CN102732187A

CN102732187A - Adhesive and adhesive sheet

Info

Publication number: CN102732187A
Application number: CN2012100886846A
Authority: CN
Inventors: 又野仁; 荒井隆行; 小泽祐树; 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: TW201245391A; KR20120112086A; KR101899378B1; JP5611880B2; TWI537360B; JP2012214544A

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 (A) with the weight average molecular weight of 8000 to 3000 thousands. In the tensile test, the breakage elongation is above 1500%, 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, and as the tackiness agent and the tackiness agent sheet of the used for optical part of polarized light piece etc.The object of the invention just provides this suitable tackiness agent and adhesion sheet.

Background technology

In general, in the liquid crystal panel, the adhering agent layers that form by the tackiness adhesion agent composition that polarized light piece and polarizer is bonded at glass substrate funeral etc. that use 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 light leak problem of (so-called day shift).

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 to be paid on the optics of polarized light piece etc.; Optics self is suppressed, perhaps, the method for the adhering agent layer that stress is little during the contraction of (2) use optics.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, form the occasion of the good adhering agent layer of such stress relaxation rate, be 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.

[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

Summary of the 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 durability of adhesion is low, the adhesion of the liquid crystal cells are contaminated, these sorts of problems by people worry.In addition, add the adhesion agent composition of ammonia ester elastomer, as want to keep intermiscibility, but the addition of ammonia ester elastomer there is the upper limit, and the inadequate tendency of improvement of stress relaxation rate is arranged.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 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.

In order to reach said purpose; The 1st; The present invention, contain make 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 obtains; The fracture degree of drawing of stretching experiment is more than 1500%, and the gel ratio is 30 to 90%.

The tackiness agent of said invention (technical scheme 1) joins the structure (supposition) that has a plurality of high molecular weight polymers (A) to insert in the three dimensional network that forms for low-molecular-weight polymkeric substance (B) glue, when big fracture degree of drawing is arranged, and 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), to said the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of said the 2nd (methyl) acrylic ester polymer (B) 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 makes the monomer that contains reactive functional group surpass 1 quality %, and 50 quality % are less than (technical scheme 3).

In the said invention (technical scheme 3), said the 2nd (methyl) acrylic ester polymer (B) preferably has and can react with the glue crosslinking agent (C) of the crosslinking base of said reactive functional group reaction and glue joins (technical scheme 4).

The 2nd, the present invention for having the adhesion sheet of base material and adhering agent layer, is characterized by said adhering agent layer, constitutes (technical scheme 5) by said tackiness agent (technical scheme 1 to 4).

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

The 3rd; The present invention is a kind of adhesion sheet, comprises 2 pieces stripping film and the adhering agent layer of being seized on both sides by the arms by said stripping film, thus; The release surface of this adhering agent layer and said 2 pieces stripping film is joined, and it is characterized in that: said adhering agent layer constitutes (technical scheme 7) by said tackiness agent (technical scheme 1 to 4)

[effect of the present 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 this three-dimensional netted structure, inferring has a plurality of high molecular weight polymers to insert, in bond between the high-molecular weight polymer; Thereby between high molecular weight polymers, glue joins structure and is formed like the plan.Thus, this tackiness agent, when big fracture degree of drawing 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.

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 field of the light leak property measuring in the polarized light piece of adhering agent layer.

[Fig. 4] expression is with the figure of the metewand of the light leak property experiment (visual) in the polarized light piece 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; Preferably; Make 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 8000 to 300,000 the 2nd (methyl) acrylic ester polymer (B) and the tackiness compsn of glue crosslinking agent (C), and is preferred especially; The tackiness compsn that further contains silane coupling agent (D) carries out glue and joins and obtain.In the said tackiness agent, in the past, used low-molecular-weight polymkeric substance as plasticizer; Making it carry out chemical glue joins; And form three-dimensional netted structure, and this three-dimensional netted structure, supposition is that a plurality of high molecular weight polymers are inserted; In bond between the high-molecular weight polymer, thus the plan that forms between the high molecular weight polymers joins structure like glue.The tackiness agent that so obtains, when big fracture degree of drawing is arranged, fixed to some extent gel ratio.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) as constituent have can with the functional group's (b1) of glue crosslinking agent (C) reaction monomer, this polymkeric substance (B) contains, and with glue crosslinking agent (C) and the functional group who reacts, is merely functional group (b1) in fact,

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

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); The carbon number of preferred alkyl is (methyl) alkyl acrylate of 1 to 20, have and the functional group's of glue crosslinking agent (C) reaction monomer (monomer that contains reactive functional group) the monomeric co-polymer of other that use as required.And the 1st (methyl) acrylic ester polymer (A) does not preferably contain the monomer with said reactive functional group.

It as the carbon number of alkyl (methyl) alkyl acrylate of 1 to 20; For example, (methyl) methyl acrylate, (methyl) vinylformic acid ethyl ester, (methyl) vinylformic acid propyl diester, (methyl) vinylformic acid n-butyl ester, (methyl) vinylformic acid n-amyl group ester, (methyl) vinylformic acid n-polyhexamethylene, (methyl) 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 n-Hexadecane 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 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 hydroxyalkyl acrylate of (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 give an example vinylformic acid, methylacrylic acid, Ba Dousuan, toxilic acid, methylene-succinic acid, the ethene property unsaturated carboxylic acid of 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, (methyl) vinylformic acid n-butyl ester amino-ethyl 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; (methyl) propenoate that the aliphatics ring is arranged that (methyl) vinylformic acid cyclohexyl etc. is arranged has (methyl) propenoate of the aromatic ring of (methyl) phenyl acrylate etc., and acrylic acid amides is arranged; The acrylic acid amides of the non-crosslinking of USAF RH-1 etc., (methyl) vinylformic acid N; N-dimethyl aminoethyl ester, (methyl) vinylformic acid N, (methyl) propenoate that the uncle of the non-crosslinking of N-dimethylaminopropyl ester etc. is amino; Vinyl acetate between to for plastic base ester, vinylbenzene etc.These can a kind use separately, and use also can combine more than 2 kinds.

