CN102888202B

CN102888202B - Tackiness composition, tackiness agent and adhesive sheet

Info

Publication number: CN102888202B
Application number: CN201210223718.8A
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: 2011-06-28
Filing date: 2012-06-28
Publication date: 2016-01-06
Anticipated expiration: 2032-06-28
Also published as: KR20130002263A; JP5613108B2; JP2013010835A; CN102888202A; TW201300476A; KR101914455B1; TWI527864B

Abstract

Have and prevent charging property and stress relaxation rate and weather resistance are all excellent when being applicable to the opticses such as polarization plate tackiness composition, tackiness agent and adhesive sheet.Described tackiness composition contains the 1(methyl that Mw is 500,000 ~ 3,000,000) acrylic ester polymer (A), Mw be 8000 ~ 300,000 2(methyl) acrylic ester polymer (B), linking agent (C) and charged preventor (D).To (A) 100 mass parts, the ratio of (B) is 5 ~ 50 mass parts.(B) containing the monomer with the functional group (b1) of reacting with (C).The ratio of this monomer in (B) more than 1 quality % and 50 quality % less than.(A) not containing have the functional group of reacting with (C) monomer or containing have also will be low than the functional group (b1) of (B) with the reactivity of (C) functional group (a1).

Description

Tackiness composition, tackiness agent and adhesive sheet

Technical field

The present invention relates to tackiness composition, tackiness agent (tackiness composition being cross-linked and the material obtained) and adhesive sheet, particularly relate to tackiness composition, tackiness agent and the adhesive sheet used for optical part that are suitable for polarized light piece etc.

Background technology

In general, in liquid crystal panel, polarized light piece and polarizer are bonded in the occasion of the glass substrate of liquid crystal cells etc., the multiplex adhering agent layer having adhesion agent composition to be formed.But, the optics of polarized light piece and polarizer etc. is easy to shrink due to heat etc., the generation of the contraction that described thermal distortion is brought, its result, the adhering agent layer that described optics is stacked can not be followed described contraction, thus peels off at interface (what is called is floated, and peels off), the stress during contraction of optics will bring the optic axis of optics to depart from, thus light leak (so-called hickie) occurs.

As the prevention method of described problem, (1) can be exemplified clinging power is high, and the optical member adhering of the excellent adhering agent layer and polarized light piece etc. of form stability, the method making the contraction of optics carry out self to suppress, or the method that the little adhering agent layer of stress during (2) contraction to optics uses.As the method for (1), the adhering agent layer that the such storage modulus using patent documentation 1 to represent is high makes effectively.On the other hand, as the method for (2), the adhering agent layer that can carry out soft corresponding stress relaxation rate excellent to the distortion of optics is used to be effective.But, in the past, using the occasion of adhering agent layer that such stress relaxation rate is excellent, be necessary that the cross-linking density in adhering agent layer was established low.But this will cause the weaken of adhering agent layer self, the problem that weather resistance degenerates.

Therefore, in patent documentation 2-4, not that the cross-linking density of adhering agent layer is established low, but plasticizer, Liquid Paraffin and polyurethane elastomer etc. are added in acrylic acid or the like tackiness agent, the adhesion agent composition obtained has the flexibility of appropriateness, give stress relaxation rate to adhering agent layer, thus, expect resistance to light leakage and weather resistance.

But the adhering agent layer that the adhesion agent composition that plasticizer or Liquid Paraffin add is formed, its plasticizer and Liquid Paraffin can ooze out in time.Thus, adhesion durability can be deteriorated, the liquid crystal cells of to-be-adhered object will be contaminated etc. various problem worry by people.In addition, with the addition of the adhesion agent composition of polyurethane elastomer, as maintained intermiscibility, the upper limit of the addition of polyurethane elastomer is limited.Thus, in the adhering agent layer having described adhesion agent composition to obtain, the improvement of stress relaxation rate just has insufficient.Further, stress relaxation rate be improved, will improve the addition of polyurethane elastomer, this will occur to be deteriorated with the intermiscibility of acrylic acid or the like tackiness agent, thus the problem of gonorrhoea etc. occurs.So, in technology in the past, it is difficult that the resistance to light leakage of the adhering agent layer formed by adhesion agent composition used for optical part and weather resistance carry out basic improvement.

But described adhering agent layer is stacked stripping film thereon, or the optics of polarized light piece and polarizer etc., be usually made up of plastic material.Therefore, electrical insulating property is high, occasion when being peeled off by stripping film etc., and electrostatic is easy to occur.Under the state that the electrostatic so occurred is remaining, as polarized light piece and polarizer etc. and liquid crystal cells are fitted, the orientation of liquid crystal molecule just has and chaotic possibility occurs, and in addition, also has the existence of electrostatic, can cause the problem of dust etc.

Therefore, someone proposes chargedly to prevent performance as will be effectively obtained, and will add charged preventor (such as patent documentation 5-8) in adhesion agent composition.

[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

[patent documentation 5] JP 2005-290357 publication

[patent documentation 6] JP 2007-316377 publication

[patent documentation 7] JP 2008-95081 publication

[patent documentation 8] JP 2009-155585 publication

But add the occasion of charged preventor in adhesion agent composition, the weather resistance of the tackiness agent obtained has the problem than being usually deteriorated.In described tackiness agent, in order to stress relaxation rate be given, cross-linking density meeting step-down, adds plasticizer etc., will weather resistance can be deteriorated further as described above.Thus, stress relaxation rate is given will become more difficult.So, in the tackiness agent having charged preventive, be in the stress relaxation rate of inverse proportional relation and weather resistance two side is good just becomes problem.

Summary of the invention

The present invention, completes in view of such actual state.The object of the invention is just to provide a kind of charged preventive that has, and, where applicable on the optics of polarized light piece etc., tackiness composition, tackiness agent and adhesive sheet that two sides of stress relaxation rate and weather resistance are excellent.

[solving the means of problem]

In order to reach described object, content of the present invention is as follows: the first technical scheme of the present invention, it is characterized in that, it contains the 1st (methyl) acrylic ester polymer (A) that weight average molecular weight is 500,000-300 ten thousand, weight average molecular weight is the 2nd (methyl) acrylic ester polymer (B) of 8000-30 ten thousand, linking agent (C) and charged preventor (D), for described 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of described 2nd (methyl) acrylic ester polymer (B) is 5-50 mass parts, described 2nd (methyl) acrylic ester polymer (B), the monomer with the functional group (b1) reacted with described linking agent (C) is contained as constituent, further, there is the ratio of the monomer of described functional group (b1), more than 1 quality % in described 2nd (methyl) acrylic ester polymer (B), and 50 quality % less than, described 1st (methyl) acrylic ester polymer (A), as constituent not containing the monomer with the functional group reacted with described linking agent (C), or contain lower than the described functional group (b1) of described 2nd (methyl) acrylic ester polymer (B) with tackiness composition (technical scheme 1) that the is monomer of reactive functional group (a1) of described linking agent (C) as constituent.

The tackiness composition of described technical scheme (technical scheme 1) carries out the crosslinked tackiness agent obtained, and can play and have charged preventive, suitable cohesive force and excellent stress relaxation rate.By having the tackiness agent of excellent stress relaxation rate described in using, when being applicable to the optics of polarized light piece etc., can obtain playing sufficient charged preventive, at the adhesive sheet that two sides of resistance to light leakage and weather resistance are excellent.

In described technical scheme (technical scheme 1), described 1st (methyl) acrylic ester polymer (A), or described 1st (methyl) acrylic ester polymer (A) and described 2nd (methyl) acrylic ester polymer (B), as the formation monomer unit of described polymkeric substance, preferably containing alkylene oxide monomer 5-50 quality % (technical scheme 2).

In described technical scheme (technical scheme 1,2), described charged preventor (D) is preferably (technical scheme 3) with ionic compound.

In described technical scheme (technical scheme 3), described ionic compound, is preferably from by containing at least a kind (technical scheme 4) selecting nitrogen salt, the group that forms containing sulfosalt, phosphorous salts, an alkali metal salt and alkali earth metal salt.

In described technical scheme (technical scheme 4), at least a kind (technical scheme 5) preferably selecting from the group that described an alkali metal salt, lithium salts and sylvite are formed.

In described technical scheme (technical scheme 1-5), described functional group (a1) in described 1st (methyl) acrylic ester polymer (A) is carboxyl, described functional group (b1) in described 2nd (methyl) acrylic ester polymer (B) is hydroxyl, and described linking agent (C) is isocyanates linking agent (technical scheme 6).

In described technical scheme (technical scheme 1-5), described 1st (methyl) acrylic ester polymer (A), as formation monomer not containing carboxyl group-containing monomer, or be preferred (technical scheme 7) as described functional group (a1) containing below carboxyl group-containing monomer 15 quality %.

