CN102119349B - Optical film with adhesive and optical laminate using same - Google Patents

Optical film with adhesive and optical laminate using same Download PDF

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Publication number
CN102119349B
CN102119349B CN200980131207.XA CN200980131207A CN102119349B CN 102119349 B CN102119349 B CN 102119349B CN 200980131207 A CN200980131207 A CN 200980131207A CN 102119349 B CN102119349 B CN 102119349B
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weight
bonding agent
methyl
blooming
acryl resin
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CN102119349A (en
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竹厚流
金容演
柳廷昊
太田阳介
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Abstract

Disclosed is an optical film with adhesive wherein an adhesive layer (20) formed from a composition that contains (A), (B), and (C) is provided on an optical film (10). (A) 100 parts by weight of an acrylic resin that is a copolymer of a monomer mixture that contains: (A-1) 80-96 wt% of a (meth)acrylic acid ester with formula (I) (I) (R1 is hydrogen or a methyl, and R2 is a C1-14 alkyl), (A-2) 3-15 wt% of an unsaturated monomer that has an aromatic ring and one olefinic double bond in the molecule, and (A-3) 0.1-5 wt% of an unsaturated monomer that has a polar functional group, where the weight average molecular weight (Mw) of the acrylic resin is 1,000,000 to 2,000,000 and the molecular weight distribution (Mw/Mn) is 3 to 7; (B) 0.2-8 parts by weight of an ionic compound that has ionic cations and the melting point of which is no more than 80 DEG C; and (C) 0.01-5 parts by weight of a crosslinking agent.

Description

With bonding agent blooming with use its optical laminate
Technical field
The present invention relates to a kind of blooming that is formed with adhesive phase.As the blooming as object in the present invention, can enumerate for example polarization plates or polarizer.The invention still further relates to the liquid crystal display optical laminate that a kind of use is formed with the blooming of this adhesive phase.
Background technology
Polarization plates is mounted in liquid crystal indicator and is widely used, it is to form adhesive phase with the stacked transparent protective film in the two sides at polaroid, on the surface of at least one party's diaphragm, and on this adhesive phase, pastes the state circulation of stripping film.In addition, also have to be pasted with stacked phase retardation film in the polarization plates of state of diaphragm on the two sides of polaroid and to make elliptic polarization plate, and paste the polarization plates of adhesive phase/stripping film in this phase retardation film side.And then, sometimes also can paste adhesive phase/stripping film on the surface of phase retardation film.Before sticking on liquid crystal cells, from these polarization plates, elliptic polarization plate, phase retardation film etc., stripping film is peeled, stick on liquid crystal cells via the adhesive phase exposing.Because such polarization plates, elliptic polarization plate or phase retardation film can produce static stripping film being peeled off while pasting on liquid crystal cells, therefore wish that developing it prevents countermeasure.
As one of its countermeasure; in Japanese kokai publication hei 6-313807 communique (patent documentation 1), proposed the stacked diaphragm in a kind of surface at polarizer membrane and be provided with the polarization plates of adhesive phase on the surface of diaphragm, this polarization plates is used the composition that comprises the ionic conductivity composition that is made up of electrolytic salt and organopolysiloxane and acrylic acid series copolymer as bonding agent.By using this bonding agent, shown antistatic behaviour, but its performance may not be abundant, and bonding persistence can not say sufficient.
On the other hand, in Japanese Unexamined Patent Application Publication 2004-536940 communique (patent documentation 2), disclose, in pressure-sensitive adhesive (bonding agent), coordinated the antistatic agent of organic salt, and give antistatic behaviour to this bonding agent.In addition, in TOHKEMY 2004-114665 communique (patent documentation 3), recorded, the salt forming by quaternary ammonium cation that to comprise by total carbon number in tackifier etc. be 4～20 and the negative ion that contains fluorine atom is given antistatic behaviour.And then, in TOHKEMY 2006-307238 communique (patent documentation 4), record, make to contain at the lower ionic liquid for liquid of room temperature (25 ℃) in bonding agent antistatic to obtain.But, when the polarization plates that is coated with bonding agent is placed for a long time, because of rheological parameters' change with time antistatic behaviour variation sometimes.The circulation of general polarization plates and holding time are 6 months from making beginning the longest, so require will keep antistatic property until client is interior during using.
In addition, band bonding agent blooming as above sticks on and on liquid crystal cells, makes liquid crystal indicator with its adhesive phase side, but with this state be placed under high temperature or hot and humid condition or repeatedly heating when cooling, the change in size that can follow blooming produces foaming or heaves or peel off etc. in generation between blooming and adhesive phase or between adhesive phase and liquid crystal cells glass at adhesive phase, therefore, require this undesirable condition not to occur and permanance is good.And then, while exposing at high temperature, act on the skewness of the residual stress of blooming, stress is concentrated in the peripheral part of blooming, result, and in the time of black demonstration, producing being called as that peripheral part bleaches leaks white phenomenon or color spot, therefore, also require to suppress this leakage in vain or color spot.And then, in addition, on liquid crystal cells when adhesive band bonding agent blooming, prepare when incomplete, once its blooming is peeled off, to again paste new film, require in the time of such peeling off adhesive phase along with blooming is peeled off and the residual adhesive on glass and do not produce fuzzy etc. so-called re-workability in unit not together.
In TOHKEMY 2007-138056 communique (patent documentation 5), record, make alkyl acrylate and contain aromatic rings monomer copolymerization, the molecular weight distribution that the weight-average molecular weight (Mw) of the resin obtaining and the ratio (Mw/Mn) of number-average molecular weight (Mn) are represented extends to 10～50, thereby suppresses the method for light leak.By using such bonding agent, can reduce light leak, but can not say fully, and, because molecular weight distribution is wide, sometimes under hot conditions, foam.
