CN102888200A - Adhesive and adhesive sheet - Google Patents

Abstract

An adhesive and an adhesive sheet which are suitable for optical components, such as polarization light panel, etc., and have good stress relaxation rate and durability. The adhesive contains first (methyl) acrylic ester polymers (A) having a Mw of 500-3000 thousands, a component which is produced by cross-linking second (methyl) acrylic ester polymers (B) having a Mw of 80000-300 thousands and an anti-charge agent (D). In the tensile test, the breakage elongation is above 1500%, and the gel fraction is from 30 to 90%.

Description

Tackiness agent and adhesive sheet

Technical field

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

Background technology

In general, in liquid crystal panel, when polarized light piece and polarizer being adhered to the glass substrate etc. of liquid crystal cells, the adhering agent layer that the normal operation adhesion agent composition forms.But, the optics of polarized light piece and polarizer etc. can be because heat etc. be easy to contraction, namely can be owing to thermal distortion shrinks, its result, adhering agent layer stacked on described optics can not be followed its contraction, thereby peels off (what is called is floated, and peels off) generation at the interface, the optic axis of the optics that causes of the stress the during contraction of optics departs from thus, thus the problem that has light leak (so-called hickie) to occur.

As the method that this is prevented, can exemplify (1) clinging power is high, and the adhering agent layer that the form stability is good is fitted to the optics of polarized light piece etc., the method that thus contraction of optics is directly suppressed, the method for the adhering agent layer that the stress when perhaps (2) use the contraction of optics is little.As the method for (1), it is effective using the high adhering agent layer of Young's modulus as patent documentation 1 expression.On the other hand, as the method for (2), the good adhering agent layer of stress relaxation rate that use can be carried out soft correspondence to the distortion of optics is effective.But in the past, the occasion that so good adhering agent layer of stress relaxation rate is formed had the necessity of the cross-linking density in its adhering agent layer being hanged down design.So just have the intensity variation of adhering agent layer self, the problem that weather resistance degenerates.

Therefore, in patent documentation 2-4, for as the low scheme of the cross-linking density of adhering agent layer, in the acrylic acid or the like tackiness agent, to add plasticizer, Liquid Paraffin, polyurethane elastomer etc., the adhesion agent composition that obtains thus has appropriate flexibility, give stress relaxation to adhering agent layer, thus, obtain anti-light leak and weather resistance.

But, the plasticizer of interpolation or the adhesion agent composition of Liquid Paraffin, the adhering agent layer of its formation has the problem that its plasticizer in time and Liquid Paraffin can ooze out.Thus, the weather resistance variation, the to-be-adhered object liquid crystal cells is contaminated etc., and various problems are worried by people.In addition, add the adhesion agent composition of polyurethane elastomer, as keeping intermiscibility, still because the upper limit of the addition of polyurethane elastomer is limited, the inadequate tendency of improvement of stress relaxation rate is arranged.Further, the stress relaxation rate be improved and increase the addition of polyurethane elastomer, will cause the intermiscibility variation with the acrylic acid or the like tackiness agent, the problem of gonorrhoea etc. occurs.So, in the technology in the past, the anti-light leak of the adhering agent layer that is formed by the adhesion agent composition of used for optical part and the basic improvement of weather resistance are difficult.

But described adhering agent layer is stacked stripping film thereon, or the optics of polarized light piece and polarizer etc., usually is made of plastic material.Thus, electrical insulating property is high, and static is easy to occur in the situation when stripping film is peeled off etc.Under the remaining state of the static that so occurs, polarized light piece and polarizer etc. are to the applying of liquid crystal cells, and the orientation of liquid crystal molecule has chaotic possibility occurs, in addition, and the existence of static, the problem that also can cause that dust is attracted etc.

Therefore, add charged preventor (for example patent documentation 5-8) in the adhesion agent composition in order effectively to obtain the charged performance that prevents, to be proposed in.

[look-ahead technique document]

[patent documentation]

[patent documentation 1] JP 2006-235568 communique

[patent documentation 2] Unexamined Patent 5-45517 communique

[patent documentation 3] Unexamined Patent 9-137143 communique

[patent documentation 4] JP 2005-194366 communique

[patent documentation 5] JP 2005-290357 communique

[patent documentation 6] JP 2007-316377 communique

[patent documentation 7] JP 2008-95081 communique

[patent documentation 8] JP 2009-155585 communique

But, in adhesion agent composition, carry out the occasion that charged preventor adds, the weather resistance of the tackiness agent that obtains has the problem than common situation variation.In described tackiness agent, carry out the occasion of giving of stress relaxation rate, the interpolation of cross-linking density step-down and plasticizer etc. can make the further variation of above-mentioned weather resistance.Thus, giving of stress relaxation rate will become more difficult.So, have in the tackiness agent of charged preventive, the stress relaxation rate of inversely proportional relation and weather resistance two sides get well just becomes a large problem.

The content of invention

The present invention, in view of such actual state forms, purpose of the present invention just provides a kind of poly-charged preventive that has, and, when being applicable to the optics of polarized light piece etc., two sides of stress relaxation rate and weather resistance are good tackiness agent and adhesive sheet.

In order to reach described purpose, the 1st, the invention provides a kind of tackiness agent, it is characterized in that: comprise weight average molecular weight be 500,000-3,000,000 the 1st (methyl) acrylic ester polymer (A) and, weight average molecular weight is the crosslinked composition that forms of the 2nd (methyl) acrylic ester polymer (B) and the charged preventor (C) of 8000-30 ten thousand, extension at break degree in stretching experiment is more than 1500%, and gel fraction is 30-90% (invention 1).

The tackiness agent of described invention (invention 1) when having charged preventive, can be brought into play suitable cohesive force and good stress relaxation rate.Use has the tackiness agent of this good stress relaxation rate, when being applied to the optics of polarized light piece etc., can obtain in the sufficient charged preventive of performance, and two sides of anti-light leak and weather resistance are good adhesive sheet.

In the described invention (invention 1), to described the 1st (methyl) acrylic ester polymer (A) 1O0 mass parts, the ratio of described the 2nd (methyl) acrylic ester polymer (B) is for the 5-50 mass parts is preferred (invention 2).

Described invention (invention 1,2) in, described the 1st (methyl) acrylic ester polymer (A), perhaps described the 1st (methyl) acrylic ester polymer (A) and crosslinked before described the 2nd (methyl) acrylic ester polymer (B), as the formation monomer unit of described polymkeric substance, preferably contain alkylene oxide group monomer 5-50 quality % (invention 3).

In described invention (invention 1-3), preferred described charged preventor (C) is ionic compound (invention 4).

In described invention (invention 4), preferred described ionic compound is for from by at least a kind (inventing 5) containing nitrogen salt, contain sulfosalt, select the group that phosphorous salts and an alkali metal salt form.

In the described invention (invention 1-5), crosslinked front described the 2nd (methyl) acrylic ester polymer (B), as constituent, it is that 1 quality % is super that the functional group of preferred reactive is contained monomer, 50 quality % are less than (invention 6).

In the described invention (invention 6), preferred described the 2nd (methyl) acrylic ester polymer (B) and has and can react and crosslinked (invention 7) with the linking agent (D) of the bridging property base of described reactive functional group's reaction.

The 2nd, the invention provides a kind of adhesive sheet with base material and adhering agent layer, it is characterized in that: the adhesive sheet (invention 8) of described adhering agent layer for being consisted of by described tackiness agent (invention 1-7).

In described invention (invention 8), preferred described base material is optics (invention 9).

The 3rd, the present invention, be a kind of adhesive sheet, it has 2 pieces of stripping films and described 2 pieces of adhering agent layers that stripping film is seized on both sides by the arms, the release surface of described adhering agent layer and described 2 pieces stripping film is joined thus, it is characterized in that: described adhering agent layer preferably consists of (invention 10) by described tackiness agent (invention 1-7).