And; The 1(methyl) monomer and the 2(methyl with reactive functional group (a1) that use of acrylate polymer (A)) monomer with reactive functional group (b1) that uses of acrylate polymer (B) and the selection that contains the monomer of reactive functional group (b2) are decided by its reactivity with the glue crosslinking agent (C) that uses.Following in detail.

At this, the 2nd (methyl) acrylic ester polymer (B) preferably contains the monomer with said reactive functional group (b1), and its amount surpasses 1 quality %, be limited on it 50 quality % less than.Preferably, contain monomer 5 to the 30 quality % of said reactive functional group (b1), especially preferably contain 10 to 20 quality %, further preferably contain 12 to 18 quality %.Through the monomer that contains reactive functional group (b1) is in the said scope; Just can make the degree of the glue couplet of the 2nd (methyl) acrylic ester polymer (B) become good; With the combination of the 1st (methyl) acrylic ester polymer (A) in; It is big that the fracture degree of drawing of the tackiness agent that obtains becomes, simultaneously, this tackiness agent be easy to have fixed gel ratio.Its result, this tackiness agent weather resistance and stress relaxation rate become good.In addition, as the monomeric amount that contains reactive functional group (b1) is below the 1 quality %, and there just have the glue that makes the 2nd (methyl) acrylic ester polymer (B) to join to be insufficient, and the gel ratio is the possibility below institute's definite value, the weather resistance step-down that can cause thus.On the other hand, the amount that contains the monomer of reactive functional group (b1) is 50 quality % when above, and the 2(methyl is arranged sometimes) glue of acrylate polymer (B) joins excessively, the little occasion of fracture degree of drawing, thus, durability can variation.And, as contain reactive functional group (b1) monomeric amount on be defined as 30 quality %, the anti-light leak property of the adhesion sheet that obtains is good.

The meaning of " functional group of essence is (b1) only " in the polymer of said (1) (B); For with other functional group's content of glue crosslinking agent (C) reaction; As long as for the reactive degree that does not hinder functional group (b1) and glue crosslinking agent (C) is admissible (this occasion, the polymer (B) of the polymer of (1) (B) and (2) repeats).That is, the 2nd (methyl) acrylic ester polymer (B), the reactivity with glue crosslinking agent (C) that does not especially preferably contain than said functional group (b1) as constituent is low functional group (b2) monomer (monomer that contains reactive functional group (b2)).But, having contained the occasion of the monomer of reactive functional group (b2) as constituent, its mass ratio will be the amount below 1/5 of the amount of the monomer that contains base (b1), special amount below 1/10 is preferred.

The 2nd (methyl) acrylic ester polymer (B), as the monomer with reactive functional group (b2) that contains surpasses at 1/5 o'clock of the monomeric amount contain reactive functional group (b1) as mass ratio, the weather resistance of the adhering agent layer that obtains might step-down.Reactive functional group (b2) in the 2nd (methyl) acrylic ester polymer (B) is like many mistakes; The also a large amount of residue of responding property functional group (b2) in the three-dimensional netted tectosome that forms thus; Thus, the intermiscibility that can infer this three-dimensional netted tectosome and the 1st (methyl) acrylic ester polymer (A) can change.Its result, Hai Si (Haze) value has the possibility of rising.In addition, the remaining three-dimensional netted tectosome of reactive functional group (b2) volume, the mobility that makes the 1st (methyl) acrylic ester polymer (A) that inserts this three-dimensional netted tectosome is by restriction exceedingly.Its result has the fracture degree of drawing of the tackiness agent that obtains to diminish, and weather resistance is possible of variation.

Further, the present embodiment, adhesive composition comprising a silane coupling agent (D) of the occasion, the silane coupling agent (D), with the first (meth) acrylate polymer (A) is a reactive functional group (a1 ) (in particular, a carboxyl group) was reacted first with a high molecular weight (meth) acrylate polymer (A) bonding the adhesive agent to obtain the body and being adhered to a glass substrate with excellent adhesion, section 2 (A yl) acrylate polymer (B) containing a reactive functional group (b2) a monomer excess silane coupling agent (D) is an alkoxysilyl group, and also the second (meth) acrylate, ester polymer (B) is a reactive functional group (b2) (particularly a carboxyl group) is reacted with the second low molecular weight (meth) acrylate polymer (B) is bonded.Its result, the adherence variation of tackiness agent that obtains and to-be-adhered object glass substrate etc., this causes, and the weather resistance of adhering agent layer is a step-down.

At this, the carbon number of alkyl is (methyl) alkyl acrylate of 1 to 20, with glue crosslinking agent (C) and monomer polymerization with reactive functional group, the 2nd (methyl) acrylic ester polymer (B) that obtains.Its polymerization methods, for co-polymer at random 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 low-molecular weight polymer.And the weight average molecular weight in this specification is for using the value of the polystyrene conversion that gel permeation chromatography (GPC) method measures.

