CN102732190B

CN102732190B - Tackiness agent and adhesive sheet

Info

Publication number: CN102732190B
Application number: CN201210089140.1A
Authority: CN
Inventors: 荒井隆行; 又野仁; 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: 2015-11-25
Anticipated expiration: 2032-03-29
Also published as: TWI527870B; JP2012214543A; JP5602670B2; KR101957306B1; TW201245392A; KR20120112099A; CN102732190A

Abstract

There is provided a kind of when being applicable to the optics of polarized light piece etc., all excellent tackiness agent of resistance to light leakage and weather resistance two aspect and adhesion thin slice.When this tackiness agent is stretched, its maximum stress is also larger than stress during fracture or when 4000% stretches, this tackiness agent, be preferably (methyl) more than acrylic ester polymer 50 quality % of 50 ten thousand to 300 ten thousand containing weight average molecular weight, gel fraction is 30 to 90%, particularly, containing the 1st (methyl) acrylic ester polymer (A) that weight average molecular weight is 50 ten thousand to 300 ten thousand, and weight average molecular weight is the composition of the 2nd (methyl) acrylic ester polymer (B) glue connection of 8000 to 30 ten thousand, to the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of (methyl) acrylic ester polymer (B) of the 2nd is preferably 5 to 50 mass parts.

Description

Tackiness agent and adhesive sheet

Technical field

The present invention, relates to tackiness agent and adhesive sheet, particularly relates to tackiness agent suitable in the optics of polarized light piece etc. and adhesive sheet.

Background technology

General, in liquid crystal panel, when polarized light piece and polarizer are bonded at glass substrate, the adhering agent layer using adhesive adhesion agent composition to be formed more.But, the optics of polarized light piece and polarizer etc. can because heat etc. easily produce contraction, there is the contraction that thermal distortion causes, its result, adhering agent layer stacked on this optics can not follow this contraction, thus produces the stripping (what is called is floated, and peels off) at interface, the departing from from optic axis of the optics of the contraction of the string stress cause of optics, the problem of light leak (so-called hickie) can be produced.

As the method preventing this problem, can exemplify, (1) just clinging power is high, and, the adhering agent layer that form stability is excellent glues to be paid in the optics of polarized light piece etc., optics self is made to carry out the method suppressed thus, or, the method for the adhering agent layer that stress is little when (2) use the contraction of optics.As the method for (1), as Patent Document 1, the adhering agent layer using storage modulus high is effective.On the other hand, as the method for (2), the adhering agent layer excellent to the stress relaxation rate that the energy of deformation of optics is flexibly corresponding is used to be effective.But in the past, the Games that form the excellent adhering agent layer of such stress relaxation rate closed, be necessary the glue connection density in this adhering agent layer to establish low.So, just have the Strong degree step-down that adhering agent layer is autologous, weather resistance is the problem be deteriorated.

Thus, in patent documentation 2 to 4, not that the glue of adhering agent layer connection density is established low, but by plasticizer, Liquid Paraffin, ammonia ester elastomer etc. makes an addition to 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 resistance to light leakage and weather resistance.

[look-ahead technique document]

[patent documentation]

[patent documentation 1] JP 2006-235568 publication

[patent documentation 2] Unexamined Patent 5-45517 publication

[patent documentation 3] Unexamined Patent 9-137143 publication

[patent documentation 4] JP 2005-194366 publication

Summary of the invention

[problem of invention]

But, add the adhering agent layer of the formation of the adhesion agent composition of plasticizer or Liquid Paraffin, have and ooze out this difficult point along with the plasticizer of time and Liquid Paraffin.Further, thus, adhesion weather resistance is step-down, and the liquid crystal cells of to-be-adhered object is contaminated etc., these problems worry by people.In addition, adding the adhesion agent composition of ammonia ester elastomer, as wanted to maintain intermiscibility, but can be limited by the upper limit of the addition of ammonia ester elastomer, have the improvement Bu Chong Fen Pour of stress relaxation rate to.Further, in order to heavily stressed relaxation rate, increase the addition of ammonia ester elastomer, with the intermiscibility step-down of acrylic acid or the like tackiness agent, the problem of white Turbid etc. will occur.So, in technology in the past, optics fundamentally improves the resistance to light leakage of the adhering agent layer having adhesion agent composition to be formed and weather resistance is difficult.

The present invention is exactly Given this produce.Object of the present invention is just to provide a kind of when being applicable to the optics of polarized light piece etc., the tackiness agent that two sides of resistance to light leakage and weather resistance are excellent and adhesive sheet.

[solving the means of problem Xie Decision]

For making described object reach, the 1st, the invention provides one when being characterized as stretching, stress when maximum stress is fracture or when 4000% stretches also wants large tackiness agent (technical scheme 1).

The tackiness agent of described invention (technical scheme 1), when significantly stretching, the loose of stress is also possible, and tackiness agent does not in the past have such character.There is the tackiness agent of so excellent stress relaxation rate when being applicable to the optics of polarized light piece etc., the adhesive sheet that two sides of resistance to light leakage and weather resistance are excellent can be obtained.

In described invention (technical scheme 1), preferred weight molecular-weight average be 50 ten thousand to 300 ten thousand (methyl) acrylic ester polymer contain more than 50 quality %, gel ratio is 30 to 90% (technical schemes 2).

Described invention (technical scheme 1,2) in, containing the 1st (methyl) acrylic ester polymer (A) that weight average molecular weight is 50 ten thousand to 300 ten thousand, and weight average molecular weight be 8000 to 30 ten thousand the 2nd (methyl) acrylic ester polymer (B) glue connection form composition, to described 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of described 2nd (methyl) acrylic ester polymer (B) is 5 to 50 mass parts (technical schemes 3).

In described invention (technical scheme 3), described 2nd (methyl) acrylic ester polymer (B) before glue connection, as constituent, containing having the monomer of reactive functional group more than 1 quality %, 50 quality % are less than (technical scheme 4).

2nd, the present invention, for having the adhesive sheet of base material and adhering agent layer, described adhering agent layer, has described tackiness agent (technical scheme 1 to 4) to form (technical scheme 5).

In described invention (technical scheme 5), described base material, preferred light member (technical scheme 6)

3rd, the present invention, the stripping film with 2 pieces and the adhering agent layer having described stripping film to seize on both sides by the arms, connect with the release surface of the stripping film of described 2 pieces thus, described adhering agent layer, has described tackiness agent (technical scheme 1 to 4) to form (technical scheme 7).

[effect of invention]

Tackiness agent of the present invention, when significantly stretching, stress loose is also that possible this tackiness agent does not in the past have.There is the use of the tackiness agent of so excellent stress relaxation rate, when being applicable to the optics of polarized light piece etc., the adhesive sheet that two sides of resistance to light leakage and weather resistance are excellent can be obtained.In addition, be suitable for adhesive sheet of the present invention, the optics that two sides of resistance to light leakage and weather resistance are excellent can be obtained.

Accompanying drawing explanation

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

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

[Fig. 3] represents the figure in the mensuration field of the light leak experiment had in the attached polarized light piece of adhering agent layer.

[Fig. 4] is with the expression figure of the metewand of light leak experiment (visual) in the polarized light piece of adhering agent layer.

Embodiment

Below, embodiments of the present invention are described.