Look-ahead technique document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 6-313807 communique
Patent documentation 2: Japanese Unexamined Patent Application Publication 2004-536940 communique
Patent documentation 3: TOHKEMY 2004-114665 communique
Patent documentation 4: TOHKEMY 2006-307238 communique
Patent documentation 5: TOHKEMY 2007-138056 communique
The summary of invention
The problem that invention will solve
Problem of the present invention is, provide a kind of when giving high antistatic behaviour its antistatic behaviour do not change when The book of Changes, even if maximize, leak the white also excellent band bonding agent blooming that is provided with bonding agent (Japanese: sticker) layer on blooming surface that suppresses.The inventor etc. have carried out wholwe-hearted research in order to solve above-mentioned problem, found that, by following composition being set as adhesive phase on the surface of blooming, can obtain the leak band bonding agent blooming of white preventive, antistatic behaviour and excellent in te pins of durability, thereby complete the present invention, described composition is take acrylate as principal ingredient, coordinates acryl resin and the specific ionic compound of structural unit of unsaturated monomer comprising from having aromatic rings in molecule.
For the means of dealing with problems
; of the present inventionly be characterised in that with bonding agent blooming; at least one side at blooming forms adhesive phase; by containing, 100 weight portions (A) acryl resin, 0.2～8 weight portion (B) have organic cation to this adhesive phase and fusing point is that 80 ℃ of following ionic compounds and the adhesive composition of 0.01～5 weight portion (C) crosslinking chemical form; this adhesive phase has the gel fraction of 70～99 % by weight
Described (A) acryl resin is in 80～96 % by weight (A-1) (methyl) acrylate, 3～15 % by weight (A-2) molecule, to have by comprising the multipolymer that monomer mixture that the unsaturated monomer of the two keys of an alkene and at least one aromatic rings and 0.1～5 % by weight (A-3) have the unsaturated monomer of polar functional group obtains, and the acryl resin that weight-average molecular weight (Mw) is 1,000,000～2,000,000, the molecular weight distribution shown in the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 3～7;
Described (A-1) (methyl) acrylate is (methyl) acrylate shown in following formula (I),
[changing 1]
(in formula, R 1represent hydrogen atom or methyl, R 2the alkyl of the carbon number 1～14 that expression can be replaced by the alkoxy of carbon number 1～10).
In addition, according to the present invention, also provide a kind of and be describedly layered in its adhesive phase side the optical laminate that glass substrate forms with bonding agent blooming.
The effect of invention
In the present invention, as the adhesive composition that is used to form adhesive phase, there is unsaturated monomer (A-2) to there is the two keys of 1 alkene and at least one aromatic rings in the molecule acryl resin (A) as constituent by collaboration, and there is the composition that organic cation and fusing point are 80 ℃ of following ionic compounds (B), can prevent by the inhomogeneous optical defect causing of stress distribution, therefore, can suppress to leak white, effectively suppress the charged of optics simultaneously, even start long-time keeping from making, also can keep the antistatic property at initial stage.
In addition, once band bonding agent blooming of the present invention is after it is layered on glass substrate, having in any ill-considered situation, when this blooming is peeled off from glass substrate together with bonding agent, on the surface of the glass substrate after peeling off, also seldom produce cull or fuzzy, can again be used as glass substrate, re-workability excellence.
And then, the acryl resin (A) that band bonding agent blooming of the present invention is 3～7 by use molecular weight distribution (Mw/Mn) is as the adhesive composition that is used to form adhesive phase, leakage can effectively prevent from forming optical laminate time is white, meanwhile, under hot conditions, also can prevent the unfavorable conditions such as foaming.And then, in addition, by the gel fraction of adhesive phase being set as to the scope of 70～99 % by weight, can improve the permanance of adhesive phase, the appearance change can suppress the tests such as, wet-heat resisting heat-resisting so that this state on the glass substrate of liquid crystal cells of sticking on bonding agent blooming is carried out, heat shock resistance time.
This for example by being layered on the glass substrate of liquid crystal cells, can provide liquid crystal display optical laminate with bonding agent blooming.This optical laminate its adhesive phase under wet heat condition absorbs and relaxes the stress being caused by the change in size of blooming and glass substrate, therefore, can alleviate local stress and concentrate, and can suppress heaving or peeling off etc. with respect to the adhesive phase of glass substrate.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section that represents the example of the preferred layer formation of optical laminate of the present invention.
Embodiment
Below, the present invention is described in detail.Of the present inventionly be formed with adhesive phase with bonding agent blooming at least one side of blooming, the adhesive composition that forms described adhesive phase by contain (A) acryl resin, (B) have organic cation and fusing point be 80 ℃ of following ionic compounds and (C) composition of crosslinking chemical form.First, the each composition that forms adhesive composition is described.
[acryl resin (A)]
In band bonding agent blooming of the present invention, the acryl resin (A) that adhesive composition uses is using the structural unit from (methyl) acrylate shown in above-mentioned formula (I) as major component, particularly, except the structural unit being somebody's turn to do from (methyl) acrylate, also comprise from the structural unit of unsaturated monomer in molecule with the two keys of 1 alkene and at least 1 aromatic rings, from having with free carboxy, hydroxyl, amino, epoxide ring is the monomer of the heterocyclic radical isopolarity functional group of representative, preferably there is the structural unit of (methyl) acrylic acid series compound of polar functional group.At this, (methyl) acrylic acid refers to be any in acrylic or methacrylic acid, and " (methyl) " while in addition, being called (methyl) acrylate etc. also has the identical meaning.
In the described formula (I) of the primary structure unit as acryl resin (A), R 1for hydrogen atom or methyl, R 2for the alkyl of carbon number 1～14.R 2hydrogen atom in each group of shown alkyl can be replaced by the alkoxy of carbon number 1～10.
In (methyl) acrylate (A-1) shown in formula (I), as R 2for (methyl) acrylate of non-substituted alkyl, specifically can illustrate: the straight chain shape alkyl acrylate of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid n-octyl, lauryl acrylate and so on; The branching shape alkyl acrylate of isobutyl acrylate, 2-EHA, Isooctyl acrylate monomer and so on; The straight chain shape alkyl methacrylate of methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, n-BMA, n octyl methacrylate, lauryl methacrylate and so on; The branching shape alkyl methacrylate of isobutyl methacrylate, 2-Ethylhexyl Methacrylate, EHMA and so on etc.
