crystal polymer films, and films.Polarized light piece wherein (polarized light film) shrinks from being easy to, and dimensional change is big, the viewpoint of anti-light leak property, as the use of the tackiness agent (said adhering agent layer 11) of this embodiment to as if suitable.

The thickness of base material 13, different according to its kind, for example the field boundary of optics closes, and is generally 10 μ m to 500 μ m, preferred 50 μ m to 300 μ m.

As stripping film 12; 12a; 12b, the polyvinylidene film of can giving an example, PP SHEET FOR OPP TAPE, polybutylenes film, polyhutadiene film, poly-methyl pentene film, polychlorostyrene for vinyl film, chloro ethylene copolymer film, pet film, gather naphthoic acid ethanol ester film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate base ester film, ionic polymer resin film, ethene (methyl) acrylic acid copolymer compound film, ethene (methyl) acrylic ester copolymerization thing film, polystyrene film, polycarbonate film, Kapton, fluorine resin film etc.In addition, these glue couplet film also can use.Further, these laminate film also can.

In the release surface of said stripping film (face that particularly contacts), carry out lift-off processing for preferred with adhering agent layer 11.The stripper that in lift-off processing, uses, the alcohol acids of can giving an example, type siloxane, fluoride compound, unsaturated polyester class, polyolefins, the stripper of wax class.

To stripping

film

12,12a, the thickness of 12b has no particular limits, and is generally about 20 to 150 μ m.

Said adhesion sheet 1A makes, and is on stripping film 12 release surface, contains the coating of the solution (coating solution) of said tackiness compsn, and heat treated after adhering agent layer 11 forms, is carried out the range upon range of of base material 13 on this adhering agent layer 11.Preferably be provided with maturation during thereafter.

And, the condition of heat treated and maturation such as said.

In addition; The manufacturing of said adhesion sheet 1B; Be on the release surface of a stripping film 12a (perhaps 12b); The described coating solution that contains the tackiness compsn is coated with, carries out after heat treated forms adhering agent layer 11, the release surface of another stripping film 12b (perhaps 12a) is overlapped on adhering agent layer 11.

As the method for the coating of said coating solution, the roller coating method of can giving an example, scraper coating method, roller coating method, scraper coating method, pressurization coating method, intaglio plate coating method etc.

At this, for example, when making the liquid crystal watch showing device that is made up of liquid crystal cells and polarized light piece, the base material 13 as adhesion sheet 1A uses polarized light piece, and the stripping film 12 of this adhesion sheet 1A is peeled off, and gets final product at the adhering agent layer that exposes 11 applying liquid crystal cells.

In addition, for example, between liquid crystal cells and polarized light piece in the manufacturing of the liquid crystal watch showing device of configuration phase difference plate; As an example; At first, the stripping film 12a (perhaps 12b) with adhesion sheet 1B peels off the polarizer of on the adhering agent layer 11 that adhesion sheet 1B exposes, fitting then.Then, will use the stripping film 12 of the adhesion sheet 1A of polarized light piece to peel off as base material 13, the adhering agent layer that exposes 11 of adhesion sheet 1A be fitted with said polarizer.Further, the stripping film 12b (perhaps 12a) with another side peels off from the adhering agent layer 11 of said adhesion sheet B, and the adhering agent layer that exposes 11 of adhesion sheet 1B is fitted with liquid crystal cells.

Above adhesion sheet 1A; The stress relaxation rate of the adhering agent layer 11 of 1B is very good; For example the field boundary as the adhesion of polarized light piece is closed; It is loose that the distortion of polarized light piece and the stress that produces can be absorbed by adhering agent layer 11, thus, can bring into play good anti-light leak property and high weather resistance (supposition).

The embodiment of more than explaining, just in order more easily to understand the present invention, the present invention is only for scheduling this.Each key element of said embodiment record ground comprises all design alterations and the equivalent that belong to technical scope of the present invention.