In described technical scheme (technical scheme 1-7), described 2nd (methyl) acrylic ester polymer (B) is 3-40 quality % as described functional group (b1) containing hydroxyl monomer is preferred (technical scheme 8).

In described technical scheme (technical scheme 6), the amount of described isocyanates linking agent is, the amount of isocyanate group to the described functional group (b1) in described 2nd (methyl) acrylic ester polymer (B) of described isocyanates linking agent is the amount of 0.1-3.5 equivalent is preferred (technical scheme 9).

2nd, the technical program, for providing the tackiness agent (technical scheme 10) that a kind of described tackiness composition (technical scheme 1-9) is crosslinked.

In described technical scheme (technical scheme 10), the sheet resistance value of described tackiness agent, with 3.0 × 10 ¹¹Ω/below sq is preferably (technical scheme 11).

3rd, technical scheme of the present invention, for provide a kind of there is base material and adhering agent layer adhesive sheet, it is characterized in that it is made up of (technical scheme 12) described tackiness agent (technical scheme 10,11) described adhering agent layer.

In described technical scheme (technical scheme 12), described base material preferred light member (technical scheme 13).

4th, the technical program, for the adhering agent layer that the stripping film and described stripping film with 2 pieces are seized on both sides by the arms, the adhesive sheet that connects with the release surface of the stripping film of described 2 pieces of described adhering agent layer thus, it is characterized in that described adhering agent layer, for described tackiness agent (technical scheme 10,11) is formed (technical scheme 14).

[effect of invention]

In the tackiness agent that tackiness composition of the present invention carries out being cross-linked and obtains, in the past, as the low-molecular-weight polymkeric substance that plasticizer uses, form the three-dimensional netted structure of chemically crosslinked structure, described three-dimensional netted structure, have the polymkeric substance of multiple high molecular to insert, the polymer of high molecular is in bond, forms crosslinked configuration (supposition) like intending between the polymkeric substance of high molecular.Thus, the tackiness agent obtained, while having charged preventive, can play suitable cohesive force and excellent stress relaxation rate.By having the tackiness agent of excellent stress relaxation rate described in being suitable for, where applicable in the optics of polarized light piece etc., had both played sufficient charged preventive, can obtain again the adhesive sheet that two sides of resistance to light leakage and weather resistance are excellent.

The simple explanation of accompanying drawing

Fig. 1 is the sectional view of the adhesive sheet of the 1st embodiment of the present invention.

Fig. 2 is the sectional view of the adhesive sheet of the 2nd embodiment of the present invention.

Fig. 3 is the expression figure in the mensuration field with the light leak experiment in the polarized light piece of adhering agent layer.

[explanation of symbol]

1A, 1B... adhesive sheet

11... adhering agent layer

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

13... base material

Embodiment

Below, embodiments of the present invention are described.

(tackiness composition)

The tackiness composition of present embodiment, the 2nd (methyl) acrylic ester polymer (B), linking agent (C) and charged preventor (D) that the 1st (methyl) acrylic ester polymer (A) containing weight average molecular weight (Mw) 500,000-300 ten thousand, weight average molecular weight (Mw) are 8000-30 ten thousand, preferably further containing silane coupling agent (E).In addition, in this specification sheets, so-called (methyl) acrylate, refers to two sides of acrylate and methacrylic ester.Other similar term too.In addition, in " polymkeric substance ", the concept also containing " co-polymer ".

In the tackiness agent that described tackiness composition is cross-linked and obtains, 2nd (methyl) acrylic ester polymer (B) (low-molecular weight polymer) forms three-dimensional netted structure between linking agent (C), in described three-dimensional netted structure, more than 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) 2 molecule, not directly with chemical bond, or insert along with few chemical bond, between polymer (A), like the bound plan of the state with degree of freedom to a certain degree, crosslinked configuration forms (supposition) (structure so inferred, hereinafter referred to as " structure X ").There is the tackiness agent of described structure X, there is charged preventive, suitable cohesive force and excellent stress relaxation rate can be played.Have the tackiness agent of so excellent stress relaxation rate, being applicable to the optics of polarized light piece etc., while resistance to light leakage is excellent, weather resistance is also excellent, can prevent floating and stripping etc. under the condition of high temperature etc.

Described (methyl) acrylic ester polymer (A) or (B), be preferably (methyl) alkyl acrylate that the carbon number of alkyl is 1-20, there is the monomer (containing alkylene oxide group monomer) at alkoxide position, with the monomer (containing reactive functional group monomer) with the functional group that linking agent (C) reacts and the co-polymer of other monomer used as required.In addition, the 1st (methyl) acrylic ester polymer (A), preferably not contain the described reactive functional group monomer that contains as component unit.In addition, the 2nd (methyl) acrylic ester polymer (B), does not preferably contain described containing alkylene oxide group monomer as component unit.

Carbon number as alkyl is (methyl) alkyl acrylate of 1-20, (methyl) methyl acrylate can be exemplified, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butylacrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid n-hexyl ester, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) isooctyl acrylate ester, (methyl) vinylformic acid positive certain herbaceous plants with big flowers base ester, (methyl) vinylformic acid dodecyl ester, (methyl) myristyl base ester, (methyl) aliphatic acrylate and (methyl) stearyl acrylate base ester etc.They may be used alone, two or more kinds can also be used in combination.

1st (methyl) acrylic ester polymer (A), as component unit, the carbon number of preferred alkyl is the amount of (methyl) alkyl acrylate of 1-20 is 5-100 quality %, particularly preferably containing 30-90 quality %, further preferably containing 40-80 quality %.The amount of described (methyl) alkyl acrylate, in the scope of 5-100 quality %, can obtain desired tackiness.In addition, the amount of described (methyl) alkyl acrylate is in the scope of 30-90 quality %, can guarantee containing alkylene oxide group monomer and containing the amount of reactive functional group monomer in polymkeric substance (A).

In addition, 2nd (methyl) acrylic ester polymer (B), as component unit, the carbon number preferably containing alkyl is (methyl) alkyl acrylate 5-99 quality % of 1-20, particularly containing 30-90 quality %, further preferably containing 40-80 quality %.The amount of described (methyl) alkyl acrylate in the scope of 5-99 quality %, can obtain desired adhesive while, the amount containing reactive functional group monomer in polymkeric substance (B) can be guaranteed.In addition, when the amount of described (methyl) alkyl acrylate is in the scope of 30-90 quality %, the amount containing alkene monomer in polymkeric substance (B) also can be guaranteed.

As containing oxyalkylene monomer, (methyl) vinylformic acid alkoxy ester of (methyl) vinylformic acid 2-methoxy ethyl ester, (methyl) vinylformic acid 2-ethoxyethyl group ester, (methyl) vinylformic acid 2-methoxy-propyl ester, (methyl) vinylformic acid 3-methoxy-propyl ester, (methyl) vinylformic acid 2-methoxy butyl acrylate, (methyl) vinylformic acid 4-methoxy butyl acrylate etc. preferably can be exemplified.Further preferably, there is (methyl) vinylformic acid alkoxy ester of the poly-alkyl diol chain of the polyglycol chain of end alkoxy group or polypropylene glycol chain etc.Wherein, due to the viewpoint that the intermiscibility of each monomer when obtaining the polymerization of polymkeric substance (A) or (B) is excellent, be particularly preferably with (methyl) vinylformic acid 2-methoxy ethyl ester.They can be used alone, but also two or more combinationally uses.

Containing alkylene oxide group monomer, preferably independent at the 1st (methyl) acrylic ester polymer (A), or the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) contain as component unit.So at least the 1st (methyl) acrylic ester polymer (A) is as component unit, containing containing alkylene oxide monomer, owing to demonstrating hydrophilic alkoxyl group position, can improve produced by charged preventor (D) chargedly prevent performance.Thus, the amount of the charged preventor (D) in the tackiness composition of present embodiment just can reduce.In addition, the occasion containing alkylene oxide monomer is contained as component unit at only the 2nd (methyl) acrylic ester polymer (B), in the forming process of the three-dimensional netted structure obtained by described polymkeric substance (B) and linking agent (D), the polarity difference of described three-dimensional netted structure part and polymkeric substance (A) increases (supposition).Like this, just optical characteristics is likely caused to be deteriorated due to being separated of two-component, or, described structure X can not be formed fully.Thus, this mode is preferably avoided.