Wherein, preferably n-butyl acrylate, particularly, forming in all monomers of acryl resin (A), preferably take n-butyl acrylate more than 50 % by weight and the mode that meets the above-mentioned regulation relevant to (methyl) acrylate (A-1) use.
As R 2for alkoxy replace alkyl time, R 2(methyl) acrylate that formula (I) during for alkoxyalkyl represents, specifically can illustrate: acrylic acid 2-methoxyl ethyl ester, acrylic acid ethoxy methyl esters, methacrylic acid 2-methoxyl ethyl ester, methacrylic acid ethoxy methyl esters etc.
These (methyl) acrylate can be distinguished separately and to use, and also can use the different multiple copolymerization of carrying out.
The unsaturated monomer (A-2) in molecule with the two keys of 1 alkene and at least one aromatic rings preferably has (methyl) acryloyl group as the group that contains the two keys of alkene.As its example, can enumerate: (methyl) benzyl acrylate, neopentyl glycol benzoic ether (methyl) acrylate etc., the unsaturated monomer that particularly preferably following formula (II) represents.
[changing 2]
In formula, R 3represent hydrogen atom or methyl, the integer that n is 1～8, R 4represent hydrogen atom, alkyl, aralkyl or aryl.R 4during for alkyl, its carbon number can be 1～9 left and right, same, and during for aralkyl, its carbon number can be 7～11 left and right, or while being aryl, its carbon number can be 6～10 left and right.
As the alkyl of carbon number 1～9, can enumerate methyl, butyl, nonyl etc., as the aralkyl of carbon number 6～11, can enumerate benzyl, phenethyl, menaphthyl etc., as the aryl of carbon number 6～10, can enumerate phenyl, tolyl, naphthyl etc.
As the unsaturated monomer of concrete formula (II), can enumerate: (methyl) acrylate, 2-(adjacent phenyl phenoxy group) ethyl (methyl) acrylate etc. of 2-phenoxy group ethyl (methyl) acrylate, 2-(2-phenoxy group ethoxy) ethyl (methyl) acrylate, oxirane modification nonyl phenol.These unsaturated monomers in molecule with the two keys of 1 alkene and at least one aromatic rings can distinguish use separately, also can be used in combination different multiple.
Wherein, preferably use 2-phenoxy group ethyl (methyl) acrylate or 2-(adjacent phenyl phenoxy group) ethyl (methyl) acrylate as form acryl resin (A) one of containing aromatic rings unsaturated monomer (A-2).
As the example of unsaturated monomer (A-3) with polar functional group, can enumerate: the unsaturated monomer with free carboxy of acrylic acid, methacrylic acid, β-propyloic acrylic ester and so on; The unsaturated monomer with hydroxyl of (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-or 3-chlorine-2-hydroxyl propyl ester, diethylene glycol list (methyl) acrylate and so on; Acryloyl morpholine, caprolactam, NVP, tetrahydrofurfuryl (methyl) acrylate, caprolactone modification tetrahydrofurfuryl acrylate, 3, the unsaturated monomer with heterocyclic radical of 4-epoxycyclohexyl methyl (methyl) acrylate, (methyl) glycidyl acrylate, DHF and so on; N, N-dimethyl aminoethyl (methyl) acrylate and so on there is the amino unsaturated monomer different from heterocycle etc.These unsaturated monomers with polar functional group can be distinguished separately and to use, and also can use different multiple.
Wherein, the polar functional group of unsaturated monomer (A-3) is preferably free carboxy, hydroxyl, amino or epoxide ring.Particularly preferably the unsaturated monomer with hydroxyl is used as to one of unsaturated monomer (A-3) containing polar functional group forming acryl resin (A).In addition, except thering is the unsaturated monomer of hydroxyl, and with thering is the unsaturated monomer of other polar functional group, the unsaturated monomer for example with free carboxy is also effective.
The content of (methyl) acrylate (A-1) that above-mentioned formula (I) represents in acryl resin (A) is made as 80～96 % by weight, more than being preferably 82 % by weight, more preferably more than 85 % by weight, be preferably in addition below 94 % by weight, more preferably below 92 % by weight.The content of the unsaturated monomer (A-2) in molecule with the two keys of 1 alkene and at least one aromatic rings in acryl resin (A) is made as 3～15 % by weight, more than being preferably 5 % by weight, more preferably more than 5.5 % by weight, more than being particularly preferably 7 % by weight, be preferably in addition below 12 % by weight, more preferably, below 9.9 % by weight, be particularly preferably below 9.5 % by weight, be further preferably below 9 % by weight.The content of the unsaturated monomer (A-3) with polar functional group in acryl resin (A) is made as 0.1～5 % by weight, more than being preferably 0.5 % by weight, is preferably in addition below 3 % by weight.
The acryl resin (A) using in the present invention can also comprise the structural unit of the unsaturated monomer (A-3) that has the unsaturated monomer (A-2) of the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1), molecule representing from above-mentioned formula described above (I) and have polar functional group monomer in addition.As their example, can enumerate: from molecule, have ester ring type structure (methyl) acrylate structural unit, from the structural unit of styrenic monomers, from the structural unit of ethene base system monomer, from the structural unit etc. of monomer in molecule with multiple (methyl) acryloyl group.
So-called ester ring type structure refers to that carbon number is generally more than 5, is preferably the naphthenic hydrocarbon structure of 5～7 left and right.As the concrete example of acrylate with ester ring type structure, can enumerate: isobornyl acrylate, cyclohexyl acrylate, acrylic acid two encircles pentyl ester, acrylic acid cyclo-dodecyl ester, acrylic methyl cyclohexyl, acrylic acid 3-methyl cyclohexanol ester, acrylic acid tert-butyl group cyclohexyl, α-ethoxy-c olefin(e) acid cyclohexyl, acrylic acid cyclohexyl phenyl ester etc., as the concrete example of methacrylate with ester ring type structure, can enumerate: isobornyl methacrylate, cyclohexyl methacrylate, methacrylic acid two encircles pentyl ester, methacrylic acid cyclo-dodecyl ester, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, methacrylic acid tert-butyl group cyclohexyl, methacrylic acid cyclohexyl phenyl ester etc.