For example, the stripping film 12 of adhesion sheet 1A dispenses also passable, the stripping film 12a among the adhesion sheet 1B, and arbitrary side of 12b can omit.

[embodiment]

Below, with embodiment etc. the present invention further being specified, scope of the present invention is not limited in these embodiment etc.

(embodiment 1)

1. the modulation of polymkeric substance (A)

To having stirrer, TM, also flowing in the reaction vessel of water cooler, dripping device and nitrogen ingress pipe; Add vinylformic acid n-butyl ester 97.0 mass parts; Vinylformic acid 3.0 mass parts, acetic acid ethyl ester 200 mass parts, and 2; 2 '-azobis isobutyronitrile 0.08 mass parts, the air in the said reaction vessel is replaced with nitrogen.Stir in this nitrogen atmosphere gas bottom, reaction soln is warming up to 60 ℃, after the reaction in 16 hours, be cooled to room temperature.At this, the portion of the solution that obtains to be carried out GPC with following method measure, the generation of the polymkeric substance of weight average molecular weight 1,500,000 (A) obtains confirming.

2. the modulation of polymkeric substance (B)

To having stirrer, TM also flows water cooler; In the reaction vessel of dripping device and nitrogen ingress pipe, add vinylformic acid n-butyl ester 85.0 mass parts, vinylformic acid 2-hydroxyethyl ester 15.0 mass parts; Acetic acid ethyl ester 200 mass parts, 2,2 '-azobis isobutyronitrile 0.16 mass parts; And 2 mercapto ethanol 0.3 mass parts, the air in the said reaction vessel is used nitrogen replacement.Stir in this nitrogen atmosphere gas bottom, the limit is warmed up to 70 ℃ with reaction soln, after the reaction in 6 hours, is cooled to room temperature.At this, the portion of the solution that obtains to be carried out GPC with following method measure, the generation of the polymkeric substance of weight average molecular weight 60,000 (B) is identified.

3. the modulation of tackiness compsn

After polymkeric substance (A) 100 mass parts (solids component scaled value) that obtain in the said operation (1) and polymkeric substance (B) 15 mass parts (solids component scaled value) that in said operation (2), obtain are mixed; As glue crosslinking agent (C); Add benzyl support vulcabond (TDI class) affixture (Japanese polyurethane corporate system, trade(brand)name " can be reined in anti-(コロネ one ト) L ") 2.21 mass parts of the TriMethylolPropane(TMP) of the hydroxyl 0.6 normal amount that is equivalent to polymkeric substance (B).At last,, add 3-glycidoxypropyltrime,hoxysilane (chemical company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ") 0.2 mass parts, fully stir, obtain the diluting soln of tackiness compsn as silane coupling agent (D).

At this, the proportioning of this tackiness compsn is as shown in table 1.And the contracted notation of table 1 record etc. as follows.

[polymkeric substance (A) and (B)]

BA: vinylformic acid n-butyl ester

AA: vinylformic acid

HEA: vinylformic acid 2-hydroxyethyl ester

4HBA: vinylformic acid 4-hydroxybutyl ester

[plasticizer]

Big (アデカサイザ one) C-8 of Ah 's jam: trimellitate class plasticizer (tri trimellitate (2-ethylhexyl) ester) (Asahi Electro-Chemical Co. Ltd's system, trade(brand)name " big (the アデカサイザ one) C-8 of Ah 's jam ")

[glue crosslinking agent (C)]

The isocyanates glue crosslinking agent

Can rein in anti-(コロネ one ト) L: the benzyl support vulcabond affixture (Japanese polyurethane corporate system, trade(brand)name " can be reined in anti-(コロネ one ト) L ") of TriMethylolPropane(TMP)

Its (タケネ one ト) D-110N of Ta Kaina: the XDI affixture of TriMethylolPropane(TMP) (Mitsui Chemicals urethane corporate system, trade(brand)name " Ta Kaina its (タケネ one ト) D-110N ")