[effect of invention]

In the tackiness agent of the present invention, the low-molecular-weight polymkeric substance that in the past was used for plasticizer is formed three-dimensional netted structure by chemically crosslinked, in its three-dimensional netted structure, there is the polymkeric substance of a plurality of high molecular to insert, the polymer of high molecular is in bond, crosslinked configuration (supposition) like formation is intended between the polymkeric substance of high molecular.Thus, described tackiness agent when both having had charged preventive and large extension at break degree, has the gel fraction of regulation, thus, can bring into play suitable cohesive force and good stress relaxation rate.By using this tackiness agent with good stress relaxation rate, when being applicable to the optics of polarized light piece etc., can obtain both can bringing into play sufficient charged preventive, and two sides of anti-light leak and weather resistance good adhesive sheet all.

Description of drawings

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 schematic diagram with mensuration field of the light leak experiment in the polarized light piece of adhering agent layer.

Embodiment

Below, embodiments of the present invention are described.

(tackiness agent)

The tackiness agent of present embodiment, contain weight average molecular weight and be 500,000-3,000,000 the 1st (methyl) acrylic ester polymer (A) and, weight average molecular weight is the crosslinked composition that forms of the 2nd (methyl) acrylic ester polymer (B) and the charged preventor (C) of 8000-30 ten thousand.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, the concept that also contains " co-polymer " in " polymkeric substance ".

In the tackiness agent of present embodiment, the 2nd (methyl) acrylic ester polymer (B) (low-molecular weight polymer) is crosslinked and form three-dimensional netted structure, in the described three-dimensional netted structure, more than the 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) 2 molecules, do not following direct chemical bond, perhaps follow few chemical bond and insert, polymer (A) is in bond at the state with degree of freedom to a certain degree, crosslinked configuration (supposition) like formation is intended (structure of so inferring is hereinafter referred to as " structure X ").Tackiness agent with described structure X, when having charged preventive and large extension at break degree, the gel fraction with regulation thus, can be brought into play suitable cohesive force and good stress relaxation rate.Tackiness agent with so good stress relaxation rate, where applicable in the optics of polarized light piece etc., when anti-light leak was good, weather resistance was also good, under the conditions such as high temperature, also can prevent from floating and peel off etc.

Described tackiness agent, preferably, make the tackiness composition of the 2nd (methyl) acrylic ester polymer (B), charged preventor (C) and the linking agent (D) of the 1st (methyl) acrylic ester polymer (A) that contains weight average molecular weight 500,000-3,000,000, weight average molecular weight Ga 8000-30 ten thousand, particularly preferred, the tackiness composition that further contains silane coupling agent (E) carries out crosslinked and obtains.Below, described tackiness composition is described.

Described (methyl) acrylic ester polymer (A) or (B), the carbon number of preferred alkyl are (methyl) alkyl acrylate of 1-20, other the co-polymer of monomer that has the monomer (containing the alkylene oxide group monomer) at alkoxide position and have the functional group's who reacts with linking agent (D) monomer (containing the reactive functional group monomer) and use as required.In addition, the 1st (methyl) acrylic ester polymer (A) does not preferably contain the described monomer that contains reactive functional group as component unit yet.In addition, preferred the 2nd (methyl) acrylic ester polymer (B) does not contain the described alkylene oxide group monomer that contains as component unit yet.

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

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

In addition, the 2nd (methyl) acrylic ester polymer (B), as component unit, the carbon number that preferably contains alkyl is (methyl) alkyl acrylate 5-99 quality % of 1-20, particularly contain 30-90 quality % for preferred, further contain promising preferred with 40-80 quality %.The amount of described (methyl) alkyl acrylate can obtain the desirable adhesive while in the scope of 5-99 quality % the time, and the amount that contains the reactive functional group monomer in the polymkeric substance (B) can be guaranteed.In addition, as the amount of (methyl) alkyl acrylate is in the scope of 30-90 quality % as described in making, and the amount that contains the alkylene oxide group monomer in the polymkeric substance (B) also can be guaranteed.

As containing the alkylene oxide group monomer, preferably exemplify (methyl) vinylformic acid alcoxyl base 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-methoxyl group butyl ester, (methyl) vinylformic acid 4-methoxyl group butyl ester etc.Further, also can preferably exemplify (methyl) vinylformic acid alcoxyl base ester of the end alkoxy group of the poly-alkyl diol chain with polyglycol chain or polypropylene glycol chain etc.Wherein, the good viewpoint of each monomer intermiscibility when obtaining polymkeric substance (A) or polymerization (B), (methyl) vinylformic acid 2-methoxy ethyl ester is for particularly preferably.They can be suitable for separately, also can be used in combination more than 2 kinds.

Contain the alkylene oxide group monomer, preferably only in the 1st (methyl) acrylic ester polymer (A), perhaps in the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), contained as component unit.So, will contain the alkylene oxide monomer such as at least the 1 (methyl) acrylic ester polymer (A) and be contained sometimes as component unit, it shows hydrophilic alkoxyl group position, and the charged performance that prevents that charged preventor (C) is obtained is enhanced.Thus, the amount of the charged preventor (C) in the tackiness composition of present embodiment is tailed off.In addition, only the 2nd (methyl) acrylic ester polymer (B) contains the occasion of alkylene oxide monomer as component unit, formed in the process of three-dimensional netted structure by described polymkeric substance (B) and linking agent (D), the poor increase of polarity (supposition) of described three-dimensional netted structure part and polymkeric substance (A), thus, being separated of two compositions can make the optical characteristics variation, perhaps might can not form fully by described structure X.Therefore, preferably do not use this mode.

The 1st (methyl) acrylic ester polymer (A), as component unit, described to contain alkylene oxide monomer 5-50 quality % preferred, and particularly 10-45 quality % contains promising preferably, further contains promising preferred with 15-35 quality %.The 2nd (methyl) acrylic ester polymer (B) will contain occasion that the alkylene oxide monomer contains as component unit too.As the amount that contains the alkylene oxide group monomer as described in the scope time, when above-mentioned good effect was obtained, described (methyl) alkyl acrylate in the tackiness composition of present embodiment and the amount that contains the reactive functional group monomer will be guaranteed.

On the other hand, as containing the reactive functional group monomer, in molecule, have the monomer (hydroxyl monomer) of hydroxyl, have the monomer (containing carboxylic monomer) of carboxyl in the molecule, have amino monomer (emulsion stability) etc. in the molecule for preferred.In addition, contain monomer as following contain reactive functional group base (a1) monomer, the monomer that contains reactive functional group base (b1) and reactive functional group base (b2), for containing the reactive functional group monomer in this narration.The selection of its kind is such as the explanation of carrying out in the project of each monomer.

As the hydroxyl monomer, may exemplify (methyl) vinylformic acid hydroxyalkyl acrylate 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. etc.They can be suitable for separately, also can be used in combination more than 2 kinds.

As containing carboxylic monomer, the alkene unsaturated carboxylic acid of possible exemplified by acrylic, methacrylic acid, β-crotonic acid, toxilic acid, methylene-succinic acid and citraconic acid etc.They can be suitable for separately, also can be used in combination more than 2 kinds.

As emulsion stability, may exemplify (methyl) acrylic-amino ethyl ester and (methyl) vinylformic acid normal-butyl amino-ethyl ester etc.They can be suitable for separately, also can be used in combination more than 2 kinds.

Further, as described other monomer, may exemplify (methyl) acrylate with aliphatics ring of (methyl) vinylformic acid cyclohexyl ester etc.; (methyl) acrylate with aromatic ring of (methyl) vinylformic acid phenyl etc.; (methyl) acrylamide of the non-crosslinked of acrylamide, 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 etc.; Vinyl-acetic ester; Vinylbenzene etc.They can be suitable for separately, also can be used in combination more than 2 kinds.

The 2nd (methyl) acrylic ester polymer (B) will have the functional group's (b1) who reacts with linking agent (D) monomer (containing reactive functional group (b1) monomer) as constituent.Described polymkeric substance (B) contains, and the functional group with linking agent (D) reaction preferably in fact only has functional group (b1).In addition, so-called " functional group (b1) is in fact only arranged ", for other functional group's amount of linking agent (D) reaction for not hindering the allowance of functional group (b1) and reactive degree of linking agent (D).