1st (methyl) acrylic ester polymer (A), preferably as component unit, contains alkylene oxide group monomer containing described in 5-50 quality %, particularly preferably containing 10-40 quality %, further preferably containing 15-35 quality %.2nd (methyl) acrylic ester polymer (B) as component unit contain containing alkylene oxide monomer occasion too.As containing alkylene oxide monomer content as described in scope, while obtaining above-mentioned excellent effect, described (methyl) alkyl acrylate in the tackiness composition of present embodiment and the amount containing reactive functional group monomer can be guaranteed.

On the other hand, as containing reactive functional group monomer, preferably can exemplify monomer (hydroxyl monomer), the carboxyl group-containing monomer (carboxyl group-containing monomer) in molecule in molecule with hydroxyl, the monomer (emulsion stability) etc. of molecule embedded amine groups.In addition, as the monomer containing following reactive functional group base (a1), the monomer containing reactive functional group base (b1) and the monomer containing reactive functional group base (b2), it is the monomer containing reactive functional group described at this.The selection of its concrete kind, is described in the project of each monomer.

As hydroxyl monomer, (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 etc. can be exemplified.These may be used alone, two or more kinds can also be used in combination.

As carboxyl group-containing monomer, can the alkene unsaturated carboxylic acid of exemplified by acrylic, methacrylic acid, β-crotonic acid, toxilic acid, methylene-succinic acid and citraconic acid etc.These may be used alone, two or more kinds can also be used in combination.

As emulsion stability, (methyl) acrylic-amino ethyl ester can be exemplified, (methyl) vinylformic acid n-butylamino ethyl ester etc.They can be suitable for separately, but also two or more combinationally uses.

Further, as other monomer described, (methyl) acrylate with aliphatics ring of (methyl) cyclohexyl acrylate etc. can be exemplified; (methyl) acrylamide of (methyl) acrylate with aromatic ring of (methyl) phenyl acrylate etc., the non-crosslinked of acrylamide and Methacrylamide etc.; (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, (methyl) vinylformic acid N, (methyl) acrylate with tertiary amine groups of the non-crosslinked of N-dimethylaminopropyl ester etc.; Vinyl-acetic ester; Vinylbenzene etc.They can be suitable for separately, but also two or more combinationally uses.

2nd (methyl) acrylic ester polymer (B), to have the monomer (monomer containing reactive functional group (b1)) of the functional group (b1) that can react with linking agent (C) as constituent.Described polymkeric substance (B) contains, and the functional group that can react with linking agent (C), preferably in fact only has functional group (b1).In addition, so-called " in fact only having functional group (b1) ", refers to that the amount of other the functional group reacted with linking agent (C) that can contain will in the reactive degree not hindering functional group (b1) and linking agent (C).

Namely, 2nd (methyl) acrylic ester polymer (B), as constituent, preferably not containing compared with described functional group (b1), there is the monomer (containing reactive functional group (b2) monomer) of the functional group (b2) low with the reactivity of linking agent (C).But, containing reactive functional group (b2) monomer by the occasion contained as constituent, as mass ratio with containing reactive functional group (b1) monomer amount less than 1/5 amount, particularly the amount of less than 1/10 is preferred.

In addition, what the 2nd (methyl) acrylic ester polymer (B) used contains reactive functional group (b

1) monomer and containing reactive functional group (b2) monomer, and the selection containing reactive functional group (a1) monomer used in following the 1st (methyl) acrylic ester polymer (A), decide by the reactive relation with the linking agent (C) used.In detail as following.

2nd (methyl) acrylic ester polymer (B) is containing the amount containing reactive functional group (b2) monomer, as exceed as mass ratio containing reactive functional group (b1) monomer amount 1/5 time, the weather resistance of the adhering agent layer obtained has the possibility of variation.As the reactive functional group (b2) in the 2nd (methyl) acrylic ester polymer (B) is too much, have reactive functional group (b2) in the three-dimensional netted tectosome formed thus remaining in a large number, the intermiscibility of described three-dimensional netted tectosome and the 1st (methyl) acrylic ester polymer (A) changes (supposition) thus.Its result, has the occasion that mist degree (haze) value rises.In addition, the three-dimensional netted tectosome that reactive functional group (b2) is remaining in a large number, the mobility inserting the 1st (methyl) acrylic ester polymer (A) of described three-dimensional netted tectosome is overly restricted (supposition).Its result, the stress relaxation rate of the tackiness agent obtained has variation, and weather resistance has the occasion degenerated.

Further, the tackiness composition of present embodiment contains the occasion of silane coupling agent (E), silane coupling agent (E), act on reactive functional group (a1) (particularly the carboxyl) of following the 1st (methyl) acrylic ester polymer (A), with the 1st (methyl) acrylic ester polymer (A) bonding of high molecular.In addition, at this said key, be not merely defined as covalent linkage, also comprise the concepts such as hydrogen bond, the interaction of Shu water-based and Fan get Hua Li.Thus, the alkoxyl silicone base section of silane coupling agent (E) and glass substrate effect, so the tackiness agent obtained can improve the adherence (supposition) with the glass substrate of to-be-adhered object etc.At this, 2nd (methyl) acrylic ester polymer (B) is as superfluous containing reactive functional group (b2) monomer, silane coupling agent (E), also act on reactive functional group (b2) (particularly the carboxyl) of the 2nd (methyl) acrylic ester polymer (B), with low-molecular-weight 2nd (methyl) acrylic ester polymer (B) bonding, thus be deprived of (supposition) with the chance that to-be-adhered object carries out bonding.Its result, the adherence of the tackiness agent obtained and the glass substrate of to-be-adhered object etc. is deteriorated, and thus, the weather resistance of adhering agent layer just has the possibility of variation.

In 2nd (methyl) acrylic ester polymer (B), the described amount containing reactive functional group (b1) monomer for more than 1 quality %, its upper limit be 50 quality % less than.Preferably, described containing being 5-40 quality % containing reactive functional group (b1) monomer, particularly preferably containing 10-30 quality %, further preferably containing 12-20 quality %.Make to be in described scope containing reactive functional group (b1) monomer, the crosslinked degree of the 2nd (methyl) acrylic ester polymer (B) improves, with the combination of the 1st (methyl) acrylic ester polymer (A), the stress relaxation rate of the tackiness agent obtained can be enhanced.Its result, obtains weather resistance and all good tackiness agent of resistance to light leakage two side.In addition, if the amount containing reactive functional group (b1) monomer is as at below 1 quality %, the 2nd (methyl) acrylic ester polymer (B's) is crosslinked insufficient, and gel fraction is low, and weather resistance has the possibility of variation thus.On the other hand, the amount containing reactive functional group (b1) monomer is more than 50 quality %, and the crosslinked meeting of the 2nd (methyl) acrylic ester polymer (B) is excessive, and stress relaxation rate has the possibility of variation.In addition, if the upper limit making the amount containing reactive functional group (b1) monomer is 30 quality %, the resistance to light leakage of the adhesive sheet obtained can become more excellent.

At this, the carbon number of alkyl is the polymerization methods of the 2nd (methyl) acrylic ester polymer (B) that (methyl) alkyl acrylate of 1-20 obtains with the monomer polymerization with the functional group reacted with linking agent (C), 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, but also two or more combinationally uses.

The weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is 8000-30 ten thousand, preferably 10,000-20 ten thousand, particularly preferably 50,000-10 ten thousand.That is, the 2nd (methyl) acrylic ester polymer (B) is low-molecular weight polymer composition.In addition, the weight average molecular weight in this specification sheets, the value of the polystyrene conversion using gel permeation chromatography (GPC) method to measure.

The weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) as described in scope, specific to the tackiness composition of present embodiment, three-dimensional netted structure will be formed, and has contribution to excellent stress relaxation rate.That is, the 2nd (methyl) acrylic ester polymer (B) weight average molecular weight as 8000 less than, good three-dimensional netted structure will be can not get.On the other hand, if the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is more than 300,000, will be deteriorated with the intermiscibility of the 1st (methyl) acrylic ester polymer (A) etc., mist degree (haze) value of adhering agent layer can rise, and optical characteristics has the occasion of variation.In addition, the insertion of the polymkeric substance (A) in the three-dimensional netted tectosome that polymkeric substance (B) is formed will be insufficient, and its result, the weather resistance of the tackiness agent obtained and reusability just have the occasion of variation.

1st (methyl) acrylic ester polymer (A), preferably, as constituent not containing having the monomer carrying out the functional group reacted with linking agent (C), or described functional group (b1) the also monomer (containing reactive functional group (a1) monomer) that is low and reactive functional group (a1) of linking agent (C) had than the 2nd (methyl) acrylic ester polymer (B) is contained as constituent, thus particularly preferably, do not have than described functional group (b1) also monomer that is high and reactive functional group of linking agent (C) containing containing as constituent.