The epoxies glue crosslinking agent

TETRAD-X:N, N, N ', N '-four glycidyl group m-p-Xylol base diamines (gas chemical company of Mitsubishi system, trade(brand)name " TETRAD-X ")

[silane coupling agent (D)]

KBM403:3-glycidoxypropyltrime,hoxysilane (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 ")

Stripping film (the Lin Deke corporate system of the lift-off processing that the single face of pet film is carried out with the type siloxane stripper; SP-PET3811; Thickness: the coating of the diluting soln of the tackiness compsn that obtains above carrying out on the lift-off processing face 38 μ m); Dried thickness is 25 μ m, and this coating is carried out with knife coater, and 90 ℃ are carried out 1 minute heat treated and form adhering agent layer.

Then; To attach that polarized light film forms by having the disk liquid crystal layer; Polarized light film and visual angle enlarge the integrated polarized light piece of film fits in adhering agent layer, adhering agent layer and disk liquid crystal layer is joined, at 23 ℃; Carry out maturation in 7 days under the 50%RH, obtain having the polarized light piece of adhering agent layer.

(embodiment 2 to 13, comparative example 1 to 5)

Each monomeric kind and ratio except the formation of tackiness compsn; Plasticizer; The kind of glue crosslinking agent and silane coupling agent and addition; And the ratio of components of polymkeric substance (A) and polymkeric substance (B) becomes beyond that kind shown in the table 1, has the manufacturing of the polarized light piece of adhering agent layer equally with embodiment 1.

At this, described weight average molecular weight (Mw) is with the weight average molecular weight of gel permeation chromatography (GPC) with the polystyrene conversion of following condition mensuration (GPC mensuration).

< condition determination >

GPC determinator: Tosoh company corporate system, HLC-8020

GPC post (passing through): Tosoh company corporate system by following order

TSK?guard?column?HXL-H

TSK?gel?GMHXL(×2)

TSK?gel?G2000HXL

Measure solvent: THF

Measure temperature: 40 ℃

(experimental example 1) (mensuration of gel ratio)

The polarized light piece that uses in the making of the polarized light piece with adhering agent layer that will in embodiment or comparative example, use is changed; Stripping film (the Lin Deke corporate system of lift-off processing has been carried out in use with the type siloxane stripper to the single face of pet film; SP-PET3801; Thickness: 38 μ m), make the adhesion sheet.Specifically, be obtain in the manufacturing processed with embodiment or comparative example by stripping film/adhering agent layer (thickness: on the adhering agent layer that exposes of the constituting body that 25 μ m) forms that said stripping film is range upon range of, be that adhering agent layer and lift-off processing face side are joined.Thus, the adhesion sheet that is made up of stripping film/adhering agent layer/stripping film is made.

The adhesion sheet that obtains at 23 ℃, carries out maturation in 7 days under the condition of 50%RH.Thereafter, this adhesion sheet is made into the sample of 80mm * 80mm, and its adhering agent layer is wrapped with polyester net (net size 200), only the quality of tackiness agent is used the precision balance weighing.At this moment quality is as M1.

Then, the tackiness agent with said polyester net newspaper is wrapped up at room temperature carries out 24 hours dippings in (23 ℃) acetic acid ethyl ester.Thereafter tackiness agent takes out, 23 ℃ of temperature, under the environment of relative humidity 50%, carry out 24 hours air-dry, carry out 12 hours dryings in the further 80 ℃ baking oven.Only the quality of dried tackiness agent is carried out weighing with precision balance.At this moment quality is as M2.Gel ratio (%) is with (M2/M1) * 100 expression.The result is as shown in table 2.