Namely, the 2nd (methyl) acrylic ester polymer (B), preferably as constituent, do not contain the monomer (monomer that contains reactive functional group (b2)) of comparing low functional group (b2) with the reactivity of linking agent (D) than described functional group (b1).But, in the occasion that contains the monomer of reactive functional group (b2) as constituent, as mass ratio, be preferably the amount below 1/5 of the amount of the monomer that contains reactive functional group (b1), particularly preferred amount below 1/10.

In addition, the monomer that contains reactive functional group (b1) that uses in the 2nd (methyl) acrylic ester polymer (B) and contain reactive functional group (b2) monomer, and the selection of the monomer that contains reactive functional group (a1) of following the 1st (methyl) acrylic ester polymer (A) use, decided by the reactive relation with the linking agent (D) that uses.Following in detail.

The 2nd (methyl) acrylic ester polymer (B), the reactive functional group that contains (b2) monomer, as as mass ratio, surpass 1/5 amount of the amount that contains reactive functional group (b1) monomer, the weather resistance of the adhering agent layer that obtains has the possibility of variation.Too much such as the reactive functional group (b2) in the 2nd (methyl) acrylic ester polymer (B), the three-dimensional netted tectosome internal reaction functional group (b2) who forms thus is remaining in a large number, thus the intermiscibility of described three-dimensional netted tectosome and the 1st (methyl) acrylic ester polymer (A) can change (supposition).Its result, the occasion that has mist degree (haze) value to rise.In addition, a large amount of remaining three-dimensional netted tectosomes of reactive functional group (b2), the excessively mobility (supposition) of the restriction three-dimensional netted tectosome the 1st of described insertion (methyl) acrylic ester polymer (A).Its result, the extension at break degree of the tackiness agent that obtains diminishes, the occasion that weather resistance degenerates.

Further, the occasion that contains silane coupling agent (E) at the tackiness composition of present embodiment, silane coupling agent (E), with reactive functional group (a1) (particularly carboxyl) reaction 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 limited to covalent linkage, also comprise hydrogen bond, the interaction of Shu water-based and Fan Dehuali etc.Thus, the alkoxyl silicone base section of silane coupling agent and glass substrate effect are so the tackiness agent that obtains is improved (supposition) with the adherence of to-be-adhered object glass substrate etc.At this, when the 2nd (methyl) acrylic ester polymer (B) surplus contains the monomer of reactive functional group (b2), the alkoxysilyl group of silane coupling agent (E) etc., also react with the reactive functional group (b2) (particularly carboxyl) of the 2nd (methyl) acrylic ester polymer (B), with low-molecular-weight the 2nd (methyl) acrylic ester polymer (B) bonding, thereby be deprived of (supposition) with chance that to-be-adhered object carries out bonding.Its result, the adherence variation of the tackiness agent that obtains and to-be-adhered object glass substrate etc. thus, just has the weather resistance variation possibility of adhering agent layer.

The 2nd (methyl) acrylic ester polymer (B) preferably contains and describedly contains reactive functional group (b1) monomer to surpass 1 quality % super, 50 quality % less than.More preferably, the described monomer that contains reactive functional group (b1) is 5-40 quality %, particularly preferably contains 10-30 quality %, further preferably contains 12-20 quality %.As the content that contains reactive functional group (b1) monomer as described in scope, the crosslinked degree of the 2nd (methyl) acrylic ester polymer (B) is good, with the combination of the 1st (methyl) acrylic ester polymer (A) in, when the extension at break degree of the tackiness agent that obtains was large, described tackiness agent was easy to have the gel fraction of regulation.Its result, the weather resistance of described tackiness agent and stress relaxation rate become good.In addition, the amount that contains reactive functional group (b1) monomer is that 1 quality % is when following, the 2nd (methyl) acrylic ester polymer (B) crosslinked insufficient, gel fraction has and becomes the following occasion of prescribed value, and weather resistance has the possibility of variation thus.On the other hand, as the amount that contains reactive functional group (b1) monomer is more than the 50 quality %, and the crosslinked meeting of the 2nd (methyl) acrylic ester polymer (B) is excessive, and the occasion that has the extension at break degree to diminish has the possibility of weather resistance variation thus.In addition, contain reactive functional group (b1) monomer amount on when being limited to 30 quality %, the anti-light leak of the adhesive sheet that obtains can become better.

At this, the carbon number of alkyl is 1-20's (methyl) alkyl acrylate and has the polymerization methods that monomer with the functional group of linking agent (D) reaction carries out the 2nd (methyl) acrylic ester polymer (B) that polymerization obtains, for random co-polymer also can, block copolymer also can.

In the present embodiment, described the 2nd (methyl) acrylic polymer (B) can a kind uses separately, also can be used in combination more than 2 kinds.

The weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is 8000-30 ten thousand, and is preferred 10,000-200,000, particularly preferred 50,000-100,000.That is, the 2nd (methyl) acrylic ester polymer (B) is the low-molecular weight polymer composition.In addition, the weight average molecular weight in this specification sheets, the value of the polystyrene conversion of measuring for gel permeation chromatography (GPC) method.

As the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) as described in the scope, the distinctive three-dimensional netted structure of the tackiness composition of present embodiment will form, thereby to having good stress relaxation rate contribution is arranged.That is, as the weight average molecular weight 8000 of the 2nd (methyl) acrylic ester polymer (B) less than, good three-dimensional netted structure just is difficult to obtain.On the other hand, the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) surpasses 300,000 as crossing, with the intermiscibility of the 1st (methyl) acrylic ester polymer (A) etc. will variation, the mist degree of adhering agent layer (haze) value will rise etc., will have the occasion of optical characteristics variation.In addition, the insertion of the polymkeric substance (A) in the three-dimensional netted tectosome that forms to polymkeric substance (B) will be insufficient, and gel fraction just has and is in the following possibility of specialized range.Its result, the tackiness agent that obtains just has the occasion of weather resistance and reusability variation.

The 1st (methyl) acrylic ester polymer (A), preferably, do not contain the monomer with the functional group who reacts with linking agent (D) as constituent, perhaps as constituent, contain with the described functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) and compare, monomer (containing reactive functional group (a1) monomer) with the reactive low functional group (a1) of linking agent (D), and then particularly preferably, as constituent, do not contain than described functional group (b1) and have monomer with the reactive high functional group of linking agent (D).

The 1st (methyl) acrylic ester polymer (A) also can not contain the monomer with the functional group who reacts with linking agent (D).But, as contain reactive functional group (a1) monomer, preferred occasion is arranged.Namely, in the described polymkeric substance (A) as contain reactive functional group (a1), possibility with the reaction that promotes the 2nd (methyl) acrylic ester polymer (B) and linking agent (D), or, the occasion that is used at silane coupling agent (E), the reactive functional group (a1) of the 1st (methyl) acrylic ester polymer (A) and described silane coupling agent (E) effect, the adhesion durability to the glass surface of liquid crystal cells etc. of the tackiness agent that obtains can further improve, so preferred occasion is arranged.

The 1st (methyl) acrylic ester polymer (A) contains the described occasion that contains reactive functional group (a1) monomer, and its amount is generally below the 20 quality %, and 15 quality % are following to be preferred, and particularly 10 quality % are following is preferred.The amount that contains reactive functional group (a1) monomer is when surpassing 20 quality %, and the glass tansition temperature (Tg) of the 1st (methyl) acrylic ester polymer (A) can be too high, and the stress relaxation rate of the tackiness agent that obtains has the possibility of variation.In addition, from give the viewpoint of reusability to tackiness agent, the amount that contains reactive functional group (a1) monomer is preferably below the 15 quality %.