Weight average molecular weight like the 2nd (methyl) acrylic ester polymer (B) is in said scope, can form the distinctive three-dimensional netted structure of tackiness compsn of this embodiment, and good stress relaxation rate is produced effect.That is, the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) be 8000 less than, can not obtain good three-dimensional netted structure.On the other hand; The weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is as surpassing 300,000; Intermiscibility is a step-down, and the insertion of the polymkeric substance (A) in the three-dimensional netted tectosome that polymkeric substance (B) forms is insufficient, and the gel ratio has the possibility lower than deciding scope.Its result, the weather resistance of the tackiness agent that obtains and reusability variation.

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 have will be low than the monomeric functional group of formation (b1) of the 2nd (methyl) acrylic ester polymer (B) and the reactivity that contains as constituent with glue crosslinking agent (C) functional group (a1), and preferred especially, do not contain than do not have the reactive high functional group's of said functional group (b1) and glue crosslinking agent (C) monomer as constituent.

The 1st (methyl) acrylic ester polymer (A) also can not contain the monomer with the functional group who reacts with glue crosslinking agent (C).But, as contain than the 2(methyl) monomer (contain reactive functional group (a1) and contain monomer) of the reactive low reactive functional group (a1) of the reactive functional group (b1) of acrylate polymer (B), preferred occasion is arranged.The polymer (A), as a reactive functional group containing (a1), can contribute to the second (meth) acrylate polymer (B) and crosslinking agent (C) reaction or a silane coupling agent (D) use of the occasion, the first (meth) acrylate polymer (A) of the reactive functional groups (a1) with the silane coupling agent (D), to give an adhesive such as a liquid crystal cell of the glass durable adhesion of the surface can be further high, preferably occasions.

The 1(methyl) acrylate polymer (A) contains the occasion of the monomer with said reactive functional group (a1), its amount, and below the common 20 quality %, 15 quality % are following to be preferred, special 10 quality % are following to be preferred.The monomeric amount that contains reactive functional group (a1) is when surpassing 20 quality %, and the glass translocation of the 1st (methyl) acrylic ester polymer (A) moves temperature (Tg) can be too high, and the stress relaxation rate of the needs of the tackiness agent that obtains might can not get.And, the viewpoint of the reusability of tackiness agent, the monomeric amount that contains reactive functional group (a1) is serving as preferred below the 15 quality %.

In addition; In the monomeric comparison that contains with the 2nd (methyl) acrylic ester polymer (B) with reactive functional group (b1); The 1st (methyl) acrylic ester polymer (A) contains has a monomeric ratio in the 1st (methyl) acrylic ester polymer (A) of reactive functional group (a1), than being that the monomeric ratio in the 2nd (methyl) acrylic ester polymer (B) with reactive functional group (b1) that contains of the 2nd (methyl) acrylic ester polymer (B) is little of good.Thus, reactive functional group (a1) that the 1st (methyl) acrylic ester polymer (A) suppresses to contain and glue crosslinking agent (C) and reaction, reactive functional group (b1) and glue crosslinking agent (C) that the 2nd (methyl) acrylic ester polymer (B) is contained carry out certain reaction.Thus, the degree of drawing that ruptures in the time of just can obtaining stretching is that the tackiness agent more than 1500% can obtain.

The 1(methyl) acrylate polymer (A); Reactivity in molecule, not contain with glue crosslinking agent (C) is the 2(methyl) the equal or above functional group of reactive functional group (b1) of acrylate polymer (B) serves as preferred; If the occasion that exists; Amount at intramolecular this functional group's monomer; With in polymer (A) to serve as preferred below the 1 quality %, special 0.5 quality % is following to be preferred.This monomeric amount is as surpassing 1 quality %, and the 2nd (methyl) acrylic ester polymer (B) that should preferentially carry out and the reaction of glue crosslinking agent (C) might be hindered.

At this, the carbon number of alkyl is (methyl) alkyl acrylate of 1 to 20, the polymerization methods 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), preferred 700,000 to 2,500,000, preferred especially 1,000,000 to 2,000,000.That is, the 1st (methyl) acrylic ester polymer (A) is high-molecular weight polymer.

Weight average molecular weight like the 1st (methyl) acrylic ester polymer (A) is in the said scope; Can for inserting, the 1st (methyl) acrylic ester polymer (A) of the three-dimensional netted structure that forms become good to the 2nd (methyl) acrylic ester polymer (B); Join structure through glue like the above plan of inserting of this polymkeric substance (A) 2 molecules; Polymkeric substance (A), in bond under the degree of freedom that has to a certain degree.In addition, polymkeric substance (A) as said, has bigger molecule, and under glue couplet state like the plan of the three-dimensional netted tectosome of keeping polymkeric substance (B) formation, molecular chain has the degree of freedom of height.Thus, the tackiness agent of formation, when big fracture degree of drawing is arranged, fixed to some extent gel ratio.Its result, this tackiness agent has suitable cohesive force and has good stress relaxation rate again, thus, and this tackiness agent, anti-light leak property is good, and the adhesion weather resistance under hot conditions is abundant, and float and peeling off etc. just can prevent.