1st (methyl) acrylic ester polymer (A), also can not containing the monomer with the functional group reacted with linking agent (C).But, as containing reactive functional group (a1) monomer, have preferred occasion.That is, contain reactive functional group (a1) in described polymkeric substance (A), have the occasion of the reaction of promotion the 2nd (methyl) acrylic ester polymer (B) and linking agent (C).Or, when silane coupling agent (E) is used, reactive functional group (a1) and the described silane coupling agent (E) of the 1st (methyl) acrylic ester polymer (A) act on, the adhesion durability of the glass surface to liquid crystal cells etc. of the tackiness agent obtained is improved further, so there is preferred occasion.

1st (methyl) acrylic ester polymer (A) is containing the described occasion containing reactive functional group (a1) monomer, its amount, usually at below 20 quality %, below 15 quality % are that preferably particularly below 10 quality % are more preferably.Containing the amount of reactive functional group (a1) monomer as more than 20 quality %, the glass transition temperature (Tg) of the 1st (methyl) acrylic ester polymer (A) can become too high, and the stress relaxation rate of the tackiness agent obtained is deteriorated to obtain possibility.In addition, from the viewpoint of giving tackiness agent reusability, be preferred containing the amount of reactive functional group (a1) monomer at below 15 quality %.

In addition, with the 2nd (methyl) acrylic ester polymer (B) contain containing compared with reactive functional group (b1) monomer, 1st (methyl) acrylic ester polymer (A) contain containing the ratio of reactive functional group (a1) monomer in described 1st (methyl) acrylic ester polymer (A), the ratio in described 2nd (methyl) acrylic ester polymer (B) containing reactive functional group (b1) monomer preferably contained than the 2nd (methyl) acrylic ester polymer (B) is little.Thus, the reactive functional group (a1) that 1st (methyl) acrylic ester polymer (A) contains and the reaction of linking agent (C) suppressed, the reactive functional group (b1) that the 2nd (methyl) acrylic ester polymer (B) can be made to contain and linking agent (C) carry out certain reaction.Thus, the stress relaxation rate of the tackiness agent obtained can be enhanced.

1st (methyl) acrylic ester polymer (A), preferably in the molecule containing being the equal above functional group of the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) with the reactivity of linking agent (C).But if the occasion contained, described functional group is by the amount containing monomer in molecule, and preferred below 1 quality % in polymkeric substance (A) is particularly more preferably with below 0.5 quality %.The amount of described monomer is as more than 1 quality %, and the 2nd (methyl) acrylic ester polymer (B) that should preferentially carry out and the reaction of linking agent (C) just have the possibility be obstructed.Its result, just has the occasion that can not get desired stress relaxation rate.

At this, the carbon number of alkyl is (methyl) alkyl acrylate of 1-20, be polymerized with the monomer containing reactive functional group, and the polymerization methods of the 1st (methyl) acrylic ester polymer (A) that obtain, 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, but also two or more combinationally uses.

The weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is 500,000-300 ten thousand, preferably 700,000-250 ten thousand, particularly preferably 1,000,000-200 ten thousand.That is, the 1st (methyl) acrylic ester polymer (A) is high-molecular weight polymer composition.

As the 1st (methyl) acrylic ester polymer (A) weight average molecular weight as described in scope, polymkeric substance (A) has the large molecular weight compared, so described structure X can be formed (supposition) well.

At this, as the 1st (methyl) acrylic ester polymer (A) weight average molecular weight 500,000 less than, the tackiness agent obtained has gel fraction low, just has the possibility of weather resistance and reusability difference.In addition, the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is more than 3,000,000, degenerate with the intermiscibility of the 2nd (methyl) acrylic ester polymer (B) etc., the stress relaxation rate of the tackiness agent obtained has the possibility of variation.

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

From the tackiness agent that the tackiness composition containing the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) with described ratio obtains, described structure X can be formed (supposition) well.

As linking agent (C), preferably exemplify isocyanates linking agent, epoxies linking agent, aziridines linking agent, metal complex class linking agent etc.

Isocyanates linking agent, at least containing polyisocyanate compounds thing.As polyisocyanate compounds, can exemplify, the aromatic poly-isocyanate of tolylene diisocyanate, diphenylmethanediisocyanate, p-Xylol group diisocyanate etc.; The aliphatic polymeric isocyanate of hexamethylene diisocyanate etc.; The ester ring type polymeric polyisocyanate etc. of isophorone diisocyanate and hydrogenation diphenylmethanediisocyanate etc., and their biuret body and chlorinated isocyanurates body, further with ethylene glycol, propylene glycol, dimethyltrimethylene glycol, TriMethylolPropane(TMP), the adducts etc. of the compound containing low molecule active hydrogen of castor-oil plant wet goods.Wherein, in order to the rigidity and the flexibility that make the crosslinked configuration obtained have appropriateness, tolylene diisocyanate (TDI class) affixture of TriMethylolPropane(TMP) is particularly preferably.

As epoxies linking agent, can 1 be exemplified, two (the N of 3-, N '-2-glycidyl ether amino methyl) hexanaphthene, N, N-, N ', N '-four glycidyl ether m-p-Xylol base diamines, ethylene glycol diglycidylether base ether, 1,6-hexane diol 2-glycidyl ether ether, TriMethylolPropane(TMP) 2-glycidyl ether ether, 2-glycidyl ether aniline, 2-glycidyl ether amine etc.

Aziridines linking agent, ditan 4 can be exemplified, 4 '-bis-(1-aziridine methane amide), trimethylolpropane tris β-aziridine propionate, tetramethylol methane three β-aziridine propionate, toluene 2,4-two (1-aziridine methane amide), Persistols, two between xylylene 1-(2-methylaziridine), three-1-(2-methylaziridine) phosphine, trimethylolpropane tris β-(2-methylaziridine) propionic ester etc.

In metal complex class linking agent, there is atoms metal to be the coordination compound of aluminium, zirconium, titanium, zinc, iron and tin etc., but be preferred from performance this point aluminium coordination compound.As aluminium coordination compound, such as, diisopropoxy aluminium list oleyl alcohol acetylacetic ester, single aluminum isopropoxide two oleyl alcohol acetylacetic ester, single aluminum isopropoxide list oleic acid list ethyl acetoacetic ester, diisopropoxy aluminium list lauryl acetoacetate, diisopropoxy aluminium list stearyl acetylacetic ester, diisopropoxy aluminium list iso stearyl acetylacetic esters etc.

The amount of linking agent (C), make the bridging property base of described linking agent (C) (such as, isocyanate group) to the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) (such as, hydroxyl) amount, be generally the amount of 0.05-5 equivalent, the amount of preferred 0.1-3.5 equivalent, the particularly amount of preferred 0.3-1.0 equivalent.The amount of described bridging property base 0.05 equivalent less than occasion, the gel fraction of the tackiness agent obtained is low, has the possibility that can not give full play to cohesive force.In addition, as described in the amount of bridging property base be more than 0.1 equivalent, particularly more than 0.3 equivalent, the tackiness agent obtained can make weather resistance become excellent further.On the other hand, as described in the amount of bridging property base be below 3.5 equivalents time, the tackiness agent obtained can become the excellent thing of reusability.Further, as as described in the amount of bridging property base be below 1.0 equivalents, linking agent (C) can be made to be formed with contribution only to the three-dimensional netted structure of polymkeric substance (B), can effectively to prevent crosslinked (supposition) of polymkeric substance (A).Its result, the stress relaxation rate of the tackiness agent obtained is excellent.

In addition, in present embodiment, as linking agent (C), if with the linking agent that reactive pass of two sides of the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) and the reactive functional group (a1) of the 1st (methyl) acrylic ester polymer (A) is consistent kind, can multiple kind using.Viewpoint is easy to the control of the three-dimensional netted structure formed by the 2nd (methyl) acrylic ester polymer (B), as such as only using isocyanates linking agent such, as functional group, the linking agent of preferred use a kind, further, as compound, only a linking agent is used to be particularly preferably.

At this, linking agent (C), with (methyl) acrylic ester polymer (A) and (B) respective containing the combination of reactive functional group monomer, in the occasion that linking agent (C) is isocyanates linking agent, as polymkeric substance (A) containing reactive functional group (a1) monomer, preferred carboxyl group-containing monomer; As polymkeric substance (B) containing reactive functional group (b1) monomer, preferred hydroxyl monomer or emulsion stability (particularly hydroxyl monomer); As the monomer containing reactive functional group (b2) of polymkeric substance (B), carboxyl group-containing monomer is preferred.

On the other hand, linking agent (C) is epoxies linking agent, the occasion of aziridines linking agent or metal complex class linking agent, as the monomer containing reactive functional group (a1) of polymkeric substance (A), preferred hydroxyl monomer, as polymkeric substance (B) containing reactive functional group (b1) monomer, preferred carboxyl group-containing monomer, as polymkeric substance (B) containing reactive functional group (b2) monomer, preferred hydroxyl monomer.