(experimental example 2) (mensuration of optical property)

As measuring sample, use with at the adhesion sheet of the mensuration of gel ratio and same adhesion sheet (maturation in 7 days has been over).About the adhering agent layer of this adhesion sheet, with Hai Si (Haze) appearance (Japanese electric look industrial system, NDH2000), by JIS K7105 mensuration Hai Si (Haze) value (%) (also slightly being called Hz (%)).The result is as shown in table 2.And the scope of preferred Hai Si (Haze) value is 0 to 5%.

(experimental example 3) (durability evaluation)

With the polarized light piece that obtains in embodiment or the comparative example, (obtain the wild super cutter of institute's corporate system of making, PN1-600) be adjusted into 233mm * 309mm size with cutting device with adhering agent layer.Stripping film is peelled off, and pays in non-alkali glass (Corning Incorporated's system, hawk XG) between the adhering agent layer that exposes is sticking, after this, in the made autoclave of the former making of chestnut, carries out at 0.5MPa, under 50 ℃, carries out pressurization in 20 minutes.

, put into the environment of 80 ℃ exsiccant durable conditions under, observe with 10 times of reading lenses after 500 hours thereafter.Cosmetic variation is with following benchmark.The result is as shown in table 2.

◎: in 4 limits, no problem

In zero: 4 limit, the position no problem more than from the peripheral end to 0.6mm

*: at least 1 limit on 4 limits, the position more than from the peripheral end to 0.6mm has and floats, peel off, foaming, the outward appearance of the sticker that the 0.1mm of striped etc. is above is unusual

(experimental example 4) (experiment of light leak property)

The polarized light piece with adhering agent layer that in embodiment or comparative example, obtains (obtains the wild super cutter of institute's corporate system of making, PN1-600) is adjusted into the sample adjustment of 233mm * 309mm size with cutting device.Stripping film is peeled off, and fitting between the adhering agent layer that exposes is non-alkali glass (Corning Incorporated's system, hawk XG), afterwards, in the made autoclave of the former making of chestnut, at 0.5MPa, under 50 ℃, carries out pressurization in 20 fens.And, said applying, in the table of non-alkali glass, the polarizing axis that make the polarized light piece with adhering agent layer is Niccol cross state (45 ° of polarizing axis: ∠, 135 ° of ∠).At this state, after carrying out under 80 ℃ of dry environments placing in 250 hours, 23 ℃, carry out under the environment of 50%RH placing in 2 hours, this as sample, is carried out the evaluation of light leak property with following method for expressing.Example is in shown in the table 2 as a result.

< light leak property evaluation: Δ L* >

MCPD-2000 with big tomb electronics corporation system measures the lightness L* in each field shown in Fig. 3 in the said sample, and luminosity equation Δ L* asks with following formula,

ΔL*＝[(b+c+d+e)/4]-a

(still, a, b, c, d and e, their A fields, B field, C field, the lightness in the measuring point of predesignating in D field and E field (each place of the central authorities in each field)) is as light leak property.The value of Δ L* is more little, and light leak is few for more.And, L*max, the lightness of the maximum in the said all areas.

< light leak property evaluation: visual >

Said sample is arranged on (the logical industry corporate system of electricity, HF-SL-A312LC, illumination: 26 at flat head lamp; 000Lux, brightness: 10,000cd) above; With two-dimentional chroma-luminance meter (but Buddhist nun's card Minolta corporate system; CA-2000) scoop up shadow, (but Buddhist nun's card Minolta corporate system CA-S20w) is transformed to the Luminance Distribution image with resolving software.The Luminance Distribution image of the sample that obtains is estimated based on metewand shown in Figure 4.

(experimental example 5) (stretching experiment)

The single face of pet film has been carried out stripping film (the Lin Deke corporate system of lift-off processing with the type siloxane stripper; SP-PET3811) on the lift-off processing face; To in embodiment and comparative example, be coated with by synthetic tackiness compsn; This dried coating thickness will be 25 μ m, carries out heating in 1 minute at 100 ℃, and adhering agent layer forms.Make this adhering agent layer with, to the single face of pet film with the type siloxane stripper carried out lift-off processing another stripping film (the Lin Deke corporate system, lift-off processing face applying SP-PET3801) obtains the sheet of adhering.