At this, be 500,000 can step-down like the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) less than, the cohesive force of the tackiness agent that obtains, weather resistance and reusability just have variation maybe.In addition, the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is for surpassing at 3,000,000 o'clock, and with the intermiscibility variation of the 2nd (methyl) acrylic ester polymer (B) etc., Hai Si (Haze) is worth rising, is difficult to obtain the stress relaxation rate of needs.

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

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 formed through the three-dimensional netted structure of glue crosslinking agent (C); To three-dimensional netted structure; Insert more than the 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) 2 molecules, be formed for there being under the state of degree of freedom to a certain degree like the bound plan glue join structure between the polymer (A).Thus, the tackiness agent that obtains, when big fracture degree of drawing is arranged, have fixed gel ratio.Its result, this tackiness agent promptly has suitable cohesive force, and good stress relaxation rate is arranged again.Thus, the tackiness agent weather resistance and the anti-light leak property that obtain are good.

As glue crosslinking agent (C), preferred isocyanate class glue crosslinking agent, epoxies glue crosslinking agent, ethylenimine class glue crosslinking agent and metal-chelating class glue crosslinking agent etc.

The isocyanates glue crosslinking agent contains polyisocyanate compounds at least.As polyisocyanate compounds, the aromatic poly-isocyanate of the benzyl of can giving an example support vulcabond, methyl diphenylene diisocyanate, p-Xylol group diisocyanate etc.; The aliphatic polymeric isocyanate of cyclohexylidene vulcabond etc.; Different fluorine and ketone vulcabond; The ester lopps polymeric polyisocyanate of hydrogenation methyl diphenylene diisocyanate etc. etc., and these biuret body and isocyanuric acid ester.The low molecule of terepthaloyl moietie, Ucar 35, dimethyltrimethylene glycol, TriMethylolPropane(TMP) and castor-oil plant wet goods of further can giving an example contains reactant affixture of active hydrogen etc.

As the epoxies glue crosslinking agent, for example, 1; Two (the N of 3-; N '-diglycidyl amino methyl) hexanaphthene, 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 and trimethylolpropane tris β-(2-methyl ethylenimine) propionic ester etc.

In the metal-chelating class glue crosslinking agent, it is aluminium that atoms metal is arranged, zirconium, and titanium, zinc, iron, the chelate compound of tin etc. is 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), to the crosslinking base (for example, NCO) of this glue crosslinking agent (C) be the 2nd (methyl) acrylic ester polymer (B) reactive functional group (b1) (for example; Hydroxyl) amount; Common 0.05 to 5 equivalent, preferred 0.1 to 3.5 equivalent, preferred especially 0.3 to 1.0 equivalent.The amount of said crosslinking base be 0.05 equivalent less than occasion, the gel ratio of the sticker that obtains be 30% less than, can not bring into play sufficient cohesive force.In addition, the amount of said crosslinking base is more than 0.1 equivalent, and more than special 0.3 equivalent, the tackiness agent weather resistance that obtains can become further good.On the other hand, the amount of said crosslinking base is 3.5 equivalents when following, can be so that the reusability of the tackiness agent that arrives is good.Further, the amount of said crosslinking base is below 1.0 equivalents, can make glue crosslinking agent (C) favourable to the formation of the three-dimensional netted structure of polymkeric substance (B), and glue that can polymkeric substance (A) joins and effectively prevented (supposition).Its result, the tackiness agent stress relaxation rate that obtains is good.

In addition, in this embodiment, as glue crosslinking agent (C), as long as reactive relation of two sides of reactive functional group (b1) and reactive functional group (a1) is the glue crosslinking agent of the kind of unanimity, also can various kinds and usefulness.The viewpoint that is easy to control of the three-dimensional netted structure that forms from the 2nd (methyl) acrylic ester polymer (B) just as only using the isocyanates glue crosslinking agent, is preferably used a kind of glue crosslinking agent.

At this; As glue crosslinking agent (C) and (methyl) acrylate polymer (A) and (B) and the combination of the monomer of the reactive functional group that contains separately; At glue crosslinking agent (C) is the occasion of isocyanates glue crosslinking agent; The monomer that contains the reactive functional group (a1) of polymer (A); Can from the monomer that contains carboxyl, select; Reactive functional group (b1) monomer that contains polymer (B) can perhaps contain amino that monomer is selected from the monomer that contains hydroxyl.

On the other hand; Glue crosslinking agent (C) is the epoxies glue crosslinking agent; The occasion of aziridine class glue crosslinking agent or metal-chelating class glue crosslinking agent; The monomer that contains the reactive functional group (a1) of polymer (A) is the monomer that contains hydroxyl; Containing the monomer of the reactive functional group (b1) of polymer (B), serves as preferred with the monomer that contains carboxyl.

From the flexibility of the key that forms between glue crosslinking agent (C) and the polymkeric substance (B) and the viewpoint that glue joins the stability of reaction; Further; The reactive basic reaction that suits with silane coupling agent (D) from polymkeric substance (A); Cohesive force to the tackiness agent that obtains improves resultful viewpoint, and glue crosslinking agent (C) can use the isocyanates glue crosslinking agent, and the monomer of reactive functional group (a1) that will contain polymkeric substance (A) is as the monomer that contains carboxyl; Reactive functional group (b1) monomer that will contain polymkeric substance (B) does not especially preferably use the monomer that contains reactive functional group (b2) as the monomer that contains hydroxyl.