(tackiness agent)

Common tackiness agent, stretching can cause the polymkeric substance orientation in turn in tackiness agent, stress little by little for rising, maximum stress when reaching fracture.But the tackiness agent of present embodiment, during stretching, maximum stress ratio, when during fracture, (Games of 4000% tension fracture closes) or 4000% stretches, the stress of (Games that 4000% stretches does not rupture closes) also wants large.That is, when describing stress-deformation curve, have maximum stress point before fracture, this is the unexistent character of tackiness agent in the past.This can be speculated as, in this tackiness agent, while stretching, and the loose generation of its stress.The tackiness agent with so excellent stress relaxation rate, when being applicable to the optics of polarized light piece etc., can obtain the adhesive sheet that two sides of resistance to light leakage and weather resistance are excellent.

Specifically, the tackiness agent of present embodiment, has and stacked etc. obtains wide 10mm, long 20mm, and the tackiness agent sheet of thickness 500 μm, when the speed of dividing with 200mm/ in stretching experiment carries out 4000% stretching, maximum stress is also larger than stress during fracture or when 4000% stretches.Further, this stretching experiment, not together with base material etc., but only carries out with independent adhering agent layer.

In addition, the tackiness agent of present embodiment, maximum stress is below 10N is preferred, and special below 5N is preferred.Maximum stress is excessive, and the Games having resistance to light leakage to be deteriorated closes.The lower value of this maximum stress, from the viewpoint of weather resistance, more than 0.1N is that preferably particularly more than 0.5N is preferred.

Further, the tackiness agent of present embodiment, maximum stress be than fracture time or 4000% stretch time stress large more than 5% be preferred, large especially more than 10% is preferred.Can infer that this value is larger, the speed of stress relaxation is also faster, and the upper limit has no particular limits, the left and right of usual 200%.

In addition, the tackiness agent of present embodiment, when described condition stretches, until fracture, more than 2000% be preferred stretching, special more than 4000% be stretched as preferred.Further, because the upper limit is not particularly limited, about 40000% is generally.

There is the tackiness agent of described characteristic, preferably, weight average molecular weight (Mw) be 50 ten thousand to 300 ten thousand (methyl) acrylic ester polymer be more than 50 quality %, gel ratio is 30 to 90%, particularly preferably, weight average molecular weight be 50 ten thousand to 300 ten thousand the 1st (methyl) acrylic ester polymer (A) and, weight average molecular weight is the composition of the 2nd (methyl) acrylic ester polymer (B) glue connection of 8000 to 30 ten thousand, to the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of the 2nd (methyl) acrylic ester polymer (B) is 5 to 50 mass parts.Further, in this specification sheets, (methyl) acrylate refers to two sides of acrylate and methacrylic ester.Other similar term too.In addition, " polymkeric substance " concept also containing " co-polymer ".

Described tackiness agent, preferably, the 1st (methyl) acrylic ester polymer (A), weight average molecular weight that to make containing weight average molecular weight be 50 ten thousand to 300 ten thousand are the 2nd (methyl) acrylic ester polymer (B) of 8000 to 30 ten thousand and the tackiness composition of glue crosslinking agent (C), particularly preferably, tackiness composition further containing silane coupling agent (D), carries out glue connection and obtains.In described tackiness agent, use in the past as the low-molecular-weight polymkeric substance of plasticizer, it is made to carry out chemical glue connection, thus form three-dimensional netted structure, this three-dimensional netted structure, supposition has the polymer of multiple high molecular to insert, in bond each other at the polymer of high molecular, thus the plan between the polymkeric substance of formation high molecular is like glue connection structure.Thus, the tackiness agent obtained, during stretching, maximum stress is, also larger than stress during fracture or when 4000% stretches.Its result, this tackiness agent, can play suitable cohesive force and excellent stress relaxation rate.Below, described tackiness composition is described.

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

(1) make the monomer with the functional group (b1) that can react with glue crosslinking agent (C) as constituent, the functional group reacted with glue crosslinking agent (C) that this polymkeric substance (B) contains, be essentially only functional group (b1)

(2) preferably have with the reactivity of glue crosslinking agent (C) for meet the functional group (b1) of following formula (I) monomer and, preferably there is the monomer of the functional group (b2) meeting following formula (I) with the reactivity of glue crosslinking agent (C) as constituent.

With the reactivity of glue crosslinking agent (C): functional group (b2) < functional group (b1) ... (I)

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

Described (methyl) acrylic ester polymer (A) or (B) is, the carbon number with alkyl is (methyl) alkyl acrylate of 1 to 20, has the monomer (monomer containing reactive functional group) of the functional group reacted with glue crosslinking agent (C), as required also other the co-polymer of monomer operable.Further, the 1st (methyl) acrylic ester polymer (A), also preferred as forming monomer not containing having the monomer with described reactive functional radical reaction.

Carbon number as alkyl is (methyl) alkyl acrylate of 1 to 20, (methyl) methyl acrylate can be exemplified, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl, (methyl) vinylformic acid n-amyl group ester, (methyl) vinylformic acid n-polyhexamethylene, (methyl) cyclohexyl acrylate, (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) myristyl base ester, (methyl) vinylformic acid n-Hexadecane ester and (methyl) stearyl acrylate base ester etc.These can a kind be used alone, also can two or more use that combines.

On the other hand, as the monomer containing reactive functional group, there is in molecule the monomer (monomer containing hydroxyl) of hydroxyl, have the monomer (monomer containing carboxyl) of carboxyl in molecule, it is preferred for having amino monomer (monomer containing amino) etc. in molecule.

As the monomer containing hydroxyl, (methyl) hydroxyalkyl acrylates etc. of (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 2-hydroxybutyl ester, (methyl) vinylformic acid 3-hydroxybutyl ester and (methyl) vinylformic acid 4-hydroxybutyl ester etc. can be exemplified.These can a kind be used alone, also can two or more use that combines.

As the monomer containing carboxyl, can the ethene unsaturated carboxylic acid of exemplified by acrylic, methacrylic acid, β-crotonic acid, toxilic acid, methylene-succinic acid and citraconic acid etc.These can a kind be used alone, also can two or more use that combines.

As containing amino monomers, (methyl) acrylic-amino ethyl ester and (methyl) n-butyl amino-ethyl ester etc. can be exemplified.These can a kind be used alone, also can two or more use that combines.

Further, as other monomer described, (methyl) acrylate having aliphatics ring of (methyl) cyclohexyl acrylate etc. can be exemplified; There is (methyl) acrylate of the aromatic ring of (methyl) phenyl acrylate etc., have acrylamide, the acrylamide of the non-crosslinking of Methacrylamide etc.; (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, (methyl) vinylformic acid N, (methyl) acrylate of the tertiary amine groups of the non-crosslinking of N-dimethylaminopropyl ester etc.; Vinyl acetate between to for plastic base ester; Vinylbenzene etc.These can a kind be used alone, also can two or more use that combines.

And, the selection of the monomer with reactive functional group (b1) that the monomer with reactive functional group (a1) used in the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) use and the monomer containing reactive functional group (b2), fixed with reactive relation Lai Decision of the glue crosslinking agent (C) used by it.Following in detail.