In addition, reactive functional group (b1) monomer that contains that contains with the 2nd (methyl) acrylic ester polymer (B) compares, the ratio in described the 1st (methyl) acrylic ester polymer (A) that contains reactive functional group (a1) monomer that the 1st (methyl) acrylic ester polymer (A) contains is less than the ratio in described the 2nd (methyl) acrylic ester polymer (B) that contains reactive functional group (b1) monomer that contains with the 2nd (methyl) acrylic ester polymer (B).Thus, the reactive functional group (a1) that the 1st (methyl) acrylic ester polymer (A) contains and the reaction of linking agent (D) are suppressed, and the reactive functional group (b1) that the 2nd (methyl) acrylic ester polymer (B) contains is positively reacted with linking agent (D).Thus, the extension at break degree is the tackiness agent more than 1500% in the time of can obtaining stretching.

The 1st (methyl) acrylic ester polymer (A) does not preferably contain the monomer that has with the equal or above functional group of the reactive functional group (b1) of reactivity and the 2nd (methyl) acrylic ester polymer (B) of linking agent (D) in molecule.But, in the occasion as containing, in molecule, have the amount of described functional group's monomer, preferably be below the 1 quality % in polymkeric substance (A), particularly 0.5 quality % is following is preferred.The amount of monomer surpasses 1 quality % as described, might hinder the possibility of the 2nd (methyl) acrylic ester polymer (B) that preferentially carry out and the reaction of linking agent (D).Its result has the occasion that can not obtain desired stress relaxation rate.

At this, the carbon number of alkyl is 1-20's (methyl) alkyl acrylate, the polymerization methods of the 1st (methyl) acrylic ester polymer (A) that carries out polymerization with the monomer that contains reactive functional group and obtain, random co-polymer also can, block copolymer also can.

In the present embodiment, described the 1st (methyl) acrylic ester polymer (A) can a kind uses separately, also can be used in combination more than 2 kinds.

The weight average molecular weight 500,000-3,000,000 of the 1st (methyl) acrylic ester polymer (A), preferred 700,000-2,500,000, particularly preferred 1,000,000-2,000,000.That is, the 1st (methyl) acrylic ester polymer (A) is the high-molecular weight polymer composition.

As the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) as described in the scope, polymkeric substance (A) has the large molecular weight of comparison, may form well described structure X (supposition) thus.

At this, be 500,000 less than, the gel fraction variation of the tackiness agent that obtains such as the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A), thereby the possibility of weather resistance and reusability variation is arranged.In addition, weight average molecular weight such as the 1st (methyl) acrylic ester polymer (A) surpasses 3,000,000, degenerate with the intermiscibility of the 2nd (methyl) acrylic ester polymer (B) etc., mist degree (haze) value rises, and the possibility that can not get desirable stress relaxation rate is arranged.

To the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of the 2nd (methyl) acrylic ester polymer (B), preferred 5-50 mass parts, 5-40 mass parts be further not preferably, and the 10-30 mass parts is for particularly preferably.

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

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

The isocyanates linking agent contains polyisocyanate compounds at least.As polyisocyanate compounds, for example, the aromatic poly-isocyanate of tolylene diisocyanate, diphenylmethanediisocyanate, p-Xylol group diisocyanate etc.; The aliphatic polymeric isocyanate of hexamethylene diisocyanate etc.; The alicyclic ring polymeric polyisocyanate of isophorone diisocyanate, hydrogenation diphenylmethanediisocyanate etc. etc. and their biuret body, chlorinated isocyanurates body; Further can exemplify with containing of ethylene glycol, propylene glycol, dimethyltrimethylene glycol, TriMethylolPropane(TMP) and castor-oil plant wet goods low molecular activity hydrogen compound react the adducts that obtains etc.Wherein, because the crosslinked configuration that obtains has rigidity and the flexibility of appropriateness, so the tolylene diisocyanate of TriMethylolPropane(TMP) (TDI class) affixture is for particularly preferably.

As the epoxies linking agent, for example, 1, two (N, the N-'-2-glycidyl ether aminomethyl) hexanaphthenes of 3-, 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.

As the aziridines linking agent, can exemplify ditan 4,4 '-two (1-aziridine methane amides), 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 and trimethylolpropane tris β-(2-methylaziridine) propionic ester etc.

Metal complex class linking agent, it is the coordination compound of aluminium, zirconium, titanium, zinc, iron and tin etc. that atoms metal is arranged, but from the performance this point, the aluminium coordination compound is preferred.As the aluminium coordination compound, can exemplify diisopropoxy aluminium list oleyl alcohol acetylacetic ester, the two oleyl alcohol acetylacetic esters of single aluminum isopropoxide, single aluminum isopropoxide list oleic acid list ethyl acetoacetic ester, diisopropoxy aluminium list lauryl acetylacetic ester, diisopropoxy aluminium list stearyl acetylacetic ester and diisopropoxy aluminium list iso stearyl acetylacetic ester etc.

The amount of linking agent (D), the bridging property base of described linking agent (D) (for example, isocyanate group) to the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) (for example, 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.Amount 0.05 equivalent of described bridging property base less than occasion, the gel fraction of the tackiness agent that obtains be 30% less than, might can not bring into play sufficient cohesive force.In addition, the amount of described bridging property base is more than 0.1 equivalent, the above occasion of 0.3 equivalent particularly, and the weather resistance of the tackiness agent that obtains may be further good.On the other hand, as described the amount of bridging property base below 3.5 equivalents, the reusability of the tackiness agent that obtains good.Further, the amount of bridging property base is below 1.0 equivalents as described, and linking agent (D) is only to the contribution that is formed with of the three-dimensional netted structure of polymkeric substance (B), may effectively prevent (supposition) to polymkeric substance (A) crosslinked.Its result, the stress relaxation rate of the tackiness agent that obtains is good.

In addition, in the present embodiment, as linking agent (D), so long as with the linking agent of the kind of reactive relationship consistency of two sides of the reactive functional group (a1) of the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) and the 1st (methyl) acrylic ester polymer (A), a plurality of kinds also may be used.The control of the three-dimensional netted structure that is formed by the 2nd (methyl) acrylic ester polymer (B) is easy to viewpoint, for example just as only using the isocyanates linking agent, preferably only use the linking agent of a kind as the functional group, further, only use 1 linking agent for particularly preferably as compound.

At this, as linking agent (D) and (methyl) acrylic ester polymer (A) and (B) separately the combination that contains the reactive functional group monomer, linking agent (D) is in the occasion of isocyanates linking agent, contain reactive functional group (a1) monomer for containing carboxylic monomer as polymkeric substance (A), contain reactive functional group (b1) monomer as polymkeric substance (B), be hydroxyl monomer or emulsion stability (particularly hydroxyl monomer), as the monomer that contains reactive functional group (b2) of polymkeric substance (B), contain carboxylic monomer for preferred.

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

From the flexibility of the key of formation and the stability of crosslinking reaction between linking agent (D) and the polymkeric substance (B), further, the reactive base of polymkeric substance (A) carries out appropriate reaction with silane coupling agent (E), adhesion durability to the tackiness agent that obtains improves contributive viewpoint, linking agent (D) uses the isocyanates linking agent, reactive functional group (a1) the monomer use that contains of polymkeric substance (A) contains carboxylic monomer, reactive functional group (b1) monomer that contains of polymkeric substance (B) uses the hydroxyl monomer, does not use to contain reactive functional group (b2) monomer for particularly preferably.

As charged preventor (C), as long as effect of the present invention is not hindered, can give the charged preventive of the tackiness agent that obtains just passable, can exemplify ionic compound and interfacial agent etc., wherein take ionic compound as preferably.Ionic compound, liquid also can, solid also can.At this, the so-called ionic compound in this specification sheets, the compound that mainly carries out combination with electrostatic attraction for positively charged ion and negatively charged ion.