As the example of styrenic monomers, except styrene, can enumerate: the ring-alkylated styrenes of methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group styrene and so on; The halogenated styrenes of fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene ethene and so on; And nitrostyrolene, acetylbenzene ethene, methoxy styrene, divinylbenzene etc.
As the example of ethene base system monomer, can enumerate: the fatty acid vinyl ester of vinyl acetate, propionate, vinyl butyrate, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate and so on; The ethylene halide of vinyl chloride or bromine ethene and so on; The inclined to one side ethylene halide of vinylidene chloride and so on; The nitrogenous aromatic vinyl of vinylpyridine, vinyl pyrrolidone, vinylcarbazole and so on; The conjugate diene monomer of butadiene, isoprene, chlorbutadiene and so on; And vinyl cyanide, methacrylonitrile etc.
As the example of monomer in molecule with multiple (methyl) acryloyl group, can enumerate: 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1, has the monomer of 2 (methyl) acryloyl groups in the molecule of 9-nonanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate and so on; In the molecule of trimethylolpropane tris (methyl) acrylate and so on, there is the monomer of 3 (methyl) acryloyl groups etc.
The unsaturated monomer (A-3) that has the unsaturated monomer (A-2) of the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1), molecule that above-mentioned formula (I) represents and have polar functional group monomer in addition can distinguish use separately, or also can combine two or more use.From the structural unit of above-mentioned (A-1)～(A-3) monomer in addition with respect to nonvolatile component 100 weight portions of acryl resin (A) with common 0～20 weight portion, preferably the ratio of 0～10 weight portion contains.
The effective constituent of bonding agent can comprise the acryl resin that has the unsaturated monomer (A-2) of the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1), molecule representing from formula as above (I) and have the structural unit of the unsaturated monomer (A-3) of polar functional group that contains of more than two kinds.And then, in aforesaid propylene acid resin, can also mix the acryl resin different from it, concrete example as for having from the structural unit of (methyl) acrylate of formula (I) and not containing the acryl resin of polar functional group etc.Comprise more than the acryl resin that has the unsaturated monomer (A-2) of the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1), molecule representing from formula (I) and have the structural unit of the unsaturated monomer (A-3) of polar functional group is preferably made as 80 % by weight with respect to whole acryl resins, more than being more preferably made as 90 % by weight.
In (methyl) acrylate (A-1), molecule being represented by contained (I), having the unsaturated monomer (A-2) of the two keys of 1 alkene and at least one aromatic rings and having multipolymer that the monomer mixture of the unsaturated monomer (A-3) of polar functional group obtains is that acryl resin (A) adopts weight-average molecular weight (Mw) that the polystyrene standard of measuring by gel permeation chromatography (GPC) the converts acryl resin in 1,000,000～2,000,000 scope.The weight-average molecular weight that polystyrene standard converts is 1,000,000 when above, the tackiness increase under hot and humid, and the possibility of heaving, peeling off between glass substrate and adhesive phase has the tendency of reduction, and the tendency that is improved of re-workability, therefore preferred.In addition, this weight-average molecular weight is below 2,000,000 time, even if sticking on the size of the blooming on described adhesive phase changes, adhesive phase is not followed its change in size yet and is changed, therefore, between the brightness of the edge part of liquid crystal cells and the brightness of central part, there is no difference, have and suppress to leak tendency white, color spot, therefore preferred.The molecular weight distribution that the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) represents is in the scope of 3～7 left and right.
In addition, for exhibit adhesiveness, aforesaid propylene acid resin (A) preferably its glass transition temperature the scope of-10～-60 ℃.The glass transition temperature of resin can utilize differential scanning calorimeter to measure conventionally.
The acryl resin (A) that forms adhesive phase can utilize the known the whole bag of tricks such as such as solution polymerization process, emulsion polymerization, mass polymerization, suspension polymerization to manufacture.In the manufacture of this acryl resin, conventionally use polymerization initiator.Total 100 weight portions of the whole monomers that use in the manufacture of polymerization initiator with respect to acryl resin are 0.001～5 weight portion left and right.
As polymerization initiator, use thermal polymerization, Photoepolymerizationinitiater initiater etc.As Photoepolymerizationinitiater initiater, for example, can enumerate: 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc.As thermal polymerization, for example can enumerate: 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (cyclohexane-1-nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-methoxyl valeronitrile), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2, the azo based compound of 2 '-azo two (2-hydroxymethyl propionitrile) and so on; Lauroyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, tert butyl peroxy benzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxy dicarbonate, tert-butyl hydroperoxide neodecanoic acid ester, tert-butyl hydroperoxide pivalate, peroxidating (3,5,5-trimethyl acetyl base) and so on organic peroxide; The inorganic peroxide of potassium persulfate, ammonium persulfate, hydrogen peroxide and so on etc.In addition, and also can be used as polymerization initiator with redox series initiators of superoxide and reductive agent etc.
As the manufacture method of acryl resin, the solution polymerization process in the method shown in preferably above.
When the concrete example of enumerating solution polymerization process describes, can enumerate following methods: desirable monomer and organic solvent are mixed, in nitrogen atmosphere, add thermal polymerization, 40～90 ℃ of left and right, preferred about 60～80 ℃ stirrings method etc. of about 3～10 hours.In addition, in order to control reaction, monomer, thermal polymerization can be added to continuously or off and in polymerization or with the state that is dissolved in organic solvent and add.At this, as organic solvent, for example can use: toluene, dimethylbenzene and so on aromatic hydrocarbon based; The ester class of ethyl acetate, butyl acetate and so on; The aliphatics alcohols of propyl alcohol, isopropyl alcohol and so on; The ketone of acetone, methyl ethyl ketone, methyl isobutyl ketone and so on etc.