At this, the 2nd (methyl) acrylic ester polymer (B), preferably containing the monomer of described reactive functional group (b1), more than 1 quality %, its upper limit be 50 quality % less than.Preferably, monomer 5 to the 30 quality % containing described reactive functional group (b1), particularly preferably containing 10 to 20 quality %, further preferably containing 12 to 18 quality %.Be in described scope by making the monomer containing reactive functional group (b1), the degree that the glue of the 2nd (methyl) acrylic ester polymer (B) is joined becomes good, and with the combination of the 1st (methyl) acrylic ester polymer (A), the stress relaxation rate of the tackiness agent obtained is excellent.In addition, the amount as the monomer containing reactive functional group (b1) is below 1 quality %, and the glue connection of the 2nd (methyl) acrylic ester polymer (B) will be insufficient, and this just has the possibility causing weather resistance step-down.On the other hand, if when the amount of the monomer containing reactive functional group (b1) is more than 50 quality %, the glue connection of the 2nd (methyl) acrylic ester polymer (B) will be excessive, and this will cause the possibility of the laminating adaptability step-down to to-be-adhered object.Further, the upper limit as the amount making the monomer containing reactive functional group (b1) is 30 quality %, and the resistance to light leakage of the adhesive sheet obtained becomes more excellent.

What is called in the polymkeric substance (B) of described (1) " in fact only has functional group (b1) ", refer to and other the functional group that glue crosslinking agent (C) reacts, as long as do not harm functional group (b1) and glue crosslinking agent (C) and reactive amount, (this Games closes, and the polymkeric substance (B) of (1) and the polymkeric substance (B) of (2) repeat) that can contain.But, 2nd (methyl) acrylic ester polymer (B), being not preferred containing the monomer (monomer containing reactive functional group (b2)) that to have than the reactivity of described functional group (b1) and glue crosslinking agent (C) be low functional group (b2) as forming monomer.But closing containing the Games of the monomer with reactive functional group (b2) as constituent, as mass ratio, for the monomer containing reactive functional group (b1) amount less than 1/5 amount, the amount of special less than 1/10 is preferred.

2nd (methyl) acrylic ester polymer (B) is, containing when there is the monomer of reactive functional group (b2), as mass ratio, as exceeded 1/5 of the amount of the monomer containing reactive functional group (b1), the weather resistance of the adhering agent layer obtained is step-down.When reactive functional group (b2) in 2nd (methyl) acrylic ester polymer (B) is too much, can infer that the reactive functional group (b2) in the three-dimensional netted tectosome that formed thus has many residues, the intermiscibility of this three-dimensional netted tectosome and the 1st (methyl) acrylic ester polymer (A) will change.Its result, Hai Si (Haze) value has the Games of rising to close.In addition, also can infer that reactive functional group (b2) is for a large amount of remaining three-dimensional netted tectosome, the mobility inserting the 1st (methyl) acrylic ester polymer (A) of this three-dimensional netted tectosome can exceedingly be limited.Thus, the tackiness agent obtained, during stretching, the Games of stress when having maximum stress is when being not more than fracture or 4000% stretches closes.Its result, what have weather resistance to be deteriorated is passable.

Further, the tackiness composition of present embodiment is that the Games containing silane coupling agent (D) closes, silane coupling agent (D), react with reactive functional group (a1) (particularly the carboxyl) of the 1st (methyl) acrylic ester polymer (A), bonding is carried out with the 1st (methyl) acrylic ester polymer (A) of high molecular, the tackiness agent that will obtain like this with by the adherence of the glass substrate of adhesion etc. become excellent, but, if the 2nd (methyl) acrylic ester polymer (B) is superfluous containing the monomer with reactive functional group (b2), the alkoxysilyl etc. of silane coupling agent (D), also also react with the reactive functional group (b2) (special carboxyl) of the 2nd (methyl) acrylic ester polymer (B), bonding is carried out with low-molecular-weight 2nd (methyl) acrylic ester polymer (B).Its result, being deteriorated with the adherence of to-be-adhered object glass substrate etc. of the tackiness agent obtained, has this to cause, the weather resistance step-down of adhering agent layer.

At this, the carbon number of alkyl be 1 to 20 (methyl) alkyl acrylate be polymerized with the monomer containing the functional group reacted with glue crosslinking agent (C), the polymerized form of the 2nd (methyl) acrylic ester polymer (B) that obtain, random co-polymer also can, block copolymer also can.

In present embodiment, described the 2nd (methyl) acrylic polymer (B), can a kind be used alone, also can two or more use that combines.

The weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is 8000 to 30 ten thousand, preferably 1 ten thousand to 20 ten thousand, particularly preferably 2 ten thousand to 15 ten thousand.That is, the 2nd (methyl) acrylic ester polymer (B) is low-molecular weight polymer composition.Further, the weight average molecular weight in this specification sheets, the value of the polystyrene conversion measured by gel permeation chromatography (GPC) method.

As the 2nd (methyl) acrylic ester polymer (B) weight average molecular weight as described in scope, in the tackiness composition of present embodiment, distinctive three-dimensional netted structure can be formed, to when stretching, the tackiness agent that maximum stress is also larger than stress during fracture or when 4000% stretches is contributive.That is, the weight average molecular weight as the 2nd (methyl) acrylic ester polymer (B) be 8000 less than, good three-dimensional netted structure just can not obtain.On the other hand, if the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is as more than 300,000, intermiscibility step-down, insertion to the polymkeric substance (A) in the three-dimensional netted tectosome of the formation of polymkeric substance (B) is insufficient, has the possibility of the tackiness agent that can not obtain described characteristic.Its result, weather resistance and reusability are deteriorated

1st (methyl) acrylic ester polymer (A), preferably, as constituent not containing the monomer with the functional group reacted with glue crosslinking agent (C), or as constituent contain have than the 2nd (methyl) acrylic ester polymer (B) described functional group (b1) be the monomer of low functional group (a1) with the reactivity of glue crosslinking agent (C), and particularly preferably, as constituent, the monomer not containing the functional group high with the reactivity of glue crosslinking agent (C) had than described functional group (b1).

1st (methyl) acrylic ester polymer (A), also can not containing the monomer with the functional group reacted with glue crosslinking agent (C).But, as containing having the monomer (monomer containing reactive functional group (a1)) with the reactive low reactive functional group (a1) of the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B), preferred Games is also had to close.If reactive functional group (a1) in described polymkeric substance (A), the reaction of the 2nd (methyl) acrylic ester polymer (B) and glue crosslinking agent (C) can be promoted, or, silane coupling agent (D) is closed by the Games used, reactive functional group (a1) and this silane coupling agent (D) of the 1st (methyl) acrylic ester polymer (A) react, the adhesion weather resistance of the glass surface of the liquid crystal cells etc. to the tackiness agent obtained can be made to be further enhanced, so there is preferred Games to close.

1st (methyl) acrylic ester polymer (A) is that the Games containing the monomer with described reactive functional group (a1) closes, its amount, be generally below 20 quality %, below 15 quality % are that preferably special below 10 quality % are preferred.The amount of the monomer containing reactive functional group (a1) is as more than 20 quality %, the glass translocation of the 1st (methyl) acrylic ester polymer (A) moves temperature (Tg) and becomes too high, just likely be difficult to obtain when stretching, the tackiness agent that maximum stress is also larger than stress during fracture or when 4000% stretches.Its result, will produce the stress relaxation rate that the tackiness agent obtained does not reach needs.Further, from the viewpoint of the imparting of the reusability of tackiness agent, the amount of the monomer preferably containing reactive functional group (a1) is preferred with below 15 quality %.