As ionic compound, to contain nitrogen salt, to contain Sulfur salt, phosphorous salts, an alkali metal salt and alkali earth metal salt as preferred.As an alkali metal salt, take lithium salts and sylvite as preferred.The concrete example of ionic compound, can exemplify phosphofluoric acid N-butyl 4-picoline, n-hexyl 4-picoline hexafluorophosphate, normal-butyl 2-hexyl pyridine perchlorate, two (fluorine sulfimide) potassium (KFSI), two (fluorine sulfimide) lithiums (LiFSI), two (trifluoromethane sulfimide) potassium, two (trifluoromethane sulfonium imide) lithium (LiTFSI), two (trifluoromethane sulphonyl) imides of normal-butyl 2-hexyl pyridine etc.Above charged preventor (C) can a kind uses separately, also can be used in combination more than 2 kinds.

The amount of the charged preventor (C) in the tackiness composition of present embodiment, 0.1-30 quality % are preferred, and particularly 0.5-20 quality % is preferred, and further 1.0-10 quality % is preferred.As described in being in such as the amount of charged preventor (C) in the scope, when charged preventive can effectively be brought into play, the composition (A) of other in the tackiness composition of present embodiment, (B) and amount (D) can be guaranteed.

In addition, charged preventor (C) is take independent use as preferred, with dispersion agent and with also preferred.The inadequate occasion of solvability of the charged preventor in the tackiness composition (C) with dispersion agent and usefulness, can make solvability be improved.

As dispersion agent, can preferably exemplify alkyl diol dialkyl ether etc.As the concrete example of alkyl diol dialkyl ether, be the ethohexadiol dibutyl ether, the ethohexadiol Anaesthetie Ether, the ethohexadiol dimethyl ether, the hexylene glycol dibutyl ether, hexylene glycol Anaesthetie Ether, hexylene glycol dimethyl ether, the TEG dibutyl ether, the TEG Anaesthetie Ether, the TEG dimethyl ether (below, also claim " four symmetrical diether "), the triethylene glycol Anaesthetie Ether, triethylene glycol dimethyl ether etc.These dispersion agent can a kind uses separately, also can be used in combination more than 2 kinds.

The use level of dispersion agent, to the mol ratio of charged preventor (C), 0.5-1.5 is preferred, and 0.7-1.2 is for more preferably, and 0.9-1.1 is for particularly preferred.

In addition, as above-mentioned, the 1st (methyl) acrylic ester polymer (A), perhaps the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), the occasion that contains the alkylene oxide group monomer as component unit can reduce the amount of charged preventor (C).Specifically, the amount in the tackiness composition of present embodiment, preferred 0.5-15 quality %, the particularly scope of preferred 1.0-5.0 quality %.

The tackiness composition of present embodiment, preferred, further contain silane coupling agent (E).As contain this silane coupling agent (E), the 1st (methyl) acrylic ester polymer (A) has the occasion of carboxyl, the carboxyl of the organic reaction base of silane coupling agent (E) etc. and the 1st (methyl) acrylic ester polymer (A) reacts, on the other hand, the to-be-adhered object face effect of alkoxysilyl group of silane coupling agent (E) etc. and glass substrate etc.Thus, such as the occasion that polarized light piece is fitted in the liquid-crystalline glasses unit etc., the adherence between tackiness agent and the liquid-crystalline glasses unit can become more good.In addition, the reactive functional group (a1) of polymkeric substance (A) is the occasion beyond the carboxyl, can be to the organic reaction base of the silane coupling agent (E) that acts on described reactive functional group (a1), can be according to selecting with described reactive functional group (a1).

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

As the concrete example of silane coupling agent (E), can the exemplified by vinyl Trimethoxy silane, the silicon compound that contains the polymerizability unsaturated group of vinyltriethoxysilane, methacryloxypropyl trimethoxy silane etc.; The silicon compound with epoxy structure of 3-glycidyl ether propyl trimethoxy silicane and 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.; The 3-TSL 8330, just (2-amino-ethyl)-3-TSL 8330 and just (2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane etc. contain amino silicon compound; The 3-r-chloropropyl trimethoxyl silane; 3-isocyanic ester propyl-triethoxysilicane etc.These get final product a kind and use separately, and use also can combine more than 2 kinds.

In described tackiness composition, as required, can add the normally used various additives of acrylic acid or the like tackiness agent, such as adhesion imparting agent, antioxidant, UV light absorber, light stabilizer, tenderizer, filling agent and specific refractory power adjusting agent etc.

Described tackiness composition, the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) are made respectively, when they are mixed, can be the stage adds linking agent (D), charged preventor (C) and silane coupling agent as required (E) and makes arbitrarily.

As preferred concrete example, (methyl) acrylic ester polymer (A) and (B) is made with common radical polymerization separately respectively.(methyl) acrylic ester polymer (A) and polymerization (B) as required, are used polymerization starter, make with solution polymerization process etc.As the polymerization solvent, can exemplify ethyl acetate, ro-butyl acetate, acetic acid isobutyl, toluene, acetone, hexane and methyl ethyl ketone etc., 2 kinds are above also with also can.

As polymerization starter, can exemplify azo compound and organo-peroxide etc., 2 kinds are above also with also can.As azo compound, can exemplify 2,2 '-the two isobutyl cyanogen, 2 of azo, 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 esters), 4,4 '-azo two (4-cyano group valeric acid), 2,2 '-azo two (2-hydroxymethyl the third cyanogen) and 2,2 '-azo two [2-(the 2-miaow is sat beautiful jade 2-yl) propane] etc.

As organo-peroxide; can exemplify benzoyl peroxide, benzoyl hydroperoxide t-butyl ester, isopropyl benzene hydroperoxide, diisopropyl peroxydicarbonate, di n propyl peroxy dicarbonate, two (2-ethoxyethyl group) peroxide two carbonic ethers, the new certain herbaceous plants with big flowers acid of peroxide t-butyl ester, peroxide trimethylacetic acid t-butyl ester, (3; 5,5-trimethyl acetyl base) superoxide, two propionyl superoxide and diacetyl superoxide etc.

In addition, in the described Polymerization Engineering, the chain of 2 mercapto ethanol etc. moves agent also can cooperate adding, and the weight average molecular weight of the polymkeric substance that obtains is regulated.

Bonding, polymkeric substance (A) and the solution (B) that obtains is mixed, add the dilution solvent.Afterwards, add linking agent (D), charged preventor (C) and add as required silane coupling agent (E), mix fully, the tackiness composition (coating solution) that dilutes with solvent is obtained.

As the tackiness composition being diluted the diluting solvent that obtains coating solution, can exemplify the aliphatic hydrocarbon of hexane, heptane and hexanaphthene etc.; The aromatic hydrocarbons of toluene, dimethylbenzene etc.; Methylene dichloride, the halohydrocarbon of 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 and acetic acid butyl etc.; The cellosolve kind solvent of ethyl cellosolve etc. etc.

So the concentration viscosity of the coating solution of modulation as long as in the possible scope of coating, particularly do not limit, can suit to select according to situation.For example, can be with the concentration dilution of tackiness composition to 10-40 quality %.In addition, in obtaining coating solution, the interpolation of diluting solvent etc. is not prerequisite, and the tackiness composition is so long as coating possibility viscosity etc. are also passable even diluting solvent does not add.This occasion, the tackiness composition can be intactly as coating solution.

Above-mentioned tackiness agent carries out described tackiness composition crosslinked and obtains.Described tackiness composition crosslinked can be undertaken by heat treated.In addition, this heat treated when the volatilizations such as the dilution solvent that makes the tackiness composition, can double as drying treatment.

In the occasion of heat treated, Heating temperature, preferred 50-150 ℃, particularly 70-120 ℃ is preferred.In addition, be heat-up time, was divided into preferably with 30 seconds-3, particularly was divided into preferred in 50 seconds-2.Further, after the heat treated, normal temperature (for example, 23 ℃, 50%RH) under, arrange during the maturation of 1-2 week degree as particularly preferably.