The tackiness compsn of this embodiment, preferred, further contain silane coupling agent (D).As contain this silane coupler (D); The 1(methyl) acrylate polymer (A) has the occasion of carboxyl; Organic reaction base of silane coupler (D) etc. and 1(methyl) carboxyl reaction of acrylate polymer (A); On the other hand, alkoxysilyl of silane coupler (D) etc. works to the surface of the to-be-adhered object of glass substrate etc.Thus, for example polarized light piece is fitted in the occasion of liquid-crystalline glasses unit etc., the adherence between sticker and the liquid-crystalline glasses unit is more good.

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

As the object lesson of silane coupling agent (D), can the exemplified by vinyl Trimethoxy silane, the polymerizability of vinyltriethoxysilane, methyl allyl acyloxypropyl trimethoxysilane etc. contains the silicon compound of unsaturated group; The silicon compound that the epoxy structure is arranged of 3-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.; 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane etc. contain amino silicon compound; The 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; The normally used various additives of acrylic acid or the like tackiness agent, the imparting agent of for example adhering, antioxidant, UV light absorber, light stabilizer, softening agent, filling agent, charged preventor and specific refractory power adjustment agent etc. can be added.

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

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

As polymerization starter, can give an example azo compound, organo-peroxide etc. also can more than 2 kinds and be used.As azo compound, for 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 benzoyl peroxide of can giving an example, 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, the card acid t-butyl ester (t-Block チ Le パ one ォキシネォデカノェ one ト) that peroxide is new, peroxide is than crust sour t-butyl ester (t-Block チ Le パ one ォキシ PVC バレ one ト); (3,5,5-trimethylammonium ketopentamethylene (ヘキサノィ Le) base) superoxide; Two propionyl superoxide, diacetyl superoxide etc.

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

The dilution of tackiness compsn is the used diluting solvent of coating solution, the aliphatic hydrocarbon of can give an example hexane, heptane, hexanaphthene etc.; The aromatic hydrocarbons of toluene, YLENE etc.; The halohydrocarbon of methylene dichloride, ethylene dichloride etc.; The alcohol of methyl alcohol, ethanol, propyl alcohol, butanols, 1-methoxyl group 2-propyl alcohol etc.; Acetone, methyl ethyl ketone, 2 pentanone, the ketone of 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.

The concentration viscosity of synthetic coating solution like this gets final product in the possible scope of coating, has no particular limits, and is according to circumstances suitable selected.The concentration that for example is diluted to the tackiness compsn is 10 to 40 quality %.And when obtaining coating solution, the interpolation of diluting solvent etc. is not a prerequisite, as long as the tackiness compsn is the possible viscosity of coating, diluting solvent does not add also can.This occasion, the adherence composition can directly become coating solution.

Described tackiness agent is that said tackiness compsn carries out glue and joins and to form thing.The glue of said tackiness compsn joins, and can carry out heat treated.And, this heat treated, also double as is handled the volatile dries such as dilution solvent of tackiness compsn simultaneously.

Carry out the occasion of heat treated, heating-up temperature, preferred 50 to 150 ℃, particularly 70 to 120 ℃ for more preferably.In addition, do heat-up time, was divided into preferably in 30 seconds to 3, was divided into preferred to 2 in special 50 seconds.Further, after the heat treated, be set in during the maturation of normal temperature (for example, 23 ℃, 50%R H) about 1 to 2 week preferred for especially.

Described heat treated (and maturation) joins according to glue crosslinking agent (C) the 2nd (methyl) acrylic ester polymer (B) glue, forms fine and close three-dimensional netted structure (supposition).And, having above the 1st (methyl) acrylic ester polymer (A) of 2 molecules directly not to be accompanied by chemical bond in its three-dimensional netted structure or seldom be accompanied by the chemical bond insertion to obtain, (A) is in bond for this polymkeric substance, and glue joined structure like formation was intended.In addition, 1(methyl) acrylate polymer (A) has the occasion of carboxyl, 1(methyl) acrylate polymer (A) and silane coupler (D) reaction, the adhesion durability to the glass substrate of liquid crystal cells etc. of the sticker that obtains can improve.

The fracture degree of drawing of the stretching experiment of the tackiness agent of this embodiment is more than 1500%, and is preferred more than 2000%, preferred especially more than 2500%.And the mensuration of this fracture degree of drawing is not for what follow base material etc. to make independent adhering agent layer is carried out.From the tackiness agent that described material obtains, big fracture degree of drawing is arranged, this tackiness agent shows good stress relaxation rate, and two sides of anti-light leak property and weather resistance become good.

Said stretching experiment, specifically, thickness 500 μ m, wide 10mm, the tackiness agent that long 75mm (wherein, measurement range is 20mm) is shaped, quilt are at 23 ℃, and under the environment of 50%RH, the speed of dividing with 200mm/ stretches.

And, the tackiness agent of this embodiment, when carrying out described stretching experiment, 1500% stress when stretching is 0.1 to 15N for preferred, and 0.3 to 10N is preferred for especially, and 0.5 to 2.5N be preferably further.This stress be 0.1N less than occasion, the cohesive force of sticker is not enough, the durability variation that causes.On the other hand, the stress is more than 15N of the occasion, the stress relaxation ratio adhesive damage resistance, light leakage was likely to deteriorate, in addition, excessive tackiness of causing aggregation becomes lower, the durability may be deteriorated.