In addition, with the 2nd (methyl) acrylic ester polymer (B) containing the comparing of monomer with reactive functional group (b1), reactive functional group (a1) that what the 1st (methyl) acrylic ester polymer (A) contained have at the ratio of monomer at the 1st (methyl) acrylic ester polymer (A), the ratio in the 2nd (methyl) acrylic ester polymer (B) with the monomer of reactive functional group (b1) preferably contained than the 2nd (methyl) acrylic ester polymer (B) is little.Thus, 1st (methyl) acrylic ester polymer (A) suppresses the reaction of reactive functional group (a1) and the glue crosslinking agent (C) contained, and the reactive functional group (b1) that the 2nd (methyl) acrylic ester polymer (B) contains and glue crosslinking agent (C) will carry out certain reaction.Thus, when can obtain stretching, the good tackiness agent that maximum stress is also larger than stress during fracture or when 4000% stretches.

1st (methyl) acrylic ester polymer (A), preferably in molecule containing being the monomer of the functional group equal or more with the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) with the reactivity of glue crosslinking agent (C), if but close at the Games contained, the amount of the monomer containing this functional group in molecule, be below 1 quality % in polymkeric substance (A) be preferred, special below 0.5 quality % is preferred.The amount of this monomer, as more than 1 quality %, just likely can hinder the reaction of the 2nd (methyl) acrylic ester polymer (B) and the glue crosslinking agent (C) that should preferentially carry out.

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 obtain with the monomer polymerization containing reactive functional group, random co-polymer also can, block copolymer also can.

In present embodiment, described the 1st (methyl) acrylic ester polymer (A), can a kind be used alone, also can two or more use that combines.

The weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is 50 ten thousand to 300 ten thousand, preferably 70 ten thousand to 250 ten thousand, particularly preferably 100 ten thousand to 200 ten thousand.That is, the 1st (methyl) acrylic ester polymer (A) is high-molecular weight polymer composition.

Weight average molecular weight as the 1st (methyl) acrylic ester polymer (A) be as described in scope, the three-dimensional netted structure that 2nd (methyl) acrylic ester polymer (B) is formed, 1st (methyl) acrylic ester polymer (A) well will insert to this three-dimensional netted structure, more than this polymkeric substance (A) 2 molecule, like plan, glue connection constructs, and polymkeric substance (A) is in the state of degree of freedom to a certain degree (presumption) in bond.In addition, polymkeric substance (A), during the large molecular weight of comparison as described, between the three-dimensional netted tectosome that polymkeric substance (B) is formed, can maintain glue like intending and join state, while have high degree of freedom as molecular chain.Thus, during stretching, maximum stress is, also larger than stress during fracture or when 4000% stretches, and obtains good tackiness agent thus.Its result, the tackiness agent of formation, has suitable cohesive force and excellent stress relaxation rate, and thus, this tackiness agent, resistance to light leakage is excellent, and in addition, also have weather resistance of adhering fully under hot conditions, float and stripping etc. just can be prevented.

At this, the weight average molecular weight as the 1st (methyl) acrylic ester polymer (A) be 500,000 less than time, the cohesive force of the tackiness agent obtained can step-down, and weather resistance and reusability just have the possibility of variation.In addition, the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is for more than 3,000,000, can be deteriorated with the intermiscibility of the 2nd (methyl) acrylic ester polymer (B) etc., Hai Si (Haze) value will for rising, and the stress relaxation rate of needs will be difficult to obtain.

To the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of the 2nd (methyl) acrylic ester polymer (B) is 5 to 50 mass parts, preferably 5 to 40 mass parts, particularly preferably 10 to 30 mass parts.

With described ratio, from the tackiness agent that the tackiness composition containing the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) obtains, 2nd (methyl) acrylic ester polymer (B) (low-molecular weight polymer) is by forming three-dimensional netted structure with glue crosslinking agent (C), this three-dimensional netted structure, that more than the 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) 2 molecule inserts and the structure of formation, between polymer (A), glue connection structure like plan bound under the state with degree of freedom to a certain degree.Thus, when obtaining stretching, the good tackiness agent that maximum stress is also larger than stress during fracture or when 4000% stretches.Its result, the tackiness agent obtained, has suitable cohesive force, while can play excellent stress relaxation rate.Thus, the weather resistance that the tackiness agent obtained has and resistance to light leakage excellent.

As glue crosslinking agent (C), isocyanates glue crosslinking agent may be exemplified, epoxies glue crosslinking agent, ethylenimine class glue crosslinking agent, metal-chelating class glue crosslinking agent etc.

Isocyanates glue crosslinking agent, at least containing polyisocyanate compounds.As polyisocyanate compounds, benzyl support vulcabond may be exemplified, methyl diphenylene diisocyanate, the aromatic poly-isocyanate of p-Xylol group diisocyanate etc., the aliphatic polymeric isocyanate of cyclohexylene diisocyanate etc., different fluorine and ketone vulcabond, the ester lopps polymeric polyisocyanate etc. of hydrogenation methyl diphenylene diisocyanate etc., and these biuret body, isocyanuric acid ester, further ethylene glycol, propylene glycol, dimethyltrimethylene glycol, the low molecule active hydrogen of TriMethylolPropane(TMP) and castor-oil plant wet goods contain compound and the affixture etc. of reactant.

As epoxies glue crosslinking agent, may exemplify, 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 diglycidyl base ether, 1,6-hexylene glycol diglycidyl ether, TriMethylolPropane(TMP) diglycidyl ether, diglycidylaniline and diglycidyl amine etc.

As ethylenimine class glue crosslinking agent, diphenyl methyl-4 can be enumerated, 4 '-bis-(1-azacyclopropane methane amide), trimethylolpropane tris β-ethylenimine propionic ester, tetramethylol methane three β-ethylenimine propionic ester, toluene 2,4-two (1-azacyclopropane methane amide), triethylene melamine, two different xylylene 1-(2-methyl-aziridinyl propane), three-1-(2-methyl-aziridinyl propane) phosphine, trimethylolpropane tris β-(2-methyl-aziridinyl propane) propionic acid etc.

In metal-chelating class glue crosslinking agent, having atoms metal to be the chelate compound of aluminium, zirconium, titanium, zinc, iron and tin etc., is preferred from performance aluminium chelate compound.As aluminium chelate compound, diisopropoxy aluminium list oleyl alcohol acetylacetate, single aluminum isopropoxide two oleyl alcohol acetylacetate, 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 acetylacetates etc. can be exemplified.

The amount of glue crosslinking agent (C), the crosslinking base of this glue crosslinking agent (C) (such as, isocyanate group) to the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) (such as, hydroxyl) amount, usual 0.05 to 5 equivalent, preferably 0.1 to 3.5 equivalent, particularly preferably 0.3 to 1.0 equivalent.The amount of described crosslinking base be 0.05 equivalent less than Games close, the gel ratio of the tackiness agent obtained will 30% less than, likely can not play sufficient cohesive force.In addition, the amount of described crosslinking base is more than 0.1 equivalent, and more than special 0.3 equivalent, the weather resistance of the tackiness agent obtained will become excellent further.On the other hand, the amount of described crosslinking base is below 3.5 equivalents, and it is excellent that the tackiness agent obtained obtains reusability.Further, when the amount of described crosslinking base is below 1.0 equivalents, glue crosslinking agent (C) will be made to be formed with contribution only to the three-dimensional netted structure of polymkeric substance (B), can to prevent the glue of polymkeric substance (A) from joining.Its result, the tackiness agent stress relaxation rate obtained is excellent.