Said adhering agent layer is carried out multilayer laminated (aggregate thickness of the adhering agent layer in the said adhesion sheet is 500 μ m, and the stripping film on the top layer of duplexer is stayed), at 23 ℃, 2 weeks of atmosphere gas held of 50% RH.Thereafter, from the multilayer laminated adhesion sheet of said adhering agent layer cut out 10mm wide * the long sample of 75mm, the range upon range of stripping film in top layer of duplexer is peeled off; Sample is installed, make measurement range be 10mm wide * 20mm is long, at 23 ℃; The environment of 50% RH down with the stretching experiment machine (auspicious corporate system difficult to understand, tensilon), draw speed is the 200mm/ branch; On length direction, stretch; Kept 100 seconds when stretching 900%, the stress (N) after keeping in 300 seconds and 1200 seconds, and 900% stress (N) that just stretched is measured.From these mensuration result, calculate the stress relaxation rate (%) after 100 seconds of tackiness agent keeping and kept in 300 seconds after stress relaxation rate (%).The result is as shown in table 2.

[table 1]

Table 1 (continuing)

[table 2]

Table 2 (continuous 1)

Table 2 (continuous 2)

From table 2 can be clear and definite find out that what obtain among the embodiment has in the adhering agent layer polarized light piece, the stress relaxation rate after when 900% of tackiness agent stretches 300 seconds keep is more than 60%, weather resistance and anti-light leak property are all good.On the other hand, in the polarized light piece that obtains in the comparative example with adhering agent layer, the stress relaxation rate after in when 900% of tackiness agent stretches 300 seconds keep be 60% less than, perhaps a certain side is bad for two sides of weather resistance and anti-light leak property.

Utilize possibility on the industry

Tackiness agent of the present invention, for example the adhesion of polarized light piece and polarizer is suitable to optics, and in addition, adhesion sheet of the present invention suits as the adhesion sheet of the used for optical part of polarized light piece and polarizer etc.

The explanation of symbol

1A, the 1B... sheet of adhering

11... adhering agent layer

12,12a, 12b... stripping film

13... base material

Claims

1. tackiness agent is characterized in that:

Contain weight average molecular weight and be 500,000 to 3,000,000 the 1st (methyl) acrylic ester polymer (A),

And weight average molecular weight is that 8000 to 300,000 the 2nd (methyl) acrylic ester polymer (B) glue joins formed composition,

In stretching experiment, make its elongation 900%, keeping the stress relaxation rate after 300 seconds is more than 60%, gel fraction is 30 to 90%.

2. according to the tackiness agent of claim 1, comprising: to said the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of said the 2nd (methyl) acrylic ester polymer (B) is 5 to 50 mass parts.

3. according to the tackiness agent of claim 1, it is characterized in that: said the 2nd (methyl) acrylic ester polymer (B) before glue joins, as constituent, contain surpass 1 quality % and 50 quality % less than the monomer with reactive functional groups.

4. according to the tackiness agent of claim 3, it is characterized in that: said the 2nd (methyl) acrylic ester polymer (B), through with have can with glue crosslinking agent (C) reaction of the crosslinking group of said reactive functional groups reaction, joined by glue.

One kind the adhesion thin slice, comprising: base material and adhering agent layer is characterized in that:

Said adhering agent layer is that each the tackiness agent by claim 1 to 4 forms.

6. according to the tackiness agent thin slice of claim 5, it is characterized in that: said base material is an optics.

7. tackiness agent thin slice comprises:

2 pieces of peeling sheet;

Adhering agent layer by said peeling sheet is seized on both sides by the arms thus, joins with the release surface of said 2 pieces of peeling sheet,

It is characterized in that: said adhering agent layer is formed by each tackiness agent of claim 1 to 4.