Further, the tackiness agent of this embodiment, when carrying out described stretching experiment, the stress when stretching to 1000%, 1500% when stretching, 2000% when stretching or 2500% the ratio of stress when stretching be that 0.5 to 3.5 be that preferably special 0.8 to 2.5 is preferred

The gel ratio of the tackiness agent of this embodiment is 30 to 90%, preferred 40 to 80%, preferred especially 45 to 75%.Like the gel ratio, promptly the degree that joins of glue is in this scope, and it is good to join the three-dimensional netted structure that forms by the glue of the 2nd (methyl) acrylic ester polymer (B), and the anti-light leak property of tackiness agent and two sides of weather resistance are good.And, the gel ratio of tackiness agent, the value of (between aging time through after) during for sticking paying.Specifically, the tackiness compsn is coated with on stripping film, after the heat treated, 23 ℃, under the environment of 50%RH, the gel ratio after the keeping in 7 days.The gel ratio of tackiness agent, before the process, its value is what change between aging time.From such viewpoint, process whether between aging period, not clear occasion again, at 23 ℃, under the environment of 50%RH, after the keeping in 7 days, becomes in the said scope gel ratio and gets final product.

More than the tackiness agent of explanation is suitable as used for optical part, for example, the adhesion of polarized light piece and polarizer, perhaps the adhesion of polarized light piece (polarized light film) and polarizer (phase-contrast film) and glass substrate is suitable.The adhering agent layer that said sticker forms; Stress relaxation rate is very good; The occasion that the change in size of to-be-adhered object is big; The stress that its change in size generates is absorbed loose by sticker; So when being difficult to for a long time peel off from to-be-adhered object, the light leak when said optics uses can prevent with being produced effect.That is, the tackiness agent of this embodiment, when optics used, anti-light leak property and weather resistance two sides can reach.

(adhesion sheet)

That kind shown in Figure 1, the adhesion sheet 1A of the 1st embodiment, order is followed successively by stripping film 12 from bottom to top, the adhering agent layer 11 of stripping film 12 release surface laminated, adhering agent layer 11 range upon range of base materials 13 constitute.

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

pieces stripping film

12a, 12b, this stripping film 12a of 2 pieces, 12b is seizing adhering agent layer 11 on both sides by the arms, and adhering agent layer 11 is in this stripping film 12a of 2 pieces thus, and the release surface of 12b is joined and is constituted.And the release surface of the stripping film in this specification sheets for the face of separability is arranged in the stripping film, and does not implement though implement face and the lift-off processing of lift-off processing, within the face that demonstrates separability also comprises.

Each sheet 1A that adheres, among the 1B, adhering agent layer 11, the tackiness agent that is formed by described tackiness compsn glue couplet constitutes.

The thickness of the adhesive layer 11, adhesive sheet according to 1A, 1B appropriate decisions purpose of use is usually 5 to 100μm, preferably in the range from 10 to 60μm, for example, optical components, in particular is used in the polarizing film with an adhesive layer case, from 10 to 50μm, particularly preferably from 10 to 30μm.

As base material 13, have no particular limits, the thing of the substrate sheets use of common conduct adhesion sheet can use.For example, outside the optics, use the woven or the non-woven fabrics of the fiber of Zantrel, vinylformic acid and polyester etc.; Last matter paper, lamination paper, impregnation paper, the stationery of White Board etc.; Aluminium, the tinsel of copper etc.; Ammonia ester foaming body; The foam of foam polyethylene etc.; Polyethylene terephthalate; Polybutylene terephthalate; The polyester film that gathers naphthoic acid glycol ester etc.; The cellulosefilm of triacetyl cellulose etc.; Polyurethane film; Polyvinylidene film; PP SHEET FOR OPP TAPE; 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 vinyl resin film; Gather the bornylene based resin film; The plastics film of cyclic olefin resins film etc.These the duplexer more than 2 kinds etc.Plastics film, an axial compression prolong or the thing of two axial compression extensions also can.

As the optical components such as polarizing plate (polarizing film), a polarizer, a retardation plate (phase difference film), viewing angle compensation films, brightness enhancement films, color contrast film, liquid crystal polymer film.Polarized light piece (polarized light film) wherein is easy to shrink, and dimensional change is big, and from the viewpoint of anti-light leak property, the object as the tackiness agent (said adhering agent layer 11) of this embodiment forms suits.

The thickness of base material 13, different according to its kind, for example in the occasion of optics, common 10 μ m to 500 μ m, preferred 50 μ m to 300 μ m.

As stripping film 12; 12a; 12b; For example, available polyethylene film, 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 and fluorine resin film etc.In addition, it is also available that these glue joins film.Further, these laminate film also can.

In the release surface of said stripping film (particularly with adhering agent layer 11 and the face that connects), preferably implement lift-off processing.The stripper that uses in the lift-off processing, for example, the stripper of alcohol acids, type siloxane, fluorine class, unsaturated polyester class, polyolefins, wax class.

Stripping

film

12,12a, the thickness of 12b, not special restriction is generally about 20 to 150 μ m.

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

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

In addition; Said adhesion sheet 1B makes; On the release surface of one stripping film 12a (perhaps 12b), contain the coating of said tackiness compsn coating solution, carry out heat treated and glue; After 11 formation of agent layer, the release surface with another stripping film 12b (perhaps 12a) on this adhering agent layer 11 overlaps.

The coating process of said coating solution, for example available beaming roller coating method, scraper coating method, roller coating method, scraper coating method, pressurization coating method, intaglio plate coating method etc.