In addition, in present embodiment, as glue crosslinking agent (C), when being consistent glue crosslinking agent with reactive pass of two sides of reactive functional group (b1) and reactive functional group (a1), can multiple types using.The control of the three-dimensional netted structure formed from the 2nd (methyl) acrylic ester polymer (B) is easy to viewpoint, such as will as only using isocyanates glue crosslinking agent, only use the glue crosslinking agent of 1 class to be preferred, further, only use a kind of glue crosslinking agent to be particularly preferably.

At this, glue crosslinking agent (C), the combination of (methyl) acrylic ester polymer (A) and (B) monomer containing reactive functional group, the Games being isocyanates glue crosslinking agent at glue crosslinking agent (C) closes, as the monomer of the reactive functional group (a1) containing polymkeric substance (A), prioritizing selection contains the monomer of carboxyl, as the reactive functional group (b1) containing polymkeric substance (B), prioritizing selection contains the monomer of hydroxyl or the monomer containing amino, as the monomer containing reactive functional group (b2) of polymkeric substance (B), prioritizing selection is wanted to contain the monomer of carboxyl.

On the other hand, glue crosslinking agent (C) is epoxies glue crosslinking agent, the Games of ethylenimine class glue crosslinking agent or metal-chelating class glue crosslinking agent closes, as the monomer of the reactive functional group (a1) containing polymkeric substance (A), prioritizing selection contains the monomer of hydroxyl, the monomer containing reactive functional group (b1) of polymkeric substance (B), prioritizing selection contains the monomer of carboxyl, as the monomer containing reactive functional group (b2) of polymkeric substance (B), the monomer containing hydroxyl is preferred.

From the flexibility of the key formed between glue crosslinking agent (C) and polymkeric substance (B), the stability of glue connection reaction, further, the reactive base of polymkeric substance (A) and silane coupling agent (D) is made to carry out suitable reaction, to the high contributive viewpoint of the weather resistance of the tackiness agent obtained, glue crosslinking agent (C) uses isocyanates glue crosslinking agent, the monomer of the reactive functional group (a1) containing polymkeric substance (A) uses the monomer containing carboxyl, the monomer of the reactive functional group (b1) containing polymkeric substance (B) uses the monomer containing hydroxyl, the monomer containing reactive functional group (b2) is not used to be particularly preferably.

The tackiness composition of present embodiment, further preferably containing silane coupling agent (D).As containing this silane coupling agent (D), 1st (methyl) acrylic ester polymer (A) is for having the Games conjunction of carboxyl, the carboxyl reaction of the organic reaction base of silane coupling agent (D) etc. and the 1st (methyl) acrylic ester polymer (A), on the other hand, the alkoxysilyl etc. of silane coupling agent (D) works to the surface of the to-be-adhered object of glass substrate etc., thus, the Games that such as polarized light piece is bonded to liquid-crystalline glasses unit etc. closes, and the adherence between tackiness agent and liquid-crystalline glasses unit can be more good.

As this silane coupling agent (D), for having the silicoorganic compound of an alkoxysilyl in molecule at least, good with the intermiscibility of tackiness agent composition, and photopermeability material, such as well transparent in fact.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 that preferably special 0.05 to 0.3 mass parts is preferred.

As the object lesson of silane coupling agent (D), there is vinyltrimethoxy silane, vinyltriethoxysilane, the polymerizability unsaturated group of methyl allyl acyloxypropyl trimethoxysilane etc. contains silicon compound, 3-glycidoxypropyltrime,hoxysilane, 2-(3, 4-epoxycyclohexyl) silicon compound with epoxy structure of ethyl trimethoxy silane etc., 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, the amino of N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane etc. contains silicon compound, 3-r-chloropropyl trimethoxyl silane and 3-isocyanic ester propyl-triethoxysilicane etc.These, can a kind be used alone, also can two or more use that combines.

In described tackiness composition, as required, normally used various additive in acrylic acid or the like tackiness agent, imparting agent of such as adhering, antioxidant, UV light absorber, light stabilizer, softening agent, filling agent, charged preventor, refractive index adjusters etc. can add.

Described tackiness composition, while 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) mix, at arbitrary section Bands, glue crosslinking agent (C) can be added and adds silane coupling agent (D) as required thus manufacture.

As preferred concrete example, (methyl) acrylic ester polymer (A) and (B), they can have common radical polymerization to modulate respectively.The polymerization of (methyl) acrylic ester polymer (A) and (B), uses polymerization starter as required, uses solution polymerization process.As polymerization solvent, such as, acetic acid ethyl ester, acetic acid n-butyl ester, i-butyl base ester, toluene, acetone, hexane and methyl ethyl ketone etc., but also two or more is also used.

As polymerization starter, azo compound can be exemplified, organo-peroxide etc., but also two or more is also used.As azo compound, can 2 be exemplified, 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, benzoyl peroxide, perbenzoic acid t-butyl ester, hydrogen phosphide cumene, peroxide two dimethyl isopropyl ester, peroxide two carbonic acid two n-propyl diester, card acid t-butyl ester (t-Block チ Le パ mono-ォキシネォデカノェ mono-ト) that peroxide two carbonic acid two (2-ethoxyethyl group) ester, peroxide are new, peroxide can be exemplified than the sour t-butyl ester of bar (t-Block チ Le パ mono-ォキシ PVC バレ mono-ト), (3,5,5-trimethylammonium cyclopentanone base) superoxide, two propionyl superoxide and diacetyl superoxide etc.

Then, the solution mixing of the polymkeric substance (A) obtained and (B), dilution solvent adds.Thereafter, add glue crosslinking agent (C) and silane coupling agent as required (D), fully mix, carry out solvent dilution, obtain tackiness composition (coating solution).

The dilution of tackiness composition is the diluting solvent of coating solution, can exemplify the aliphatic hydrocarbon of hexane, heptane, hexanaphthene etc.; The aromatic hydrocarbons of toluene, dimethylbenzene 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-amylalcohol, different fluorine and the ketone of ketone, cyclopentanone etc.; Acetic acid ethyl ester, the ester of acetic acid butyl etc.; The cellosolve type solvents etc. of ethyl cellosolve etc.

The concentration of the coating solution of modulation like this and viscosity, as long as be coated with possible scope, have no particular limits, and can according to circumstances be suitable for selected.Such as, the concentration of tackiness composition can be diluted is 10 to 40 quality %.Further, when obtaining coating solution, the interpolation of diluting solvent etc. is not prerequisite, as long as tackiness composition is be coated with possible viscosity, does not add diluting solvent and can yet.This Games closes, and tackiness composition can intactly as coating solution.

Described tackiness agent, for described tackiness composition carry out glue connection formed.The glue connection of described tackiness composition, heat treated is carried out.Further, this heat treated, makes the volatilizations such as the dilution solvent of tackiness composition double as drying treatment.