By described heat treated (and maturation), when making the 2nd (methyl) acrylic ester polymer (B) crosslinked by linking agent (D), have the 1st (methyl) acrylic ester polymer (A) to insert in its three-dimensional netted structure, described structure X is formed (supposition).The 1st (methyl) acrylic ester polymer (A) has the occasion of carboxyl, the reaction of the 1st (methyl) acrylic ester polymer (A) and silane coupling agent (E), the tackiness agent that obtains is enhanced to the adhesion durability of the glass substrate of liquid crystal cells etc.

The stretching experiment extension at break degree of the tackiness agent of present embodiment is more than 1500%, and is preferred more than 2000%, particularly preferred more than 2500%.In addition, the mensuration of this extension at break degree is that the independent adhering agent layer that does not have base material etc. is carried out.The tackiness agent that above-mentioned material consists of has described large extension at break degree, and therefore described tackiness agent shows good stress relaxation rate, and two sides of anti-light leak and weather resistance are good.

Described stretching experiment specifically, is to form thickness 500 μ m, wide 10mm, the length of prolonging direction is that the tackiness agent of 75mm (length of wherein, measuring the position is 20mm) is at 23 ℃, under the environment of 50%RH, carry out with the speed elongation that 200mm/ divides.

The gel fraction of the tackiness agent of present embodiment is 30-90%, preferred 40-80%, particularly preferred 45-75%.Such as gel fraction, namely crosslinked degree is in this scope, and the crosslinked three-dimensional netted structure that forms of the 2nd (methyl) acrylic ester polymer (B) will form well, and tackiness agent is all good two sides of anti-light leak and weather resistance.In addition, the gel fraction of tackiness agent, the value of (during the maturation through after) when attaching.Specifically, be that the tackiness composition is coated with to stripping film, after the heat treated, 23 ℃, carry out the gel fraction of keepings on the 7th after (maturation) under the environment of 50%RH, the gel fraction of tackiness agent, during maturation through before, its value changes.From such viewpoint, the not clear occasion through whether during the maturation will be again at 23 ℃, the environment of 50%RH is lower carry out keeping on the 7th after, as gel fraction at this moment as described in get final product in the scope.

The sheet resistance value of the tackiness agent of present embodiment, preferred 3.0 * 10 ¹¹Below Ω/sq, particularly preferred 1.0 * 10 ¹¹Below Ω/sq, further preferred 8.0 * 10 ¹⁰Below Ω/sq.Below described value, sufficient charged preventive just can be brought into play such as sheet resistance value.In addition, in the present embodiment, the charged preventor (C) in the described tackiness composition though amount below 3 quality %, also can be such as described, bring into play sufficient charged preventive.

The clinging power of the tackiness agent of present embodiment, to the clinging power of non-alkali glass take 0.1-50N/25mm as preferred, particularly take 0.5-30N/25mm for preferred, further take 3.0-20N/25m m as preferably.In addition, in this said clinging power, for pressing 180 ° of peel adhesion (peeling rate 300mm/min) of JISZ0237,0.5MPa 50 ℃ are carried out pressurization in 20 minutes, after to-be-adhered object attaches, 23 ℃, carry out under the condition of 50%RH placing in 24 hours, and measure.In described scope, when the optics of applicable and polarized light piece etc., float and peeling off etc. just can be prevented such as clinging power.

Tackiness agent described above, be preferred as used for optical part, for example, bonding between the optics of polarized light piece (polarizing film) and polarizer (phase-contrast film) etc., or the bonding optimum of polarized light piece (polarizing film) and polarizer (phase-contrast film) and glass substrate.The tackiness agent of present embodiment, owing to having charged preventive, static is difficult to occur, and can effectively suppress the fault that occurs owing to static.In addition, the adhering agent layer that is formed by described tackiness agent, the stress relaxation rate is very good, even the occasion that the dimensional change of to-be-adhered object is large, the stress that occurs owing to dimensional change also can be absorbed mitigation by adhering agent layer, even therefore life-time service also is difficult to peel off from to-be-adhered object, light leak also can be prevented effectively when described optics uses simultaneously.That is, the tackiness agent of present embodiment had both had charged preventive, had again anti-light leak and weather resistance.

(adhesive sheet)

As shown in Figure 1, the adhesive sheet 1A of the 1st embodiment is to consist of like this,, from bottom to top, is stripping film 12 that is, and the adhering agent layer 11 that is stacked on the release surface of stripping film 12 has been stacked base material 13 on the adhering agent layer 11.

In addition, as shown in Figure 2, the adhesive sheet 1B of the 2nd embodiment comprises 2 pieces of stripping film 12a, 12b; Described 2 pieces of stripping film 12a, the adhering agent layer 11 that the 12b To is seized on both sides by the arms, thus, adhering agent layer 11 with shown in 2 pieces stripping film 12a, the release surface of 12b is joined.In addition, the release surface of the so-called stripping film in this specification sheets, refer to the face that separability is arranged in the stripping film, though implemented the face of lift-off processing and do not carry out the face that lift-off processing still has separability, just comprise in the concept of release surface in this manual.

Adhering agent layer 11 in any one of adhesive sheet 1A and 1B all is that the tackiness agent (the crosslinked tackiness agent that forms of above-mentioned tackiness composition) by present embodiment consists of.

The thickness of adhering agent layer 11, can be according to adhesive sheet 1A, the application target of 1B suits to determine, be generally 5-100 μ m, the scope of preferred 10-60 μ m, for example, as optics, particularly the occasion used of the adhering agent layer used of polarized light piece is 10-50 μ m, and particularly 10-30 μ m is preferred.

As base material 13, have no particular limits, the substrate sheets of the adhesive sheet of usefulness can be used usually.Outside desirable optics, can also exemplify woven or the non-woven fabrics of the fiber of artificial silk, acrylic resin and polyester etc.; The stationery of upper matter paper, glassine paper, impregnation paper, art paper etc.; The tinsel of aluminium, copper etc.; The foam of polyurethane foaming body and 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., the polyvinyl dichloride film, polyvinylidene chloride film, the polyvinyl alcohol film, the vinyl-vinyl-acetic ester co-polymer film, polystyrene film, polycarbonate film, the acrylic resin film, the plastics film of norbornene type resin film and cyclenes resin film etc.; These the stack more than 2 kinds etc.Plastics film, an axle stretch or Biaxially stretchedly also can.

As optics, can exemplify polarized light piece (polarizing film), polarisation, polarizer (phase-contrast film), angle of visibility benefit reward film, briliancy raising film, contrast gradient raising film, liquid crystal polymer film, diffusion film and semi-penetration film etc.Polarized light piece (polarizing film) wherein is easy to shrink, and dimensional change is large, from the viewpoint of anti-light leak, as the tackiness agent (described adhering agent layer 11) that uses present embodiment to as if suitable.

The thickness of base material 13, according to its kind and difference, for example the occasion of optics is generally 10-500 μ m, preferred 50-300 μ m.

As stripping film 12,12a and 12b can exemplify polyethylene film, polypropylene film, the polybutene film, the polyhutadiene film, poly-methyl pentene film, the polyvinyl dichloride film, chloroethylene copolymer compound film, pet film, polyethylene naphthalate film, the polybutylene terephthalate film, polyurethane film, ethene vinyl acetate base film, the amberlite membrane of lipoprotein, ethene-(methyl) acrylic copolymer film, ethene-(methyl) acrylic ester copolymerization thing film, polystyrene film, polycarbonate film, Kapton and fluorine resin film etc.In addition, these crosslinked film also can be used.Further, these overlay film also can.

The release surface of described stripping film (face that particularly joins with adhering agent layer 11) preferably is subjected to lift-off processing.As the stripper that is used in lift-off processing, may exemplify the stripper of alcohol acids, type siloxane, fluorine class, unsaturated polyester class, polyolefins and wax class.

Stripping film 12,12a, the thickness of 12b has no particular limits, and is generally 20-150 μ m degree.

When making described adhesive sheet 1A, be on the release surface of stripping film 12, the solution (coating solution) that will contain described tackiness composition is coated with, and after heat treated formed adhering agent layer 11, stacked base material 13 was stacked on its adhering agent layer 11.Afterwards, during the preferred maturation.