The flexibility of the key formed between linking agent (C) and polymkeric substance (B), and the stability of crosslinking reaction, further, reactive base and the silane coupling agent (E) of polymkeric substance (A) react appositely, useful viewpoint is improved to the adhesion durability of the tackiness agent obtained, make linking agent (C) for isocyanates linking agent, what make polymkeric substance (A) is carboxyl group-containing monomer containing reactive functional group (a1) monomer, what make polymkeric substance (B) is hydroxyl monomer containing reactive functional group (b1) monomer, and not use containing reactive functional group (b2) monomer as particularly preferred.

As charged preventor (D), only otherwise have obstruction to effect of the present invention, can give the thing of charged preventive to the tackiness agent obtained, can exemplify ionic compound, interfacial agent etc., wherein ionic compound is preferred.Ionic compound, liquid also can, solid also can.At this, the so-called ionic compound in this specification sheets is positively charged ion and negatively charged ion, mainly with the compound that electrostatic attraction combines.

As ionic compound, preferably contain nitrogen salt, containing sulfosalt, phosphorous salts, an alkali metal salt and alkali earth metal salt.In addition, as an alkali metal salt, lithium salts and sylvite are preferred.As the concrete example of described charged preventor (D), phosphofluoric acid N-butyl 4-picoline can be exemplified, n-hexyl 4-picoline hexafluorophosphate, normal-butyl 2-hexyl pyridine perchlorate, two (fluorine sulfimide) potassium (KFSI), two (trifluoromethanesulfonimide) potassium (KTFSI), two (fluorine sulfimide) lithium (LiFSi), two (trifluoromethane sulfonium imide) lithium (LiTFSI), two (trifluoromethane sulphonyl) imides of normal-butyl 2-hexyl pyridine etc.Above charged preventor (D), can a kind be used alone, but also two or more combinationally uses.

The amount of the charged preventor (D) in the tackiness composition of present embodiment, preferred 0.1-30 quality % is particularly preferably with 0.5-20 quality %, is particularly preferably further with 1.0-10.0 quality %.As make the amount of charged preventor (D) as described in scope, while can effectively playing charged preventive, the amount of other composition (A)-(C) in the tackiness composition of present embodiment can be guaranteed.

In addition, charged preventor (D), it is used alone as preferably, but with dispersion agent and with also preferred.The occasion that the solvability of the charged preventor (D) in tackiness composition is insufficient, by dispersion agent and use, solvability can be improved.

As dispersion agent, such as, alkyl diol dialkyl ether etc. are preferred.As the concrete example of alkyl diol dialkyl ether, ethohexadiol dibutyl ether can be exemplified, ethohexadiol Anaesthetie Ether, ethohexadiol dimethyl ether, hexylene glycol dibutyl ether, hexylene glycol Anaesthetie Ether, hexylene glycol dimethyl ether, TEG dibutyl ether, TEG Anaesthetie Ether, TEG dimethyl ether (following, also to claim " four symmetrical diether "), triethylene glycol Anaesthetie Ether, triethylene glycol dimethyl ether etc.These dispersion agents, can a kind be used alone, but also two or more combinationally uses.

As the use level of dispersion agent, preferred with 0.5-1.5 to the mol ratio of charged preventor (D), 0.7-1.2 is more preferably, is particularly preferably with 0.9-1.1.

In addition, as above-mentioned, 1st (methyl) acrylic ester polymer (A), or the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), as constituent, containing the occasion of alkylene oxide group monomer, the amount of charged preventor (D) can be made to reduce.Specifically, the amount in the tackiness composition of present embodiment, preferred 0.1-10.0 quality %, particularly preferred 0.5-5.0 quality %, the further scope of preferred 1.0-3.0 quality %.

The tackiness composition of present embodiment, preferably, further containing silane coupling agent (E).As contained this silane coupling agent (E), 1st (methyl) acrylic ester polymer (A) has the occasion of carboxyl, the organic reaction base etc. of silane coupling agent (E) reacts with the carboxyl of the 1st (methyl) acrylic ester polymer (A), on the other hand, the alkoxysilyl group etc. of silane coupling agent (E) acts on the to-be-adhered object face of glass substrate etc.Thus, such as polarized light piece is carried out on liquid-crystalline glasses unit etc. the occasion of fitting, the adherence between tackiness agent and liquid-crystalline glasses unit can become more good.In addition, the reactive functional group (a1) of polymkeric substance (A) is the occasion beyond carboxyl, and the silane coupling agent (E) with the organic reaction base acted on described reactive functional group (a1) is suitable for choice for use.

As this silane coupling agent (E), for having the silicoorganic compound of an alkoxysilyl group in molecule at least, good with the intermiscibility of tackiness agent composition, and there is the thing of photopermeability, such as transparent in fact thing is preferred.The addition of such silane coupling agent (E), to the 1st (methyl) acrylic ester polymer (A) 100 mass parts, is preferably with 0.01-1.0 mass parts, is particularly more preferably with 0.05-0.5 mass parts.

As the concrete example of silane coupling agent (E), can exemplified by vinyl Trimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane etc. containing polymerizability unsaturated group have silicon compound; The silicon compound with epoxy structure of 3-glycidyl ether propyl trimethoxy silicane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.; 3-TSL 8330, just (2-amino-ethyl)-3-TSL 8330, just (2-amino-ethyl)-3-amino propyl methyl dimethoxysilane etc. containing aminosilicon compounds; 3-r-chloropropyl trimethoxyl silane; 3-isocyanic ester propyl-triethoxysilicane etc.These, get final product a kind and be used alone, but also two or more use that combines.

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

(manufacture method of tackiness composition)

Described tackiness composition, the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) is made to manufacture respectively, while they are mixed, can in the arbitrary stage, by linking agent (C), charged preventor (D) and add silane coupling agent (E) as required thus obtained.

As preferred concrete example, (methyl) acrylic ester polymer (A) and (B) can be manufactured with common radical polymerization respectively.The polymerization of (methyl) acrylic ester polymer (A) and (B), uses polymerization starter as required, carries out with solution polymerization process etc.As polymerization solvent, ethyl acetate, ro-butyl acetate, Sucrose Acetate base ester, toluene, acetone, hexane and methyl ethyl ketone etc. can be exemplified, more than 2 kinds also with also can.

As polymerization starter, can azo compound and organo-peroxide etc. be exemplified, more than 2 kinds also can be used together.As azo compound, can 2 be exemplified, 2 '-azobisisobutylonitrile cyanogen, 2, 2 '-azo two (2-methyl fourth cyanogen), 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 ester), 4, 4 '-azo two (4-cyano group valeric acid (valericacid)), 2, 2 '-azo two (2-hydroxymethyl propionitrile) and 2, 2 '-azo two [2-(2-imidazoles beautiful jade-2-base) propane] etc.

As organo-peroxide; such as; benzoyl peroxide, benzoyl hydroperoxide t-butyl ester, isopropyl benzene hydroperoxide, peroxide two dimethyl isopropyl ester, peroxide two carbonic acid diη-propyl ester, peroxide two carbonic acid two (2-ethoxyethyl group) ester, peroxide new certain herbaceous plants with big flowers acid t-butyl ester, peroxide trimethylacetic acid t-butyl ester (tert-Butylperoxypivalate), (3; 5,5-trimethyl acetyl base) superoxide, two propionyl superoxide and diacetyl superoxide etc.

In addition, in described Polymerization Engineering, coordinate the chain of 2 mercapto ethanol etc. to move agent, can regulate the weight average molecular weight of the polymkeric substance obtained.

Then, the solution of the polymkeric substance (A) obtained and (B) is mixed, adds dilution solvent.Afterwards, by linking agent (C), charged preventor (D) and add silane coupling agent (E) as required, fully mixes, obtains the tackiness composition (coating solution) diluted with solvent.

The dilution of tackiness composition is become the diluting solvent of coating solution, the aliphatic hydrocarbon of hexane, heptane and hexanaphthene etc. can be exemplified; The aromatic hydrocarbons of toluene and dimethylbenzene etc.; The halohydrocarbon of methylene dichloride, ethylene dichloride etc.; The alcohol of methyl alcohol, ethanol, propyl alcohol, butanols and 1-methoxyl group 2-propyl alcohol etc.; The ketone of acetone, methyl ethyl ketone, 2 pentanone, isophorone, pimelinketone etc.; The ester of ethyl acetate, acetic acid butyl etc.; The cellosolve type solvents etc. of ethyl cellosolve etc.