The Games carrying out heat treated closes, and Heating temperature, preferably 50 to 150 DEG C, particularly 70 to 120 DEG C is more preferably.In addition, heat-up time is that coating in 30 seconds to 3 points is preferred, within special 50 seconds, is divided into preferably to 2.Further, after heat treated, be particularly preferably during the maturation of normal temperature (such as, 23 DEG C, 50%RH) 1 to 2 week left and right is set.

Described heat treated (and maturation), glue crosslinking agent (C) can be used to be joined by the 2nd (methyl) acrylic ester polymer (B) glue, thus fine and close three-dimensional netted structure is formed.And, the 1st (methyl) acrylic ester polymer (A) in its three-dimensional netted structure more than 2 molecules is not direct chemical bond, or obtain along with few chemical bond carries out inserting, this polymkeric substance (A) is in bond, and like plan, glue connection structure is formed.Thus, when obtaining stretching, maximum stress is, the tackiness agent also larger than stress during fracture or when 4000% stretches.In addition, 1st (methyl) acrylic ester polymer (A) is for having the Games conjunction of carboxyl, 1st (methyl) acrylic ester polymer (A) and silane coupling agent (D) react, and the adhesion weather resistance of the glass substrate to liquid crystal cells etc. of the tackiness agent obtained is able to height.

The gel ratio of the tackiness agent of present embodiment, 30 to 90% is preferably, and special 40 to 80% is that preferably further 45 to 75% is preferred.As gel ratio, the degree of glue connection is in this scope, and the three-dimensional netted structure that the glue of the 2nd (methyl) acrylic ester polymer (B) joins and obtains can well be formed, during stretching, maximum stress, the tackiness agent also larger than stress during fracture or when 4000% stretches.Thus, this tackiness agent, two sides of its resistance to light leakage and weather resistance are excellent.Further, the gel ratio of tackiness agent is the value of (through later between aging time) during sticky paying.Specifically, tackiness composition is applied to stripping film, after heat treated, 23 DEG C, carries out the gel ratio after keeping in 7 days under the environment of 50%RH.The gel ratio of tackiness agent, through front between aging time, its value is what change.From such viewpoint, whether process between aging time, not clear Games closes, and again at 23 DEG C, after carrying out keeping in 7 days under the environment of 50%RH, gel ratio is in described scope.

Tackiness agent described above, preferred as the optics used time, such as, the adhesion of polarized light piece and polarizer, or the adhesion of polarized light piece (polarized light film) and polarizer (phase-contrast film) and glass substrate.The adhering agent layer formed by described tackiness agent, stress relaxation rate is very excellent, the dimensional change being attached body is that large Games closes, the stress obtained by its dimensional change is absorbed loose by adhering agent layer, so while can not peeling off from to-be-adhered object for a long time, as as described in, when using in optics, light leak can prevent effectively.That is, the tackiness agent of present embodiment, when using in optics, resistance to light leakage and weather resistance can be reached simultaneously.

(adhesive sheet)

Shown in Fig. 1, the adhesive sheet 1A of the 1st embodiment, order from bottom to top, is made up of laminated substrate 13 on adhering agent layer 11 stacked in stripping film 12, stripping film 12 release surface, adhering agent layer 11.

In addition, shown in Fig. 2, the adhesive sheet 1B of the 2nd embodiment, by the stripping film 12a of 2 pieces, 12b, with the release surface phase ground connection of the stripping film 12a of 2 pieces, 12b by this stripping film 12a of 2 pieces, the adhering agent layer 11 that 12b seizes on both sides by the arms and being formed.Further, the release surface of the stripping film in this specification sheets, though for having the face of separability, carrying out lift-off processing and do not carry out the face that lift-off processing also has separability in stripping film.

No matter adhesive sheet 1A, in 1B that, adhering agent layer 11 is all the tackiness agent carrying out glue connection from described tackiness composition and obtain.

The thickness of adhering agent layer 11, can carry out Shi Yi Decision according to the application target of adhesive sheet 1A, 1B fixed, usual 5 to 100 μm, the preferably scope of 10 to 60 μm, such as, optics, the Games used particularly as the adhering agent layer of polarized light piece closes, and 10 to 50 μm, special 10 to 30 μm is preferred.

As base material 13, be not particularly limited, the thing that the substrate sheets usually used as adhesive sheet uses can use.Such as, outside optics, use artificial silk, vinylformic acid, the woven that the fiber of polyester etc. is made or non-woven fabrics; Upper matter paper, glassine 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 of poly-naphthoic acid ethanol ester etc., the cellulosefilm of triacetylcellulose film etc., polyurethane film, polyethylene film, polypropylene film, polychlorostyrene for vinyl film, polychloride inclined vinyl film, polyvinyl alcohol film, ethylene-vinyl acetate base ester co-polymer film, polystyrene film, polycarbonate film, acrylic resin films, poly-bornylene based resin film, the plastics film of cyclic olefin resins film etc.; These duplexer of more than two kinds etc.Plastics film, the thing that an axial compression is prolonged or two axial compressions are prolonged is also passable.

As optics, can exemplify polarized light piece (polarized light film), polarisation, polarizer (phase-contrast film), depending on Jiao Fill Compensation film, luminance brightness-improving film, comparative improves film, liquid crystal polymer film etc.Wherein, polarized light piece (polarized light film), be easy to shrink, dimensional change is large, and from the viewpoint of resistance to light leakage, it is suitable to liking that the tackiness agent (described adhering agent layer 11) as present embodiment is formed.

The thickness of base material 13, different according to its kind, such as, in the Games of optics closes, usual 10 μm to 500 μm, preferably 50 μm to 300 μm.

As stripping film 12, 12a, 12b, polyethylene film can be exemplified, polypropylene film, polybutene film, polybutadiene membrane, poly-methyl pentene film, polychlorostyrene is for vinyl film, chloroethylenes co-polymer film, pet film, poly-naphthoic acid ethanol ester film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate base ester film, ionic polymer resin film, ethene (methyl) acrylic copolymer film, ethene (methyl) acrylic ester copolymerization thing film, polystyrene film, polycarbonate film, Kapton etc., fluorine resin film etc.In addition, these glue connection film also can use.Further, these laminate film also can be used.

In the release surface (special adhering agent layer 11 and the face connect) of described stripping film, it is preferred for carrying out lift-off processing.The stripper that lift-off processing uses, can exemplify, the stripper of alcohol acids, type siloxane, fluorine class, unsaturated polyester class, polyolefins and wax class.

The thickness of stripping film 12,12a, 12b, is not particularly limited, and is generally about 20 to 150 μm.

The manufacture of described adhesive sheet 1A is in stripping film 12 release surface, will be coated with containing described tackiness composition solution (coating solution), and heat treated, after forming adhering agent layer 11, its adhering agent layer 11 carries out the stacked of base material 13.Thereafter, be preferred during maturation is set.

Further, the condition of heat treated and maturation, as described in.

In addition, described adhesive sheet 1B manufactures, in the release surface of the stripping film 12a (or 12b) of, coating solution containing described tackiness composition is coated with, after heat treated becomes adhering agent layer 11, at the another side of its adhering agent layer 11, the release surface of stripping film 12b (or 12a) is overlapping.

The method of the coating of described coating solution, can exemplify roller coating method, scraper for coating method, roller coating method, scraper for coating method, press coatings method and gravure coating process etc.