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

In addition, for example, between liquid crystal cells and polarized light piece; The occasion that the liquid crystal watch showing device of polarizer configuration is made is as an example, at first; The stripping film 12a (perhaps 12b) of adhesion sheet 1B is peeled off, the adhering agent layer that exposes 11 of adhesion sheet 1B is fitted with polarizer.Then, will use the stripping film 12 of the adhesion sheet 1A of polarized light piece to peel off, the adhering agent layer 11 that exposes of adhesion sheet 1A will be fitted with said polarizer as base material 13.Further, from the adhering agent layer 11 of said adhesion sheet 1B another stripping film 12b (perhaps 12a) is peeled off, the adhering agent layer that exposes 11 of adhesion sheet 1B is fitted with liquid crystal cells.

According to

above adhesion sheet

1A, 1B, adhering agent layer 11 stress relaxation rates are very good; For example be suitable for the occasion of the adhesion of polarized light piece; The stress that is produced by the distortion of polarized light piece is absorbed loose by adhering agent layer 11, thus, good anti-light leak and high durability are able to performance.

More than mode is executed in explanation, is more easily to understand for of the present invention, and the present invention is not limited thereto.So disclosed each key element of said embodiment comprises whole design alteration and the equivalents of scope that belongs to technology of the present invention.

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

[embodiment]

Below, come the present invention is further specified with embodiment, of the present inventionly be not limited to this.

(embodiment 1)

1. the modulation of polymkeric substance (A)

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 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 on the limit under this nitrogen atmosphere gas, and reaction soln heats up 60 ℃, after the reaction in 16 hours, is cooled to room temperature.At this, the some 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) is identified.

2. the modulation of polymkeric substance (B)

Have 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 replaced with nitrogen.Stir on the limit in this nitrogen atmosphere gas, and the limit is warming up to 70 ℃ with reaction soln, after the reaction in 6 hours, and cool to room temperature.At this, the some of the solution that obtains is carried out GPC mensuration with following method, and the generation of the polymkeric substance of weight average molecular weight 60,000 (B) is identified.

3. the modulation of tackiness compsn

Said step (1) the resulting polymer (A) 100 parts by mass (solid content conversion value) and, in the step (2) the resulting polymer (B) 15 parts by mass (solid content conversion value) After mixing, as crosslinking agent (C), the polymer (B) is equivalent to 0.6 equivalent amount of hydroxyl trimethylol propane benzyl support diisocyanate (TDI class) adduct (Nippon Polyurethane Co., Ltd., trade name "Le resistant to (CORONATE coat) L ") adding 2.21 parts by mass.At last, as silane coupling agent (D), 3-glycidoxypropyltrime,hoxysilane (chemical company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ") 0.2 mass parts is added, and fully stirs, and obtains the diluting soln of tackiness compsn.

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

[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 (ァデカサィザ one) C-8 of Ah 's jam: trimellitate class plasticizer (three (2 ethylhexyl) trimellitate) (Asahi Electro-Chemical Co. Ltd's system, trade(brand)name " big (the ァデカサィザ 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 ")

Carry out stripping film (the Lin Deke corporate system of lift-off processing with the type siloxane stripper with the single face of pet film; SP-PET3811; Thickness: on the lift-off processing face 38 μ m), the diluting soln of the tackiness compsn that obtains is coated with knife coater, it is 25 μ m that coating will proceed to the dried thickness of film; 90 ℃ of 1 minute heat treated, adhering agent layer forms.

Then, will have that the polarized light film of discoid liquid crystal layer constitutes, polarized light film is fitted with the visual angle incorporate polarized light piece of expansion film; So that adhering agent layer and discoid liquid crystal layer join; 23 ℃, 50%R H carries out maturation in 7 days, obtains the polarized light piece with adhering agent layer.

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

Formation each monomeric kind and ratio with the 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) lists in table 1, except that this changes, with embodiment 1 equally with the manufacturing of the polarized light piece of adhering agent layer.

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

< condition determination >

GPC determinator: Tosoh corporate system, HLC-8020

GPC post (passing through): Tosoh company corporate system with 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)

In embodiment or comparative example; Replace the polarized light piece that uses in the making of the polarized light piece that has adhering agent layer; Stripping film (the Lin Deke corporate system that a face of use pet film obtains with type siloxane stripper lift-off processing; SP-PET3801, thickness: 38 μ m), make the adhesion sheet.Specifically, (thickness: the constituting body that 25 μ m) constitutes exposes on the adhering agent layer that forms the stripping film/adhering agent layer that in the manufacturing processed of embodiment or comparative example, obtains, and said stripping film is folded established, so that lift-off processing face side is joined.Thus, the adhesion sheet of the formation of stripping film/adhering agent layer/stripping film is made into.

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

Then, the tackiness agent of said polyester net bag is at room temperature carried out 24 hours dippings in (23 ℃) acetic acid ethyl ester.Take out tackiness agent thereafter, 23 ℃ of temperature, under the environment of relative humidity 50%, 24 hours are air-dry, carry out 12 hours dryings in the further 80 ℃ baking box.The quality of dried tackiness agent is used the precision balance weighing.The quality of this moment is as M2.Gel ratio (%) is with (M2/M1) * 100 expression.The result lists in table 2.