So, as the concentration viscosity of the coating solution of modulation, as long as in the scope that coating is possible, particularly do not limit, suitable selection according to circumstances can be carried out.Such as, can by the concentration dilution of tackiness composition to 10-40 quality %.In addition, when worth coating solution, the interpolation of diluting solvent etc. is not prerequisite, as long as have can application viscosity etc. for tackiness composition, does not add diluting solvent passable yet.In this occasion, tackiness composition can intactly use as coating solution.

(tackiness agent)

The tackiness agent of present embodiment, forms by described tackiness composition is crosslinked.Being cross-linked of described tackiness composition, can be undertaken by heat treated.In addition, this heat treated, can double as the drying treatment of the volatilization of the dilution solvent making tackiness composition etc.

Carrying out the occasion of heat treated, Heating temperature, is that preferably particularly 70-120 DEG C is more preferably with 50-150 DEG C.In addition, heat-up time, be divided into preferably with 30 seconds-3, particularly within 50 seconds-2, be divided into more preferably.Further, after heat treated, for particularly preferably during normal temperature (such as, 23 DEG C, 50%RH) arranges the maturation of 1-2 week degree.

By described heat treated (and maturation), by linking agent (C) by while crosslinked to the 2nd (methyl) acrylic ester polymer (B), in three-dimensional netted structure, insert the 1st (methyl) acrylic ester polymer (A), form described structure X (supposition).1st (methyl) acrylic ester polymer (A) has the occasion of carboxyl, 1st (methyl) acrylic ester polymer (A) and silane coupling agent (E) react, and the adhesive durability of the glass substrate to liquid crystal cells etc. of tackiness agent can be made to improve.

The surface resistivity of the tackiness agent of present embodiment, with 3.0 × 10 ¹¹Ω/below sq is preferably, particularly 1.0 × 10 ¹¹Ω/below sq is more preferably, further with 8.0 × 10 ¹⁰Ω/below sq is most preferably.As surface resistivity as described in value below time, charged preventive can be given full play to.In addition, in present embodiment, the charged preventor (D) in described tackiness composition even if amount at below 3 quality %, also as described, charged preventive can be given full play to.

The clinging power of the tackiness agent of present embodiment is, being preferably to the clinging power of non-alkali glass with 0.1-50N/25mm, be particularly preferred with 0.5-30N/25mm, is more preferably further with 3.0-20N/25mm.In addition, clinging power described herein is the 180 ° of stretch release clinging powers (peeling rate 300mm/miN) according to JISZ0237.Adhesion body attaches, at 0.5MPa, 50 DEG C carry out 20 points of pressurizations after, at 23 DEG C, under the condition of 50%RH, after carrying out placing for 24 hours, carry out measuring.Clinging power, in described scope, when being applicable to the optics of polarized light piece etc., can prevent from floating and stripping etc.

In addition, the tackiness agent of present embodiment, the preferred 30-90% of gel fraction, being particularly preferably with 40-80%, is preferred further with 45-75%.The gel fraction of the tackiness agent of present embodiment, namely as crosslinked degree as described in scope, by the crosslinked of the 2nd (methyl) acrylic ester polymer (B), three-dimensional netted structure that is that formed can be formed well, and tackiness agent is all excellent two sides of resistance to light leakage and weather resistance.

In addition, the gel fraction of tackiness agent, being the value of (during maturation) during attaching, specifically, is be coated with on stripping film by tackiness composition, after heat treated, at 23 DEG C, carries out the gel fraction after keeping on the 7th under the environment of 50%RH.This is the gel fraction due to tackiness agent, and through front during maturation, its value is variation.From such viewpoint, occasion not clear through whether during maturation, can again, at 23 DEG C, after carrying out keeping on the 7th under the environment of 50%RH, now gel fraction as described in scope, just no problem.

Tackiness agent described above, preferably be applicable to optics, such as, bonding between the optics of polarized light piece (polarizing film) and polarizer (phase-contrast film) etc., or polarized light piece (polarizing film) and polarizer (phase-contrast film) and glass substrate is bonding just very applicable.The tackiness agent of present embodiment, owing to having charged preventive, electrostatic is difficult to occur, thus effectively can suppress the problem that electrostatic causes.In addition, the adhering agent layer formed by described tackiness agent, stress relaxation rate is very excellent, even if so the large occasion of the dimensional change of to-be-adhered object, also can carry out absorption to the stress occurred by dimensional change by adhering agent layer and relax.Therefore long-term do not peel off from to-be-adhered object while, can to by described such effectively preventing for light leak during optics.That is, the tackiness agent of present embodiment, existing charged preventive, can make again resistance to light leakage and weather resistance two side all good.

(adhesive sheet)

As shown in Figure 1, the adhesive sheet 1A of the 1st embodiment, from lower, is followed successively by stripping film 12, the adhering agent layer 11 that the release surface of stripping film 12 is stacked, and the base material 13 that adhering agent layer 11 is stacked is formed.

In addition, as shown in Figure 2, the adhesive sheet 1B of the 2nd embodiment, comprises 2 pieces of stripping film 12a, 12b and by these 2 pieces of stripping film 12a, and the adhesive layer 11 that 12b seizes on both sides by the arms, thus described adhesive layer 11 and 2 pieces of stripping film 12a, the release surface of 12b connects.In addition, the release surface of so-called stripping film in this specification sheets, for having the face of separability at stripping film, though it contains the face of having carried out lift-off processing and does not implement lift-off processing, also demonstrates face two side of separability.

At any one adhesive sheet 1A, in 1B, adhering agent layer 11 is all make above-mentioned tackiness composition carry out crosslinked tackiness agent.

The thickness of adhering agent layer 11, can according to adhesive sheet 1A, the application target of 1B carries out suitable selection, be generally 5-100 μm, the scope of preferred 10-60 μm, such as, as optics, particularly as the adhering agent layer of polarized light piece and the occasion used, with 10-50 μm, be particularly preferred with 10-30 μm.

As base material 13, have no particular limits, the thing usually used as the substrate sheets at adhesive sheet can use.Such as, as required, outside optics, woven or the non-woven fabrics of the fiber of artificial silk, vinylformic acid, polyester etc. can be used; Upper matter paper, glassine paper, impregnation paper, the stationery of art paper etc.; Aluminium, the tinsel of copper etc.; Polyurethane foaming body, the foam of foam polyethylene etc.; Polyethylene terephthalate, polybutylene terephthalate, the polyester film of PEN etc., polyurethane film, polyethylene film, polypropylene film, the cellulosefilm of triacetyl cellulose etc., poly-ethylene dichloride base film, poly-inclined chloroethylenes base film, polyvinyl alcohol film, ethylene vinyl acetate base co-polymer film, polystyrene film, polycarbonate film, acrylic resin films, norbornene type resin film, the plastics film of cyclenes resin film etc.; These the body etc. that is stacked of more than two kinds also can use.Plastics film, can use an axial compression to prolong or two axial compressions are prolonged.

As optics, polarized light piece (polarizing film), polarisation can be exemplified, polarizer (phase-contrast film), angle of visibility mend reward film, briliancy improves film, contrast gradient improves film, liquid crystal polymer film, diffusion film and semi-penetration film etc.Wherein polarized light piece (polarizing film), is suitable for contraction, and dimensional change is large, from the viewpoint of resistance to light leakage, as the tackiness agent (described adhering agent layer 11) of present embodiment formation to as if suitable.

The thickness of base material 13, different according to its kind, in the occasion of such as optics, be generally 10 μm-500 μm, be preferably 50 μm-300 μm.

As stripping film 12, 12a and 12b, polyethylene film can be exemplified, polypropylene film, polybutene film, polybutadiene membrane, poly-methyl pentene film, poly-ethylene dichloride base film, ethylene dichloride base co-polymer film, pet film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate base film, amberlite membrane of lipoprotein, ethene (methyl) acrylic copolymer film, ethene (methyl) acrylic ester copolymerization thing film, polystyrene film, polycarbonate film, polyamide layer, fluorine resin film etc.In addition, these crosslinked film is also suitable for.Further, these laminate film also can use.

In the release surface (face particularly connected with adhering agent layer 11) of described stripping film, preferably impose lift-off processing.The stripper used in lift-off processing, 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 has no particular limits, and is generally 20-150 μm of degree.

The manufacture of described adhesive sheet 1A is in the release surface of stripping film 12, is coated with by the solution (coating solution) containing described tackiness composition, carry out heat treated make adhering agent layer 11 formed after, on adhering agent layer 11, base material 13 is stacked.Afterwards, during preferably maturation being set.

In addition, about the condition of heat treated and maturation, as above-mentioned.