[ionic compound (B)]
In the present invention, on the basis of above-described acryl resin (A), using fusing point is 80 ℃ of following ionic compounds (B).This ionic compound (B) has organic cation.
The cation constituent that forms ionic compound (B) is to meet to form the organic cation that fusing point is 80 ℃ of following ionic compounds, is not particularly limited in addition.For example can enumerate: glyoxaline cation, pyridylium, ammonium cation, sulfonium cation, phosphonium cation etc., while being used for the adhesive phase of blooming, from being difficult for charged viewpoint when stripping film is thereon peeled off and considering arranging, preferably pyridylium, glyoxaline cation.The molecular weight of ionic compound (B) is not particularly limited, for example, be preferably molecular weight below 700, more preferably below 500.
On the other hand, in ionic compound (B), the anion component that becomes the counter ion counterionsl gegenions of above-mentioned cation constituent is that 80 ℃ of following ionic compounds are just not particularly limited as long as meet formation fusing point, it can be inorganic anion, also can be organic anion, for example, can enumerate following ion.
Cl anion (Cl -),
Bromine anions (Br -),
Iodine negative ion (I -),
Tetrachloro aluminic acid negative ion (AlCl 4 -),
Heptachlor two aluminic acid negative ion (Al 2cl 7 -),
Tetrafluoro boric acid negative ion (BF 4 -),
Hexafluorophosphoric acid negative ion (PF 6 -),
Perchloric acid negative ion (ClO 4 -),
Nitric acid negative ion (NO 3 -),
Acetate anion (CH 3cOO -),
Trifluoracetic acid negative ion (CF 3cOO -),
Loprazolam negative ion (CH 3sO 3 -),
Trifluoromethayl sulfonic acid negative ion (CF 3sO 3 -),
P-toluenesulfonic acid negative ion (p-CH 3c 6h 4sO 3 -),
Two (trifluoromethane sulfonyl group) acid imide negative ion ((CF 3sO 2) 2n -),
Three (trifluoromethane sulfonyl group) methane negative ion ((CF 3sO 2) 3c -),
Hexafluoroarsenate negative ion (AsF 6 -),
Hexafluoro-antimonic acid negative ion (SbF 6 -),
Hexafluoro niobic acid negative ion (NbF 6 -),
Hexafluoro tantalic acid negative ion (TaF 6 -),
Dimethyl phosphinic acids negative ion ((CH 3) 2pOO -),
(gathering) hydrogen fluorine fluoride anion (F (HF) n -) (n is 1～3 left and right),
Dicyanamide anion (dca) ((CN) 2n -),
Sulphur cyanogen negative ion (SCN -),
Perfluorinated butane sulfonic acid anion (C 4f 9sO 3 -),
Two (pentafluoroethane sulfonyl) acid imide negative ion ((C 2f 5sO 2) 2n -),
Perfluorobutyric acid negative ion (C 3f 7cOO -),
(trifluoromethane sulfonyl group) (fluoroform carbonyl) acid imide negative ion ((CF 3sO 2) (CF 3cO) N -) etc.
Wherein, the anion component that contains fluorine atom is preferably to use from the ionic compound consideration that can obtain antistatic property excellence, particularly preferably hexafluorophosphoric acid negative ion or two (trifluoromethane sulfonyl group) acid imide negative ion.
The concrete example of the ionic compound using in the present invention can suitably be selected from the combination of above-mentioned cation constituent and anion component.As the compound of the combination of concrete cation constituent and anion component, can enumerate following compound.
N-hexyl pyridine hexafluorophosphate,
N-octyl group pyridine hexafluorophosphate,
N-butyl-4-picoline hexafluorophosphate,
N-octyl group-4-picoline hexafluorophosphate,
N-methyl-4-hexyl pyridine hexafluorophosphate,
N-butyl-N-crassitude hexafluorophosphate,
1-ethyl-3-methylimidazole hexafluorophosphate,
TBuA hexafluorophosphate,
1-ethyl-3-methylimidazole tosilate,
TBuA tosilate,
1-butyl-3-methylimidazole methane sulfonates,
(2-hydroxyethyl) trimethyl ammonium dimethyl phosphinates,
Two (trifluoromethane sulfonyl group) acid imides of (2-hydroxyethyl) trimethyl ammonium,
Two (trifluoromethane sulfonyl group) acid imides of N-methyl-4-hexyl pyridine,
Two (trifluoromethane sulfonyl group) acid imides of N-hexyl-4-picoline,
Two (trifluoromethane sulfonyl group) acid imides of tetrahexyl ammonium,
Two (trifluoromethane sulfonyl group) acid imides of tricaprylmethylammonium,
Two (trifluoromethane sulfonyl group) acid imides of tributyl-methyl phosphonium ammonium etc.
Such ionic compound (B) can use separately also can combine two or more use.The example of ionic compound (B) is not limited to the above compound of enumerating.
Fusing point is that 80 ℃ of following ionic compounds (B) are described above, is effective giving the adhesive phase that formed by the composition that comprises acryl resin (A) using maintenance in antistatic behaviour in each physical property of bonding agent.When the fusing point of this ionic compound is too high, and the compatibility variation of acryl resin (A), therefore, preferably there are 80 ℃ of following fusing points, more preferably there are 70 ℃ of following fusing points.In addition, consider from the viewpoint of the long-time stability of antistatic behaviour, ionic compound (B) preferably has 30 ℃ of above fusing points, more preferably has 35 ℃ of above fusing points is favourable.Thus, compared with being at normal temperatures the ionic compound of liquid, can keep for a long time the antistatic property of the adhesive phase that is combined with it at the lower ionic compound (B) for solid of normal temperature (25 ℃).