At this, such as, the manufacture of the liquid crystal display device that liquid crystal cells and polarized light piece are formed, the base material 13 of adhesive sheet 1A uses polarized light piece, and the stripping film 12 of this adhesive sheet 1A is peeled off, the adhering agent layer 11 exposed and liquid crystal cells and carry out fitting.

In addition, such as, the manufacture of the liquid crystal display device of polarizer is set between liquid crystal cells and polarized light piece, as an example, first, the stripping film 12a (or 12b) of the one side of adhesive sheet 1B is peeled off, adhesive sheet 1B is exposed adhering agent layer 11 and polarizer laminating.Then, be stripped by the stripping film 12 of the adhesive sheet 1A used as base material 13 polarized light piece, adhesive sheet 1A expose adhering agent layer 11 and described polarizer is fitted.Further, the stripping film 12b (or 12a) of another side peels off by the described adhering agent layer 11 from adhesive sheet 1B, and the adhering agent layer 11 exposed of adhesive sheet 1B and liquid crystal cells are fitted.

Above adhesive sheet 1A, 1B, adhering agent layer 11 is that stress relaxation rate is very excellent, so such as close at the Games of the adhesion being suitable for polarized light piece, the stress adhering agent layer 11 that can carry out because the distortion of polarized light piece produces absorbs loose, thus, excellent resistance to light leakage and high weather resistance are played.

Embodiment described above, does to understand the present invention.The present invention is not limited.So described embodiment discloses each key element, contain whole design alterations and the equivalent of the scope of the technology originally belonging to invention.

Such as, the stripping film 12 of adhesive sheet 1A can omit, and any one of the stripping film 12a in adhesive sheet 1B, 12b also can be omitted.

[embodiment]

Below, carry out the present invention further illustrate by embodiment etc., scope of the present invention is not limited to these embodiment.

(embodiment 1)

1. the modulation of polymkeric substance (A)

To having stirrer, thermometer, also flow water cooler, in the reaction vessel of dripping device and nitrogen ingress pipe, add n-butyl 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 nitrogen in described reaction vessel is replaced.In under this nitrogen atmosphere gas, limit is stirred, while make reaction soln be warming up to 60 DEG C, after reaction in 16 hours, is cooled to room temperature.At this, the some of the solution obtained is carried out GPC mensuration by following method, the polymkeric substance (A) confirming weight average molecular weight 1,500,000 is generated.

2. the modulation of polymkeric substance (B)

To having stirrer, thermometer, also flow water cooler, in the reaction vessel of dripping device and nitrogen ingress pipe, add n-butyl 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 nitrogen in described reaction vessel is replaced.This nitrogen atmosphere gas stirs below, while make reaction soln be warming up to 70 DEG C, after reaction in 6 hours, and cool to room temperature.At this, measured by the following method GPC of the portion of the solution obtained, the generation of the polymkeric substance (B) of weight average molecular weight 60,000 is identified.

3. the modulation of tackiness composition

Polymkeric substance (A) 100 mass parts (solids component scaled value) that above-mentioned operation (1) is obtained and, after polymkeric substance (B) 15 mass parts (solids component scaled value) mixing that described operation (2) obtains, as glue crosslinking agent (C), benzyl support vulcabond (TDI class) affixture (Japanese polyurethane Inc., trade(brand)name " can strangle resistance to (コロネ mono-ト) L ") 2.21 mass parts of the TriMethylolPropane(TMP) of the amount that hydroxyl 0.6 equivalent of polymkeric substance (B) is suitable is added.Finally, 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, obtains the diluting soln of tackiness composition.

At this, the component of this tackiness composition is as shown in table 1.Further, the detailed content of contracted notation etc. recorded of table 1 is as follows.

[polymkeric substance (A) and (B)]

BA: n-butyl

AA: vinylformic acid

HEA: vinylformic acid 2-hydroxyethyl ester

4HBA: vinylformic acid 4-hydroxybutyl ester

[plasticizer]

Ah 's jam large (Ah 's jam large (ァデカサィザ mono-)) C-8:

Trimellitate class plasticizer (tri trimellitate (2 ethylhexyl) ester) (Asahi Electro-Chemical Co. Ltd's system, trade(brand)name " large (the ァデカサィザ mono-) C-8 of Ah 's jam ")

[glue crosslinking agent (C)]

Isocyanates glue crosslinking agent

Resistance to (コロネ mono-ト) L can be strangled: benzyl support vulcabond affixture (Japanese polyurethane Inc., trade(brand)name " can strangle resistance to (コロネ mono-ト) L ") of TriMethylolPropane(TMP)

Its (タケネ mono-ト) D-110N of Ta Kaina: the Xylene Diisocyanate affixture of TriMethylolPropane(TMP) (Mitsui Chemicals urethane Inc., trade(brand)name " Ta Kaina its (タケネ mono-ト) D-110N ")

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 ")

The one side of pet film has carried out with type siloxane stripper stripping film (the Lin get Ke Inc. of lift-off processing, SP-PET3811, thickness: 38 μm) lift-off processing face on the diluting soln knife coater of the tackiness composition obtained is coated with, coating layer thickness is after the drying made to be 25 μm, then, carry out 1 minute heat treated at 90 DEG C, adhering agent layer is formed.

Then, by what be made up of the polarized light film with disc liquid crystal layer, polarized light film and visual angle expand the polarized light piece of film integration, fit, adhering agent layer and disk liquid crystal layer are connected, 23 DEG C, 50%RH carries out maturation in 7 days, thus the obtained polarized light piece with adhering agent layer.

(embodiment 2 to 12, comparative example 1 to 5)

Kind and the ratio of each monomer of tackiness composition will be formed, plasticizer, the kind of glue crosslinking agent and silane coupling agent and addition, and beyond as shown in table 1 such of the ratio of components of polymkeric substance (A) and polymkeric substance (B) change, similarly to Example 1, the polarized light piece with adhering agent layer is made

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

< condition determination >

GPC determinator: Inc. of Tosoh company, HLC-8020

GPC post (following sequentially passes through): Inc. of Tosoh company

TSKguardcolumnHXL-H

TSKgelGMHXL(×2)

TSKgelG2000HXL

Measure solvent: tetrahydrofuran (THF)

Measure temperature: 40 DEG C

(experimental example 1) (mensuration of gel ratio)

The polarized light piece used in the making of the polarized light piece with adhering agent layer in embodiment or comparative example is changed to, stripping film (Lin get Ke Inc. by type siloxane stripper lift-off processing has been carried out to the one side of pet film, SP-PET3801, thickness: 38 μm) make adhesive sheet.Specifically, on the adhering agent layer exposed of the constituting body that the stripping film/adhering agent layer (thickness: 25 μm) obtained in the manufacturing processed of embodiment or comparative example is exactly formed, foldedly establish described stripping film, side, lift-off processing face is connected.Thus, make by the adhesive sheet formed of stripping film/adhering agent layer/stripping film.

The adhesive sheet obtained, at 23 DEG C, carries out maturation in 7 days under the condition of 50%RH.Thereafter, this adhesive sheet is made into the sample of the size of 80mm × 80mm, and its adhering agent layer polyester net (mesh 200) is wrapped, and carries out the quality precision balance weighing to tackiness agent.Using quality at this moment as M1.