In addition, manufacture described adhesive sheet 1B to make, in the release surface of a stripping film 12a (or 12b), carry out the coating of the coating solution containing described tackiness composition, after carrying out heat treated, after adhering agent layer 11 is formed, another release surface of its adhering agent layer 11 and stripping film 12b (or 12a) overlaps.

Described method of coating solution being carried out be coated with, can exemplify rod and be coated with method, scrape the skill in using a kitchen knife in cookery, rolling method, scraper plate coating method, die coating methods, gravure coating method etc.

At this, such as, when manufacturing the liquid crystal display device having liquid crystal cells and polarized light piece to form, the base material 13 as adhesive sheet 1A uses polarized light piece, by the stripping film 12 of described adhesive sheet 1A, the adhering agent layer 11 exposed and liquid crystal cells is carried out fitting.

Such as, in addition, when manufacturing the liquid crystal display device of configuration phase difference plate between liquid crystal cells and polarized light piece, as an example, first, peeled off by the stripping film 12a (or 12b) of of adhesive sheet 1B, the adhering agent layer 11 exposed of adhesive sheet 1B is fitted with polarizer.Then, will the stripping film 12 of the adhesive sheet 1A of polarized light piece be used to peel off as base material 13, the adhering agent layer 11 exposed of adhesive sheet 1A be fitted with described polarizer.Further, from the adhering agent layer 11 of described adhesive sheet B, another stripping film 12b (or 12a) is peeled off, the adhering agent layer 11 exposed of adhesive sheet B is fitted with liquid crystal cells.

, because adhering agent layer 11 has charged preventive, not easily there is electrostatic in above adhesive sheet 1A, 1B, that can effectively suppress electrostatic to cause be bad.In addition, the stress relaxation rate of adhering agent layer 11 is very excellent, even if so using the bonding occasion of such as polarized light piece, the stress adhering agent layer 11 that the distortion due to polarized light piece can be occurred absorbs mitigation, thus, excellent resistance to light leakage and high-durability (supposition) can be played.

Embodiment described above, record, but they does not limit the present invention in order to the present invention of understanding of the present invention better.Therefore, each key element that described embodiment is recorded comprises all design alterations and the equivalent of the scope belonging to technology of the present invention.

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

[embodiment]

Below, by embodiment etc., the present invention is further illustrated, but scope of the present invention is not limited to these embodiment etc.

(embodiment 1)

1. the modulation of polymkeric substance (A)

To in the reaction vessel with stirrer, thermometer, reflux cooler, dripping device and nitrogen ingress pipe, add n-butylacrylate 75.0 mass parts, vinylformic acid 2-methoxy ethyl ester 20.0 mass parts, vinylformic acid 5.0 mass parts, ethyl acetate 200 mass parts and 2,2 '-azobisisobutylonitrile cyanogen 0.08 mass parts, the air nitrogen replacement in described reaction vessel.Stir under this nitrogen atmosphere, reaction soln is warming up to 60 DEG C, after reaction in 16 hours, be cooled to room temperature.At this, a part for the solution obtained carries out molecular weight determination by following method, confirms that weight average molecular weight is the generation of the polymkeric substance (A) of 1,200,000.

2. the modulation of polymkeric substance (B)

To having agitator, thermometer, reflux cooler, in the reaction vessel of dripping device and nitrogen ingress pipe, add n-butylacrylate 85.0 mass parts, vinylformic acid 2-hydroxyethyl ester 15.0 mass parts, ethyl acetate 200 mass parts, 2,2 '-azobisisobutylonitrile cyanogen 0.16 mass parts and 2 mercapto ethanol 0.3 mass parts, the air nitrogen in described reaction vessel is replaced.Stir under this nitrogen atmosphere, reaction soln is warming up to 70 DEG C of intensifications, after reaction in 6 hours, is cooled to room temperature.At this, a part for the solution obtained carries out molecular weight determination by following method, confirms the generation of the polymkeric substance (B) of weight average molecular weight 60,000.

3. the modulation of tackiness composition

By polymkeric substance (A) 100 mass parts (solids component scaled value) obtained in described engineering (1) with after polymkeric substance (B) 15 mass parts (solids component scaled value) that described engineering (2) obtains mixes, as linking agent (C), add tolylene diisocyanate (TDI class) affixture (Japanese polyurethane Inc., trade(brand)name " CORONET-L ") 2.21 mass parts being equivalent to the TriMethylolPropane(TMP) of the amount of hydroxyl 0.6 equivalent of polymkeric substance (B).Finally, as charged preventor (D), add phosphofluoric acid normal-butyl 4-picoline 2.0 mass parts, and as silane coupling agent (E), add 3-glycidyl ether propyl trimethoxy silicane (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ") 0.2 mass parts, fully stirs, obtains the diluting soln of tackiness composition.

At this, the formula of described tackiness composition is as shown in table 1.In addition, the contracted notation etc. recorded in table 1, details is as follows.

[polymkeric substance (A) and (B)]

BA: n-butylacrylate

AA: vinylformic acid

MA: methacrylic acid

MEA: vinylformic acid 2-methoxy ethyl ester

HEA: vinylformic acid 2-hydroxyethyl ester

4HBA: vinylformic acid 4-hydroxybutyl ester

PhEA: PhEA

[isocyanates linking agent (C)]

CORONET-L: the tolylene diisocyanate affixture (Japanese polyurethane Inc., trade(brand)name " CORONET-L ") of TriMethylolPropane(TMP)

CORONET-HX: hexamethylene diisocyanate class chlorinated isocyanurates (Japanese polyurethane Inc., trade(brand)name " CORONET-HX ")

DURANATE24A-100: hexamethylene diisocyanate class biuret (chemical company of Asahi Chemical Industry system, trade(brand)name " DURANATE24A-100 ")

[charged preventor (D)]

Pyridine: phosphofluoric acid normal-butyl 4-picoline

KFSI: two (fluorine sulfimide) potassium (KFSI): four symmetrical diether=1: the use level in the mixing solutions ※ table of 1 (mass ratio), is only the value of KFSI

LiTFSI: two (trifluoromethane sulfonium imide) lithium (LiTFSI): four symmetrical diether=1: the use level in the mixing solutions ※ table of 1 (mass ratio) is only the value of LiTFSI

AS-804: the first industrial pharmaceutical Inc., salt charged preventor, trade(brand)name " AS-804 "

[silane coupling agent (E)]

KBM403:3-glycidyl ether propyl trimethoxy silicane (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ")

KBE9007:3-isocyanic ester propyl-triethoxysilicane (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBE9007 ")

X-41-1059A: oligopolymer one type of silane coupler (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " X-41-1059A ")

Stripping film (Lindeke Co., Ltd's system of lift-off processing has been carried out at a face type siloxane stripper of pet film, SP-PET3811, thickness: 38 μm) lift-off processing face on, the diluting soln scraper for coating method of the tackiness composition obtained is coated with, dried thickness is made to be 25 μm, afterwards at 90 DEG C, carry out the heat treated in 1 point, adhering agent layer is formed.

Then, the polarized light piece that the polarizing film form the polarized light film with disc-like liquid crystal layer and angle of visibility expand film integration is fitted, and adhering agent layer and disc-like liquid crystal layer are connected, 23 DEG C, 50%RH carries out maturation in 7 days, obtains the polarized light piece being with adhering agent layer.

(embodiment 2-26, comparative example 1-3)

Form kind and the ratio of each monomer of tackiness composition, linking agent, beyond what the proportioning of the kind of charged preventor and silane coupling agent and use level and polymkeric substance (A) and polymkeric substance (B) was as described in Table 1 change like that, carry out the manufacture of the polarized light piece being with adhering agent layer similarly to Example 1.

At this, above-mentioned weight average molecular weight (Mw), for carrying out the weight average molecular weight of the polystyrene conversion measuring (GPC mensuration) by following condition with gel permeation chromatography (GPC).

< condition determination >

GPC determinator: Tosoh Inc., HLC-8020

GPC post (sequentially passing through with following): Tosoh Inc.

TSKguardcolumNHXL-H

TSKgelGMHXL(×2)

TSKgelG2000HXL

Measure solvent: tetrahydrofuran (THF)

Measure temperature: 40 DEG C

(experimental example 1) (mensuration of gel fraction)

In embodiment or comparative example, the polarized light piece used in the making of the polarized light piece of band adhering agent layer is replaced, use stripping film (Lindeke Co., Ltd's system of pet film face type siloxane stripper having been carried out lift-off processing, SP-PET3801, thickness: 38 μm), carry out the making of adhesive sheet.Specifically, on the adhering agent layer exposed of the tectosome be made up of the stripping film/adhering agent layer obtained in the manufacturing processed of embodiment or comparative example (thickness: 25 μm), described stripping film is carried out stacked, tack coat is connected with side, lift-off processing face.Thus, the adhesive sheet of the formation into stripping film/adhering agent layer/stripping film is obtained.