With respect to the nonvolatile component of aforesaid propylene acid resin (A) (from the total amount of the structural unit of above-mentioned A-1, A-2 and A-3) 100 weight portions, the ionic compound (B) of the ratio that contains 0.2～8 weight portion.With respect to nonvolatile component 100 weight portions of acryl resin (A), while containing the above ionic compound of 0.2 weight portion (B), antistatic property improves, therefore preferred, in addition, its amount is that 8 weight portions are when following, easily keep permanance, therefore preferred.Be preferably 0.5 weight portion with respect to the amount of the ionic compound (B) of nonvolatile component 100 weight portions of acryl resin (A) above and below 3 weight portions.
[crosslinking chemical (C)]
In above-described acryl resin (A) and ionic compound (B), further coordinate crosslinking chemical (C), as adhesive composition.Crosslinking chemical (C) in molecule, have at least 2 can and acryl resin (A) in particularly from the compound of the crosslinked functional group of the structural unit of unsaturated monomer with polar functional group, specifically can illustrate: isocyanates based compound, epoxy based compound, metal-chelate syzygy compound, aziridine based compound etc.
Isocyanates based compound for have the compound of at least 2 isocyanate group (NCO) in molecule, for example, can be enumerated: toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenation of benzene dimethyl diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate etc.In addition, make the adducts of polyol reaction gained such as these isocyanate compounds and glycerine, trimethylolpropane and dimer, the tripolymer etc. of isocyanate compound also can be with the crosslinking chemical that acts on bonding agent.Also can mix two or more isocyanates based compound uses.
Epoxy based compound is the compound in molecule with at least 2 epoxy radicals, for example can enumerate: bisphenol A type epoxy resin, ethylene glycol bisthioglycolate glycidyl ether, polyglycol diglycidyl ether, glycerine diglycidyl ether, glycerine triglycidyl group ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane tris glycidyl ether, N, N-diglycidylaniline, N, N, N ', N '-four glycidyl group m-xylene diamine, 1, two (N, N-diglycidyl amino methyl) cyclohexanes of 3-etc.Also can be mixed with two or more epoxy based compound.
As metal-chelate combination compound, for example, can enumerate: compound of coordination diacetone or ethyl acetoacetate etc. on the polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium.
Aziridine based compound is in molecule, to have at least 2 compounds also referred to as the 3 ring skeletons that are made up of 1 nitrogen-atoms and 2 carbon atoms of ethylenimine, for example can enumerate: diphenyl methane-4, 4 '-bis-(1-aziridine formamides), Toluene-2,4-diisocyanate, 4-two (1-aziridine formamide), triethylenemelamine, isophthaloyl base is two-1-(2-methylaziridine), three-1-aziridine phosphine oxide, hexa-methylene-1, 6-two (1-aziridine formamide), trimethylolpropane-tri--β-aziridine propionate, tetramethylol methane-tri--β-aziridine propionate etc.
In these crosslinking chemicals, preferably use isocyanates based compound, particularly xylylene diisocyanate, toluene diisocyanate or hexamethylene diisocyanate; Or the adduct of the polyol reaction gained such as these isocyanate compounds and glycerine or trimethylolpropane; Dimer, the tripolymer etc. of isocyanate compound; The potpourri of these isocyanates based compounds etc.Contain the unsaturated monomer (A-3) of polar functional group in the time thering is the polar functional group being selected from free carboxy, hydroxyl, amino and epoxide ring, particularly, as crosslinking chemical (C) at least one, preferably use isocyanates based compound.As preferred isocyanates based compound, can enumerate: the adduct of toluene diisocyanate, toluene diisocyanate and polyol reaction gained; The dimer of toluene diisocyanate and the tripolymer of toluene diisocyanate; In addition, the adduct of hexamethylene diisocyanate, hexamethylene diisocyanate and polyol reaction gained; The dimer of hexamethylene diisocyanate and the tripolymer of hexamethylene diisocyanate.
Crosslinking chemical (C) is take the ratio cooperation as 0.01～5 weight portion with respect to acryl resin (A) 100 weight portions.The use level of crosslinking chemical (C) is preferably 0.1～5 weight portion left and right with respect to acryl resin (A) 100 weight portions, more preferably 0.2～3 weight portion left and right.With respect to the amount of the crosslinking chemical (C) of acryl resin (A) 100 weight portions be 0.01 weight portion above, in particular for 0.1 weight portion when above, the permanance of adhesive phase is tended to improve, therefore preferred, in addition, be that 5 weight portions are when following, leakage leucismus when being applied to liquid crystal indicator with bonding agent blooming obtains not obvious, therefore preferred.
[forming other composition of bonding agent]
In the adhesive composition that is used to form adhesive phase of the present invention, in order to improve the adaptation of adhesive phase and glass substrate, preferably contain silane based compound (D), contain silane based compound (D) particularly preferably in coordinating in crosslinking chemical acryl resin before.
As silane based compound (D), for example can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group dimethoxy-methyl silane, 3-glycidoxy propyl group ethoxy dimethylsilane etc.Can use two or more silane based compound (D).
Silane based compound (D) can be the silane based compound of silicone oligomeric.While representing silicone oligomer by the form of multipolymer, can enumerate for example following compound.
3-mercaptopropyl trimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-mercaptopropyl trimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-mercaptopropyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing mercapto propyl group of 3-mercaptopropyltriethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
Thiopurine methyltransferase trimethoxy silane-tetramethoxy-silicane alkyl copolymer,
Thiopurine methyltransferase trimethoxy silane-tetraethoxy-silicane alkyl copolymer,
Thiopurine methyltransferase triethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing thiopurine methyltransferase of thiopurine methyltransferase triethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-methacryloxypropyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl triethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing methacryloxypropyl of 3-methacryloxypropyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-acryloxy propyl trimethoxy silicane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl trimethoxy silicane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl-triethoxysilicane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl-triethoxysilicane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing acryloxy propyl group of 3-acryloxy propyl group methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
Vinyltrimethoxy silane-tetramethoxy-silicane alkyl copolymer,
Vinyltrimethoxy silane-tetraethoxy-silicane alkyl copolymer,
Vinyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,
Vinyltriethoxysilane-tetraethoxy-silicane alkyl copolymer,
Vinyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
Vinyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
Vinyl methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing vinyl of vinyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-TSL 8330-tetramethoxy-silicane alkyl copolymer,
3-TSL 8330-tetraethoxy-silicane alkyl copolymer,
APTES-tetramethoxy-silicane alkyl copolymer,
APTES-tetraethoxy-silicane alkyl copolymer,
3-aminopropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-aminopropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-aminopropyl methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-aminopropyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on containing amino multipolymer etc.