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

In addition, when carrying out the manufacturing of described adhesive sheet 1B, on the release surface of a stripping film 12a (perhaps 12b), the coating solution that will contain described tackiness composition is coated with, after heat treated forms adhering agent layer 11, adhering agent layer 11 overlapped with the release surface of another stripping film 12b (perhaps 12a) get final product.

As the method that described coating solution is coated with, may use and for example utilize that rod is coated with method, scrape the skill in using a kitchen knife in cookery, rolling method, plate is coated with method, die coating method, notch board coating method etc.

At this, for example, make the occasion of the liquid crystal display device of liquid crystal cells and polarized light piece formation, base material 13 as adhesive sheet 1A, use polarized light piece, peel off the stripping film 12 of described adhesive sheet 1A this moment, and the adhering agent layer 11 that exposes and liquid crystal cells are fitted and got final product.

In addition, for example, when being manufactured on the liquid crystal display device of the poor plate of configuration phase between liquid crystal cells and the polarized light piece, as an example, at first, the stripping film 12a (perhaps 12b) of adhesive sheet 1B is peeled off, the adhering agent layer that exposes 11 and the polarizer of adhesive sheet 1B are fitted.Then, will use the stripping film 12 of the adhesive sheet 1A of polarized light piece to peel off as base material 13, the adhering agent layer that exposes 11 of adhesive sheet 1A and described polarizer be fitted.Further, the stripping film 12b (perhaps 12a) with another peels off from the adhering agent layer 11 of described adhesive sheet B, and the adhering agent layer that exposes 11 and the liquid crystal cells of adhesive sheet B are fitted.

According to above adhesive sheet 1A, 1B, adhering agent layer 11 has charged preventive, and static just is difficult to occur, and the fault that static causes just can effectively be suppressed.In addition, the stress relaxation rate of adhering agent layer 11 is very good, for example be used in the bonding occasion of polarized light piece, contingent stress is absorbed by adhering agent layer 11 and relaxes (supposition) owing to the distortion of polarized light piece, thus, just may bring into play good anti-light leak and high weather resistance.

Embodiment described above for easy to understand of the present invention is put down in writing, does not have any restriction to the present invention.Therefore, disclosed each key element of described embodiment comprises all design alterations and the equivalent of the scope that belongs to technology of the present invention.

For example, the stripping film 12 of adhesive sheet 1A also can be omitted, the stripping film 12a among the adhesive sheet 1B, and one among the 12b also may be omitted.

[embodiment]

Below, by embodiment etc. the present invention is carried out further specific description, scope of the present invention is not limited to these embodiment etc.

(embodiment 1)

1. the modulation of polymkeric substance (A)

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 '-two isobutyl cyanogen 0.08 mass parts of azo.Air nitrogen replacement in the described reaction vessel.Stir on the lower one side of this nitrogen atmosphere, on one side reaction soln is warming up to 60 ℃, after carrying out reacting in 16 hours, cool to room temperature.At this, the part of the solution that obtains is carried out the mensuration of molecular weight with following method, weight average molecular weight is that the generation of 1,200,000 polymkeric substance (A) is identified.

2. the modulation of polymkeric substance (B)

In the reaction vessel with stirrer, thermometer, reflux cooler, 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 '-two isobutyl cyanogen 0.16 mass parts of azo and 2 mercapto ethanol 0.3 mass parts.Air in described reaction vessel nitrogen replacement.Under this nitrogen atmosphere, Yi Bian stir, Yi Bian reaction soln is warming up to 70 ℃, after carrying out reacting in 6 hours, be cooled to room temperature.At this, the part of the solution that obtains to be measured molecular weight with following method, the generation of the polymkeric substance of weight average molecular weight 60,000 (B) is identified.

3. the modulation of tackiness composition

After polymkeric substance (B) 15 mass parts (solids component scaled value) mixing that obtains in polymkeric substance (A) 100 mass parts (solids component scaled value) that will in described engineering (1), obtain and the described engineering (2), as linking agent (D), tolylene diisocyanate (TDI class) affixture (Japanese polyurethane company system, the trade(brand)name: CORONET) 2.21 mass parts of TriMethylolPropane(TMP) of amount that will be equivalent to hydroxyl 0.6 equivalent of polymkeric substance (B).At last, will be as phosphofluoric acid N-butyl 4-picoline 2.0 mass parts of charged preventor (C) and as 3-glycidyl ether propyl trimethoxy silicane (chemical industrial company of the SHIN-ETSU HANTOTAI system of silane coupling agent (E), trade(brand)name " KBM403 ") 0.2 mass parts is added, stir fully, obtain the diluting soln of tackiness composition.

At this, the cooperation of described tackiness composition is as shown in table 1.In addition, the contracted notation of table 1 record etc. is following described.

[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 (D)]

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

CORONET-HX: hexamethylene diisocyanate class chlorinated isocyanurates (Japanese polyurethane company system, 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 (C)]

Pyridine: phosphofluoric acid N-butyl 4-picoline

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

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

AS-804: the first industrial drugmaker system, 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 ")

Diluting soln with the tackiness composition that obtains, impose stripping film (Lindeke Co., Ltd's system of the pet film of lift-off processing with the type siloxane stripper at a face, SP-PET3811, thickness: on the lift-off processing face 38 μ m), be coated with method with cutter and be coated with, it is 25 μ m that this coating will make dried coat-thickness.90 ℃ are carried out heat treated between 1 minute, and adhering agent layer forms.

Then, to be consisted of by discoid polarizing film with liquid crystal layer, the polarized light piece that polarizing film and angle of visibility expansion film become one is fitted, exposing surface and the discoid liquid crystal layer surface of described adhering agent layer are joined, at 23 ℃, carry out maturation on the 7th under the 50%RH, obtain having the polarized light piece of adhering agent layer.

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

Except the kind of the kind of each monomer of consisting of the tackiness composition and ratio, linking agent, charged preventor and silane coupling agent and use level, polymkeric substance (A) and the proportioning of polymkeric substance (B) having been carried out change as shown in table 1, has similarly to Example 1 the manufacturing of the polarized light piece of adhering agent layer.

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

＜condition determination 〉

GPC determinator: TOSOH company system, HLC-8020

GPC post (following order is passed through): TOSOH company system

TSK?guard?columN?HXL-H

TSK?gel?GMHXL(×2)

TSK?gel?G2000HXL

Measure solvent: tetrahydrofuran (THF)

Measure temperature: 40 ℃

(experimental example 1) (mensuration of gel fraction)

In embodiment or comparative example, the polarized light piece that replacement is used in the making of the polarized light piece with adhering agent layer, use unilateral stripping film (Lindeke Co., Ltd's system of having been carried out lift-off processing with the type siloxane stripper of pet film, SP-PET3801, thickness: 38 μ m), carry out the making of adhesive sheet.Specifically, be that (thickness: on the adhering agent layer that exposes of the tectosome that 25 μ m) consists of, stacked described stripping film joins lift-off processing face side and adhering agent layer by the stripping film/adhering agent layer that obtains in the manufacturing processed of embodiment or comparative example.Thus, obtain being the adhesive sheet that stripping film/adhering agent layer/stripping film consists of.

The adhesive sheet that obtains carries out maturation on the 7th at 23 ℃ under the condition of 50%RH.Afterwards, described adhesive sheet is made the sample of the size of 80mm * 80mm, its adhering agent layer is wrapped up with polyester net (net size 200), only the quality of tackiness agent is carried out weighing with precision balance.With this quality as M1.

Then, will be with the tackiness agent of described polyester net parcel, at room temperature (23 ℃) carry out 24 hours dippings in ethyl acetate.Afterwards tackiness agent is taken out, 23 ℃ of temperature, under the environment of relative humidity 50%, carry out 24 hours air-dry, further in 80 ℃ baking oven, carry out 12 hours dryings.Only the quality of dried tackiness agent is carried out weighing with precision balance.With this moment quality as M2.Gel fraction (%) represents with (M2/M1) * 100.The result is shown in table 2.