Then, by the tackiness agent of described polyester net bag, under room temperature, (23 DEG C) flood 24 hours with vinyl acetic monomer.Thereafter tackiness agent is removed, temperature 23 DEG C, under the environment of relative humidity 50%, carry out 24 hours air-dry, carry out in the baking oven of 80 DEG C further 12 hours dry.Only weighing is carried out to the quality precision balance of dried tackiness agent.Using quality at this moment as M2.Gel ratio (%), represents with (M2/M1) × 100.The results are shown in table 2.

(experimental example 2) (mensuration of optical property)

As mensuration sample, prepare the adhesive sheet (7 day maturation be over) same with the adhesive sheet in the mensuration of gel ratio.About the adhering agent layer of this adhesive sheet, by Hai Si (Haze) instrument (Japanese electricity Se industrial system, NDH2000), according to JISK7105, Hai Si (Haze) value (%) (being also Hz (%) by its abbreviation) is measured.The results are shown in Table 2.Further, the scope of preferred Hai Si (Haze) value, 0 to 5%.

(experimental example 3) (durability evaluation)

The polarized light piece cutting device with adhering agent layer obtained in embodiment or comparative example (the super cutter of Huo Ye manufacturing company system, PN1-600) is adjusted to the size adjusting of 233mm × 309mm.Peeled off by stripping film, pay in non-alkali glass (Corning Incorporated's system, hawk XG) between the adhering agent layer exposed is sticky, afterwards, with the made autoclave of the former making of chestnut at 0.5MPa, 50 DEG C are carried out 20 points of pressurizations.

Thereafter, drop under dropping into the environment of 80 DEG C of dry durable conditions, observe with 10 times of magnifying glasses after 500 hours.The following benchmark of appearance change is evaluated.Result is as shown in table 2.

In ◎: 4 limits, no problem

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

×: at least 1 limit on 4 limits, the position more than from peripheral end to 0.6mm, has and floats, and peels off, and foaming, the outward appearance Iso of the tackiness agent of more than the 0.1mm of striped etc. is normal

(experimental example 4) (light leak experiment)

The polarized light piece with adhering agent layer obtained in embodiment or comparative example, with cutting device (the super cutter of Huo Ye manufacturing company system, is adjusted to PN1-600) 233mm × 309mm.Peeled off by stripping film, between sticky pair of the adhering agent layer exposed in non-alkali glass (Corning Incorporated's system, hawk XG), only the made autoclave of the former making of rear chestnut is at 0.5MPa, 50 DEG C, carries out 20 points of pressurizations.Further, described laminating, in the table of non-alkali glass, making the polarized light piece with adhering agent layer become polarizing axis is Niccol cross state (polarizing axis: ∠ 45 °, ∠ 135 °).In this state, after carrying out under 80 DEG C of dry environments placing for 250 hours, at 23 DEG C, the environment of 50%RH is placed for lower 2 hours, using this as sample, carries out the evaluation of light leak by method shown in following.Result is as shown in table 2.

< light leak is evaluated: Δ L ^*>

Use the MCPD-2000 of great Zhong electronics corporation, the lightness L in each field shown in the Fig. 3 in described sample ^*determined, luminosity equation Δ L ^*, use formula

ΔL ^*＝[(b+c+d+e)/4]-a

But (, a, b, c, d and e, respectively in A field, B field, C field, the lightness in the prespecified measuring point (1 place of the central part in each field) in D field and E field.) obtain, as light leak.Δ L ^*value less, light leak is fewer.Further, L ^*max, represents the maximum lightness in described full field.

< light leak is evaluated: visual >

Described sample is arranged at flat head lamp (electric flux industry Inc., HF-SL-A312LC, illumination: 26,000Lux, brightness: 10,000cd) on, tieing up color luminance meter by binary (can Ni Ka Minolta Inc., CA-2000) carry out a pinch shadow, be transformed to Luminance Distribution image with parsing software (can Ni Ka Minolta Inc., CA-S20w).The metewand of the Luminance Distribution image Fig. 4 of the sample obtained is evaluated.

(experimental example 5) (stretching experiment)

At the one side to pet film, stripping film (the Lin get Ke Inc. of lift-off processing is carried out with type siloxane stripper, SP-PET3811) the tackiness composition that lift-off processing face is modulated in coating Examples and comparative example, dried coating thickness is made to be 25 μm, carry out heating in 1 minute at 100 DEG C, adhering agent layer is formed.Fitting in the lift-off processing face that the one side type siloxane stripper of its adhering agent layer and pet film carries out another stripping film (Lin get Ke Inc., SP-PET3801) of lift-off processing, obtains adhesive sheet.

Carry out multilayer laminated to described adhering agent layer, make the aggregate thickness of the adhering agent layer in described adhesive sheet be 500 μm, and only make the stripping film on the most top layer of duplexer remain, at 23 DEG C, under the atmosphere gas of humidity 50%, place a night.Thereafter, from the adhesive sheet that described adhering agent layer is multilayer laminated cut out 10mm wide × the long sample of 75mm, stripping film stacked for the most top layer of duplexer is peeled off, sets up sample, make measurement range be 10mm wide × 20mm is long, at 23 DEG C, under under the environment of 50%RH, with tensile testing machine (Ao Rui Inc., tensilon), draw speed 200mm/ divides, and 4000% stretches, and counter stress (N) is measured.Stress during 4000% stretching or when rupturing, and maximum stress is as shown in table 2.

[table 1]

Table 1 (Continued)

Table 2

Table 2 (Continued)

Can learn clearly from table 2, the band obtained in embodiment is by adhering agent layer polarized light piece, and stress when maximum stress stretches than 4000% or when rupturing is also large, and weather resistance and resistance to light leakage are all excellent.But on the other hand, in the polarized light piece of the band adhering agent layer obtained in comparative example, when maximum stress and 4000% stretches or fracture time stress identical, two sides of weather resistance and resistance to light leakage or side's poor performance.

[utilizing possibility in industry]

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

[explanation of symbol]

1A, 1B... adhesive sheet

11... adhering agent layer

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

13... base material

Claims

1. a tackiness agent, is characterized in that:

Containing the 1st (methyl) acrylic ester polymer (A) that weight average molecular weight is 50 ten thousand to 300 ten thousand, and weight average molecular weight is the 2nd (methyl) acrylic ester polymer (B) crosslinked composition of 8000 to 30 ten thousand

To described 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of described 2nd (methyl) acrylic ester polymer (B) is 5 to 50 mass parts;

Described 2nd (methyl) acrylic ester polymer (B) before crosslinked is random co-polymer, as constituent, there are more than 5 quality % and 50 quality % less than the monomer containing reactive functional group;

During stretching, maximum stress is also larger than stress during fracture or when 4000% stretches.

2. tackiness agent according to claim 1, is characterized in that: be (methyl) more than acrylic ester polymer 50 quality % of 50 ten thousand to 300 ten thousand containing weight average molecular weight, gel fraction is 30 to 90%.

3. an adhesion thin slice, has base material and adhering agent layer, it is characterized in that:

Described adhering agent layer, is formed by the tackiness agent of claim 1 or 2.

4. adhesion thin slice according to claim 3, is characterized in that: described base material is optics.

5. an adhesion thin slice, comprising: the peeling sheet of 2 pieces, and by the adhering agent layer that this peeling sheet is seized on both sides by the arms, connects thus with the release surface of described 2 pieces of peeling sheet,

It is characterized in that: described adhering agent layer is formed by the tackiness agent of claim 1 or 2.