These silane based compounds (D) are in most cases liquid.The use level of the silane based compound in bonding agent is with respect to nonvolatile component 100 weight portions (using in situation of more than two kinds as it adds up to weight) of acryl resin (A), be generally 0.01～10 weight portion left and right, be preferably 0.03～1 weight portion.With respect to the amount of the silane based compound of nonvolatile component 100 weight portions of acryl resin be 0.01 weight portion above, in particular for 0.03 weight portion when above, the adaptation raising of adhesive phase and glass substrate, therefore preferred.In addition, its amount is below 10 weight portions, when following in particular for 1 weight portion, has and suppresses the tendency that silane based compound oozes out from adhesive phase, therefore preferred.
In bonding agent described above, can and then coordinate crosslinking catalyst, weather-proof stabilizing agent, tackifier, plastifier, softening agent, dyestuff, pigment, inorganic filler, acryl resin (A) resin in addition etc.In addition, in bonding agent combined with ultraviolet radiation curability compound, after adhesive phase forms, irradiation ultraviolet radiation solidifies it and to make harder adhesive phase be also useful.Wherein, if coordinate crosslinking catalyst together with crosslinking chemical in bonding agent, can prepare adhesive phase by the slaking of short time, in the band adhesive resin film that can suppress to obtain, between resin molding and adhesive phase, produce and heave, peel off or foam in adhesive phase, in addition, re-workability is also better sometimes.As crosslinking catalyst, for example can enumerate: the aminated compounds of hexamethylene diamine, ethylenediamine, polyethylene imine based, hexamethylene tetramine, diethylene triamine, trien, isophorone diamine, trimethylene diamines, poly-amino resins, melamine resin and so on etc.While coordinating as the aminated compounds of crosslinking catalyst, as crosslinking chemical, be preferably isocyanate ester compound in bonding agent.
The above-mentioned each composition that forms bonding agent forms adhesive composition under the state that is dissolved in solvent, is coated on suitable base material and makes it dry, makes adhesive phase.
[gel fraction of adhesive phase]
As the above content of being narrated in the present invention, the gel fraction that makes adhesive phase is 70～99 % by weight.At this, gel fraction is based on following (I)～(IV) value of mensuration.
(I) wire gauze being made up of SUS304 of the adhesive phase of the area of about 8cm × about 8cm and about 10cm × about 10cm (using its weight as Wm) is fitted.
(II) weigh the weight of the laminating thing obtaining in above-mentioned (I), using this weight as Ws, then to wrap into the mode of adhesive phase folding 4 times and weighing after fixing with contract Keyes (stapler) suddenly, using this weight as Wb.
(III) in glass container, pack into by above-mentioned (II) and use the securing silk screen of contract Keyes suddenly, add after ethyl acetate 60mL dipping, this glass container is at room temperature preserved 3 days.
(IV) silk screen is taken out from glass container, at 120 ℃, be dried 24 hours, weigh, using its weight as Wa, divide rate based on following formula calculated for gel.
Gel fraction (% by weight)=[Wa-(Wb-Ws)-Wm}/(Ws-Wm)] × 100
The gel fraction that makes adhesive phase is 70～99 % by weight.Its gel fraction is 70 % by weight when above, and the permanance of adhesive phase improves, therefore preferred, and in addition, its gel fraction is 99 % by weight when following, easily manufactures, therefore preferred.
The gel fraction of adhesive phase can be for example that the kind of acryl resin (A) and the amount of crosslinking chemical are adjusted according to the effective constituent of adhesive phase.Particularly, when making the amount increase of the unsaturated monomer with polar functional group (A-3) in acryl resin (A) or making the amount increase of the crosslinking chemical (C) in adhesive composition, gel fraction increases, therefore, regulate gel fraction according to thering is the unsaturated monomer of polar functional group and/or the amount of crosslinking chemical.Therefore, about the unsaturated monomer (A-3) with polar functional group, from the scope of 0.1～5 % by weight according to and form the combination of other composition of acryl resin (A) and the combination of the kind of crosslinking chemical and amount, select and regulate the amount of the unit of the unsaturated monomer with described polar functional group (A-3) deriving from acryl resin (A) with gel fraction in the mode of above-mentioned scope.In addition, about the amount of crosslinking chemical (C), preferably select the use level of the crosslinking chemical of nonvolatile component 100 weight portions (being its total amount while using two or more) with respect to the acryl resin (A) of formation adhesive phase according to the kind of acryl resin from the scope of 0.1～5 weight portion left and right.
[band bonding agent blooming]
Of the present inventionly be provided with at least one side of blooming the adhesive phase being formed by adhesive composition as above with bonding agent blooming.Blooming used herein is the film with optical characteristics, for example, can enumerate polarization plates, phase retardation film etc.
Polarization plates refers to that the incident lights such as relative natural light have the blooming of the function that penetrates polarized light.In polarization plates, have: have and absorb the straight line polarization plates that there is the rectilinearly polarized light of vibration plane of certain orientation and transmission and have the character of the rectilinearly polarized light of perpendicular vibration plane; There is the polarized light separation membrane that reflection has the rectilinearly polarized light of vibration plane of certain orientation transmission and have the character of the rectilinearly polarized light of perpendicular vibration plane; Be laminated with the elliptic polarization plate of polarization plates and phase retardation film described later etc.As polarization plates, the particularly rectilinearly polarized light film preferred concrete example of (being sometimes called as polaroid or polarizer membrane), can be set forth in the polarization plates of adsorbing the dichromatism pigments such as orientation iodine or dichroic dye in the polyvinyl alcohol resin film of uniaxial tension.