(experimental example 2) (mensuration of optical property)

As measure sample, adhesion sheet that preparation is used and same adhesion sheet (maturation in 7 days is over) in the mensuration of gel ratio is used.The adhering agent layer of this adhesion sheet, use Hai Si (Haze) appearance (Japanese electric look industrial system, NDH2000), by JIS K7105 mensuration Hai Si (Haze) value (%) (situation about having is Hz (%) slightly).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)

The polarized light piece of the band adhering agent layer that obtains in embodiment or the comparative example, (reed open country makes the super cutter of institute's corporate system, PN1-600) is adjusted into the size of 233mm * 309mm with cutting device.Stripping film is peeled off, and pays in non-alkali glass (Corning Incorporated's system, hawk XG) between the tackiness agent that exposes is sticking, then, in the made autoclave of the former making of chestnut, at 0.5MPa, under 50 ℃, pressurizes 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, from the position no problem more than the peripheral end 0.6mm

*: at least 1 limit on 4 limits,, have and float, peel off, foaming, the outward appearance abnormal problem of the tackiness agent that the 0.1mm of striped etc. is above from the position more than the peripheral end 0.6mm

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

The polarized light piece that has adhering agent layer that will in embodiment or comparative example, obtain, (reed open country makes the super cutter of institute's corporate system, PN1-600) is adjusted into the size of 233mm * 309mm with cutting device.Stripping film is peeled off, and glues between the adhering agent layer that exposes and pays at non-alkali glass (Corning Incorporated's system, hawk XG), afterwards, uses the made baking oven of the former making of chestnut at 0.5MPa, 50 ℃, carries out pressurization in 20 fens.And, said applying, in the table of non-alkali glass, the polarized light piece that has adhering agent layer is that Niccol cross state (45 ° of polarizing axis: ∠, 135 ° of ∠) carries out with the polarizing axis.This state, after 80 ℃ of dry environments were placed in following 250 hours, 23 ℃, the environment of 50%RH was placed in following 2 hours, and this as sample, is carried out the evaluation of light leak property with method shown in following.The result is as shown in table 2.

The evaluation of light leak property: Δ L*＞

Use the MCPD-2000 of big tomb electronics corporation system, the lightness L* in each field shown in Figure 3 in the said sample is measured,, use formula luminosity equation Δ L*

ΔL*＝[(b+c+d+e)/4]-a

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

The evaluation of light leak property: visual＞

Said sample is arranged on flat head lamp (the logical industry corporate system of electricity; HF-SL-A312LC; Illumination: 26; 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 carried out the conversion of Luminance Distribution image with resolving software.The Luminance Distribution image of the sample that obtains, metewand as shown in Figure 4 is estimated.

(experimental example 5) (stretching experiment)

To the one side of pet film with the type siloxane stripper carry out lift-off processing stripping film (Lin Deke corporate system; SP-PET3811) lift-off processing face carries out the coating of synthetic tackiness compsn in embodiment and the comparative example; Making dried coating thickness is 25 μ m; 100 ℃ of heating in 1 minute, adhering agent layer forms.With adhering agent layer, (the Lin Deke corporate system, lift-off processing face SP-PET3801) is fitted, and obtains the sheet of adhering to have carried out another stripping film of lift-off processing with a face of pet film with the type siloxane stripper.

Said adhering agent layer is multilayer laminated, and the aggregate thickness that makes the adhering agent layer in the said adhesion sheet is 500 μ m, and only makes the stripping film on top layer of duplexer residual, and 23 ℃, 2 weeks placed under the atmosphere gas of 50%RH., carry out multilayer laminated adhesion sheet from said adhering agent layer thereafter, cut out 10mm wide * the long sample of 75mm; The range upon range of stripping film in top layer of duplexer is peeled off, load sample make its measurement range be 10mm wide * 20mm is long, 23 ℃; (auspicious corporate system difficult to understand tensilon) stretches with draw speed 200mm/ branch the environment of 50%RH, when measuring 1000% stretching with the stretching experiment machine down; 1500% when stretching, and 2000% when stretching and 2500% stress (N) and maximum stress in when stretching.In addition, stress that will be when stretching with 1000%, 1500% when stretching, 2000% when stretching or 2500% the ratio of stress when stretching calculate.The result is as shown in table 2.

[table 1]

Table 1 (continuing)

[table 2]

Table 2 (continuous 1)

Table 2 (continuous 2)

Can learn that from table 2 in the polarized light piece that has adhering agent layer that obtains among the embodiment, the fracture degree of drawing of tackiness agent is more than 1500%, weather resistance and anti-light leak property all good.On the other hand, in the polarized light piece that has adhering agent layer that obtains in the comparative example, the fracture degree of drawing of tackiness agent is 1500% less than, two sides of weather resistance and anti-light leak property or bad on the one hand.

[utilizing on the industry possibility]

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

[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; It 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 the composition that forms; In stretching experiment, its extension at break degree is more than 1500%, and gel fraction is 30 to 90%.

2. according to the tackiness agent of claim 1, it is characterized in that: 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 is as constituent, comprise surpass 1 quality % and 50 quality % less than the monomer that contains reactive functional group.

4. according to the tackiness agent of claim 3, it is characterized in that: 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.

5. an adhesion thin slice has base material and adhering agent layer, and it is characterized in that: said adhering agent layer is formed by each tackiness agent of claim 1 to 4.

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

One kind the adhesion thin slice, comprising:

2 pieces peeling sheet,

The adhering agent layer that said peeling sheet is seized on both sides by the arms thus, joins with the release surface of said 2 pieces peeling sheet, it is characterized in that: said adhering agent layer is formed by each tackiness agent of claim 1 to 4.