By the adhesive sheet that obtains at 23 DEG C, under the condition of 50%RH, carry out maturation on the 7th.Afterwards, described adhesive sheet is made the sample of the size of 80mm × 80mm, its adhering agent layer polyester net (net size 200) is wrapped up, only weighing is carried out to the quality precision balance of tackiness agent.Using this quality as M1.

Bonding, by the tackiness agent with described polyester net parcel, at room temperature under (23 DEG C), carry out 24 h immersion by ethyl acetate.Afterwards tackiness agent is taken out, 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 to the quality of dried tackiness agent, carry out weighing with precision balance.Quality is now as M2.Gel fraction (%), represents with (M2/M1) × 100.The results are shown in table 2.

(experimental example 2) (light leak experiment)

By the polarized light piece of band adhering agent layer obtained in embodiment or comparative example, be adjusted to 233mm × 309mm size with cutting device (the super cutter of Di Ye manufacturing company system, PN1-600).Stripping film is peeled off, after being attached at by the adhering agent layer exposed on non-alkali glass (Corning Incorporated's system, hawk XG), in the still that the former making of chestnut is made, at 0.5MPa, 50 DEG C, carries out pressurization in 20 minutes.In addition, described laminating, make the polarized light piece with adhering agent layer be Niccol cross state (polarizing axis: ∠ 45 °, ∠ 135 °) with polarizing axis.In this state, under the dry environment of 80 DEG C, after carrying out placing for 250 hours, 23 DEG C, to carry out under the environment of 50%RH placing for 2 hours, as sample, carry out light leak evaluation by method shown below.The results are shown in table 2.

< light leak is evaluated: Δ L*>

Use the MCPD-2000 of great Zhong electronics corporation, measure the brightness L* in each field shown in the Fig. 3 in described sample, luminance difference Δ L* following formula is asked, as light leak:

ΔL*＝[(b+c+d+e)/4]-a

(a, b, c, d and e, be respectively A field, B field, C field, the brightness of the prespecified measuring point (middle body 1 place in each field) in D field and E field), it can be used as light leak.The less light leak of value of Δ L* is less.

(experimental example 3) (durability evaluation)

By the polarized light piece with adhering agent layer obtained in embodiment or comparative example, with cutting device (the super cutter of Di Ye manufacturing company system, PN1-600), be adjusted to 233mm × 309mm size.By stripping film peel off, the adhering agent layer exposed is attached on non-alkali glass (Corning Incorporated's system, hawk XG), with in the still that the former making of chestnut is made at 0.5MPa, at 50 DEG C, carry out 20 points of pressurizations.

Afterwards, under dropping into the environment of following each durable condition, observe with 10 times of magnifying glasses after 500 hours.The change of outward appearance is base Huaihe River with following.Result represents at table 2.

In ◎: 4 limits, no problem.

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

×: at least 1 limit on 4 limits, the position of more than 0.6mm from peripheral end, have float, peel off, foam, the abnormal appearance of the tackiness agent of more than the 0.1mm of striped etc.

The durable condition > of <

80 DEG C of dryings

60 DEG C, relative humidity 90%RH

(experimental example 4) (mensuration of clinging power)

The polarized light piece of the band adhering agent layer obtained in embodiment or comparative example, by severing, makes 25mm wide, the sample that 100mm is long.From this sample, stripping film is peeled off, on non-alkali glass (Corning Incorporated's system, hawk XG), described sample is attached between the adhering agent layer exposed, after this, at 0.5MPa in the automatic still of Li Yuan manufacturing company system, 50 DEG C, carry out pressurization in 20 minutes.Afterwards, at 23 DEG C, carry out under the condition of 50%RH placing for 24 hours, then tensile testing machine (Ao Rui Inc. is used, TENSILON), at peeling rate 300mm/min, under the condition that peel angle is 180 °, (clinging power after 1 day is attached to clinging power; N/25mm) measure.The results are shown in table 2.

(experimental example 5) (mensuration of sheet resistance value)

The polarized light piece of the band adhering agent layer obtained in embodiment or comparative example is cut into the size of 50mm × 50mm, the sample obtained, the temperature of 23 DEG C, carries out under the humidity of 50%RH placing for 24 hours.Afterwards, peeled off by stripping film, the adhering agent layer surface resistrivity meter (analytical technology Inc. of Mitsubishi Chemical, high resistance instrument UPMCP-HT450 type) exposed, measures by JISK6911 effects on surface resistance value (Ω/sq).The results are shown in table 2.

Table 1

Table 1 (Continued)

[table 2]

From table 2 can be clear and definite learn, the polarized light piece of the band adhering agent layer obtained in an embodiment, while having sufficient clinging power and charged preventive, show excellent stress relaxation rate, resistance to light leakage and weather resistance are all fine.

[utilizing possibility in industry]

Tackiness composition of the present invention and tackiness agent, be used in optics, such as when the bonding of polarized light piece and polarizer, can use well, in addition, adhesive sheet of the present invention, the adhesive sheet used for optical part as polarized light piece and polarizer etc. can be suitable for well.

Claims

1. a tackiness composition, is characterized in that:

Containing the 2nd (methyl) acrylic ester polymer (B), linking agent (C) and charged preventor (D) that weight average molecular weight be 500,000 ~ 3,000,000 the 1st (methyl) acrylic ester polymer (A), weight average molecular weight is 8000 ~ 300,000

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

Described 2nd (methyl) acrylic ester polymer (B), the monomer with the functional group (b1) of reacting with described linking agent (C) is contained as constituent, further, there is the ratio of the monomer of described functional group (b1), be more than 5 quality % in described 2nd (methyl) acrylic ester polymer (B), and 50 quality % less than

Described 1st (methyl) acrylic ester polymer (A), as constituent not containing the monomer with the functional group of reacting with described linking agent (C), or contain the monomer of the functional group (a1) had also will be low than the described functional group (b1) of described 2nd (methyl) acrylic ester polymer (B) with the reactivity of described linking agent (C) as constituent.

2. tackiness composition according to claim 1, it is characterized in that: described 1st (methyl) acrylic ester polymer (A), or described 1st (methyl) acrylic ester polymer (A) and described 2nd (methyl) acrylic ester polymer (B), as the formation monomer unit of these polymkeric substance, containing 5 ~ 50 quality % containing alkylene oxide group monomer.

3. tackiness composition according to claim 1, is characterized in that: described charged preventor (D) is ionic compound.

4. tackiness composition according to claim 3, is characterized in that: described ionic compound, for from by containing at least a kind that selects in nitrogen salt, the group that forms containing sulfosalt, phosphorous salts, an alkali metal salt and alkali earth metal salt.

5. tackiness composition according to claim 4, is characterized in that: described an alkali metal salt is at least a kind that selects from the group be made up of lithium salts and sylvite.

6. tackiness composition according to claim 1, it is characterized in that: the described functional group (a1) in the 1st (methyl) acrylic ester polymer (A) is carboxyl, the described functional group (b1) of described 2nd (methyl) acrylic ester polymer (B) is hydroxyl, and described linking agent (C) is isocyanates linking agent.

7. tackiness composition according to claim 1, it is characterized in that: described 1st (methyl) acrylic ester polymer (A), as forming the monomer unit of this polymkeric substance not containing carboxyl group-containing monomer, or contain carboxyl group-containing monomer as described functional group (a1) with the amount of below 15 quality %.

8. tackiness composition according to claim 1, is characterized in that: described 2nd (methyl) acrylic ester polymer (B), containing 5 ~ 40 quality % as described in the hydroxyl monomer of functional group (b1).

9. tackiness composition according to claim 6, it is characterized in that: the amount of described isocyanates linking agent is, to the amount of the described functional group (b1) in described 2nd (methyl) acrylic ester polymer (B), the isocyanate group of this isocyanates linking agent becomes the amount of 0.1 ~ 3.5 equivalent.

10. a tackiness agent, it forms for the tackiness composition described in any one of claim 1 ~ 9 is crosslinked.

11. tackiness agents according to claim 10, is characterized in that: the sheet resistance value of described tackiness agent, are 3.0 × 10 ¹¹Ω/below sq.

12. 1 kinds of adhesive sheets, have base material and adhering agent layer, it is characterized in that: described adhering agent layer, are made up of tackiness agent according to claim 10.

13. adhesive sheets according to claim 12, is characterized in that: described base material is optics.

14. an adhesive sheet, the adhering agent layer having 2 pieces of stripping films and seized on both sides by the arms by this stripping film, described adhering agent layer connects with the release surface of described 2 pieces of stripping films thus, it is characterized in that: described adhering agent layer is made up of tackiness agent according to claim 10.