(experimental example 2) (light leak experiment)

The polarized light piece with adhering agent layer that will obtain in embodiment or comparative example, (reed open country makes the super cutter of institute's company's system, PN1-600) is adjusted into the size of 233mm * 309mm with cutting device.Stripping film is peeled off, after the adhering agent layer that exposes is attached at non-alkali glass (Corning Incorporated's system, hawk XG), in the made still of the former making of chestnut, at 0.5MPa, under 50 ℃, carried out pressurization in 20 minutes.In addition, in described applying, the polarizing axis that make the polarized light piece with adhering agent layer is Niccol cross state (45 ° of polarizing axis: ∠, 135 ° of ∠).Under this state, after carrying out under 80 ℃ of dry environments placing in 250 hours, at 23 ℃, carry out under the environment of 50%R H placing in 2 hours, be sample with it, carry out the light leak evaluation with method shown in following.The results are shown in table 2.

＜light leak evaluation: Δ L* 〉

Use the MCPD-2000 of large tomb electronics corporation system, the brightness L* in each field that the Fig. 3 in the described sample is represented measures, and luminance difference Δ L* calculates with formula.

ΔL*＝[(b+c+d+e)/4]-a

(still, a, b, c, d and e, difference A field, B field, C field, the brightness in the measuring point of predesignating in D field and E field (central part 1 place in each field)) finds the solution, as light leak.The less light leak of the value of Δ L* is fewer.

(experimental example 3) (durability evaluation)

What obtain in embodiment or the comparative example has an adhering agent layer polarized light piece, and (the wild super cutter of institute's company's system of making of reed PN1-600) is adjusted into 233mm * 309mm size with cutting device.Stripping film is peeled off, be attached on the non-alkali glass (Corning Incorporated's system, hawk XG) between the adhering agent layer that exposes, afterwards, use the made still of the former making of chestnut at 0.5MPa, 50 ℃ of In carry out pressurization in 20 minutes

Afterwards, under the environment of each following durable condition, drop into, observe with 10 times of magnifying glasses after 500 hours.The appearance change case is following to be the evaluation of basic Huaihe River, the results are shown in table 2.

◎: in 4 limits, no problem

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

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

＜durable condition 〉

80 ℃ of dryings

60 ℃, relative humidity 90%RH

(experimental example 4) (mensuration of clinging power)

To carry out severing at the polarized light piece with adhering agent layer that embodiment or comparative example kind obtain, wide to making 25mm, the sample that 100mm is long.From this sample stripping film is peeled off, be attached at non-alkali glass (Corning Incorporated's system, hawk XG) between the adhering agent layer that exposes, after described sample attaches, carry out 0.5MPa with the automatic still of the former making institute's company's system of chestnut, 50 ℃, pressurization in 20 minutes.Afterwards, 23 ℃, carry out under the condition of 50%RH placing in 24 hours, with the stretching experiment machine (Ao Rui company system, TENSILON), take peeling rate as 300m m/min, the condition that peel angle is 180 ° (attaches the clinging power behind 1 order 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 with adhering agent layer that obtains in embodiment or the comparative example is cut to the size of 50mm * 50mm, the sample that obtains carries out under the humidity of 50%RH placing in 24 hours 23 ℃ temperature.Afterwards, stripping film is peeled off, and to the adhering agent layer surface of exposing, uses resistrivity meter (Mitsubishi Chemical analytical technology company system, high resistance instrument UP MCP-HT450 type), according to ISK6911 effects on surface resistance value (Ω/sq) measure.The results are shown in table 2.

(experimental example 6) (mensuration of extension at break degree)

Tackiness composition with the modulation that obtains in embodiment or the comparative example, carried out stripping film (Lindeke Co., Ltd's system of the pet film of lift-off processing with the type siloxane stripper at a face, SP-PET3811) be coated with on the lift-off processing face, making dried coating thick is 25 μ m, carry out heating between 1 minute at 100 ℃, adhering agent layer forms.(Lindeke Co., Ltd's system, lift-off processing face SP-PET3801) is fitted, and obtains adhesive sheet with another stripping film that has carried out the pet film of lift-off processing with the type siloxane stripper to make this adhering agent layer.

A plurality of layer is carried out stacked, the aggregate thickness that makes the adhering agent layer in the described adhesive sheet is 500 μ m, and only makes the stripping film on the top layer that is stacked body remaining.Make described adhering agent layer at 23 ℃, carried out for 2 weeks under the atmosphere of 50%RH and place.Afterwards, the adhesive sheets that described adhering agent layer is stacked from a plurality of layer cut out 10mm wide * long sample of 75mm, peel off being stacked on the top layer of body stacked stripping film, sample is loaded, make the sample determination position be 10mm wide * 20mm long (prolonging direction), 23 ℃, under the environment of 50%RH with stretching experiment machine (Ao Rui company system, TENSILON) draw speed that divides with 200mm/ stretches, and (%) measures to the extension at break degree.The results are shown in table 2.

Table 1

Table 1 (continuing)

[table 2]

[table 2]

Can clearly draw from table 2, in the polarized light piece with adhering agent layer that obtains among the embodiment, when having sufficient clinging power and charged preventive, the extension at break degree is more than 1500%, demonstrate good stress relaxation rate, anti-light leak and weather resistance is all good thus.

[utilizing on the industry possibility]

Tackiness agent of the present invention can be used in optics well, and for example polarized light piece and polarizer is bonding.In addition, adhesive sheet of the present invention can be suitable for well as the adhesive sheet of the used for optical part of polarized light piece and polarizer etc.

[explanation of symbol]

1A, the 1B... adhesive sheet

11... adhering agent layer

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

13... base material.

Claims (10)

1. tackiness agent, it is characterized in that: contain weight average molecular weight and be 500,000～3,000,000 the 1st (methyl) acrylic ester polymer (A), weight average molecular weight and be 8000～300,000 the crosslinked composition that forms of the 2nd (methyl) acrylic ester polymer (B) and charged preventor (C), it is characterized in that: in the stretching experiment, its extension at break degree is more than 1500%, and gel fraction is 30～90%.

2. tackiness agent according to claim 1, it is characterized in that: to described the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of described the 2nd (methyl) acrylic ester polymer (B) is 5～50 mass parts.

3. according to claim 1 described tackiness agent, it is characterized in that: the 1st (methyl) acrylic ester polymer (A), perhaps described the 1st (methyl) acrylic ester polymer (A) and crosslinked before described the 2nd (methyl) acrylic ester polymer (B), as the monomer unit that consists of these polymkeric substance, what contain 5～50 quality % contains the alkylene oxide group monomer.

4. tackiness agent according to claim 1, it is characterized in that: charged preventor (C) is ionic compound.

5. tackiness agent according to claim 4 is characterized in that: described ionic compound is for from planting at least a kind that selects by the group that contains nitrogen salt, contains sulfosalt, phosphorous salts and an alkali metal salt consist of.

6. tackiness agent according to claim 1 is characterized in that: described the 2nd (methyl) acrylic ester polymer (B) before crosslinked, as constituent, contain and surpass 1 quality %, 50 quality % less than the monomer that contains reactive functional groups.

7. tackiness agent according to claim 6, it is characterized in that: described the 2nd (methyl) acrylic ester polymer (B), by reacting with the linking agent (D) of the bridging property base of described reactive functional group reactions and crosslinked with having.

8. an adhesive sheet has base material and adhering agent layer, it is characterized in that: described adhering agent layer is made of each described tackiness agent of claim 1～7.

9. adhesive sheet according to claim 8, it is characterized in that: described base material is optics.

10. adhesive sheet, the adhering agent layer that has 2 pieces of stripping films and seized on both sides by the arms by described stripping film, thus, the release surface of described adhering agent layer and described 2 pieces stripping film is joined, it is characterized in that described adhering agent layer is made of each described tackiness agent of claim 1～7.

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