Phase retardation film refers to the anisotropic blooming of display optical, for example, can enumerate: by the polymeric membrane being made up of polyvinyl alcohol (PVA), polycarbonate, polyester, polyarylate, polyimide, polyolefin, cyclic polyolefin, polystyrene, polysulfones, polyethersulfone, Kynoar/polymethylmethacrylate, liquid crystal polyester, cellulose acetate, ethylene-vinyl acetate copolymer saponated material, Polyvinylchloride etc. being stretched as to stretched film that 1.01～6 times of left and right obtain etc.Wherein, the polymeric membrane that preferably uniaxial tension or biaxial stretch-formed polycarbonate membrane or cyclic polyolefin mesentery form.There is the film that is called as single shaft phase retardation film, Wide-angle phase retardation film, low light elastic modulus phase retardation film etc., can be suitable for any.
In addition, show optically anisotropic film or show optically anisotropic film by the coating of inorganic layered compounds and also can be used as phase retardation film by coating, the orientation of liquid crystal compounds.This phase retardation film has the film that is called as temperature compensating type phase retardation film, and the film being formed with the rod shaped liquid crystal twisted-oriented of the trade name sale of " LC film " by Shin Nihon Oil Co., Ltd, the film that the rod shaped liquid crystal tilted alignment of being sold with the trade name of " NH film " by Shin Nihon Oil Co., Ltd equally forms, the film that the discoid liquid crystal tilted alignment of being sold with the trade name of " WV film " by Fuji Photo Film Co., Ltd. forms, the film of the complete biaxial orienting type of being sold with the trade name of " VAC film " by Sumitomo Chemical Co, the film of the biaxial orienting type of being sold with the trade name of " new VAC film " by Sumitomo Chemical Co equally etc.
And then the film that is pasted with diaphragm on these bloomings also can be used as blooming.As diaphragm; use transparent resin molding; as this transparent resin, for example, can enumerate methacrylic resin take Triafol T or cellulose diacetate as the acetate fiber prime system resin of representative, take polymethylmethacrylate as representative, vibrin, polyolefin-based resins, polycarbonate resin, polyether-ether-ketone resin, polysulfone resin etc.Can in the resin that forms diaphragm, coordinate the ultraviolet light absorbers such as salicylate based compound, benzophenone based compound, benzotriazole based compound, triazine based compound, cyanoacrylate based compound, nickel complex salt compounds.As diaphragm, preferably use the cellulose acetate resin films such as three cellulose acetate membrane.
In blooming described above, straight line polarization plates is used mainly with the state that for example, is pasted with diaphragm at the one or both sides that form its polaroid, the polarizer membrane that is made up of polyvinyl alcohol resin greatly.In addition, above-mentioned elliptic polarization plate is the polarization plates that is laminated with straight line polarization plates and phase retardation film, and this polarization plates is also mostly the state that is pasted with diaphragm at the one or both sides of polarizer membrane.Form adhesive phase of the present invention on this elliptic polarization plate time, conventionally form adhesive phase in its phase retardation film side.
Preferably paste stripping film on the surface of its adhesive phase with bonding agent blooming, until protect adhesive layer surface while using.The band bonding agent blooming that is provided with like this stripping film can be manufactured by for example following methods: on stripping film, be coated with above-mentioned adhesive composition and form adhesive phase, the method for further laminated optical film on the adhesive phase obtaining; On blooming, coating adhesive composition forms adhesive phase, then on its bonding agent face, pastes stripping film protection, obtains method with bonding agent blooming etc.Stripping film used herein for example can, for the film to be made up of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylates is as base material, be implemented the film of the demoulding processing gained of silicone-treated and so on etc. to the composition surface of this base material and adhesive phase.
The thickness of adhesive phase is not particularly limited, is preferably generally below 30 μ m, in addition, and more than being preferably 10 μ m, more preferably 15～25 μ m.The thickness of adhesive phase is that 30 μ m are when following, tackiness under hot and humid improves, between glass substrate and adhesive phase, produce the possibility of heaving or peel off and tend to step-down, and, re-workability tends to improve, therefore preferred, in addition, its thickness is 10 μ m when above, changes even if paste the size of blooming thereon, and bonding coat is also followed this change in size and changed, therefore, between the brightness of the edge part of liquid crystal cells and the brightness of central part, there is no difference, have the tendency that suppresses to leak white or color spot, therefore preferred.At present, the Standard General that is pasted on the thickness of the adhesive phase of liquid crystal cells glass is 25 μ m, in the present invention, even this thickness is set as, below 20 μ m, also bringing into play sufficient performance as adhesive phase.
Band bonding agent blooming of the present invention is bonded in glass substrate and forms after optical laminate, exist any imappropriate and when this blooming is peeled off from glass substrate, adhesive phase is followed blooming and is stripped from, surface at the glass substrate being connected with adhesive phase produces fuzzy or cull etc. hardly, therefore, easy adhesive band bonding agent blooming again again on the glass substrate after peeling off., so-called re-workability excellence.
[optical laminate]
Band bonding agent blooming of the present invention can be laminated on glass substrate with its adhesive phase, makes optical laminate.For example, while making optical laminate in glass substrate,, peeling stripping film from the band bonding agent blooming obtaining as described above by stacked band bonding agent blooming, the adhesive phase exposing is fitted in to the surface of glass substrate.At this, as glass substrate, for example, can enumerate: the glass substrate of liquid crystal cells, anti-dazzle glass, the sunglasses glass etc. used.Wherein, on the glass substrate of the front face side (identification side) of liquid crystal cells, stacked band bonding agent blooming (upper deflection board), stacked other band bonding agent blooming (lower polarizing plate) forms on the glass substrate of the rear side of liquid crystal cells optical laminate can be with the panel (liquid crystal panel) that acts on liquid crystal indicator, therefore preferred.As the material of glass substrate, for example, can enumerate: soda-lime glass, glass with lower alkali content, alkali-free glass etc.
For optical laminate of the present invention, the example that several preferred layers are formed is shown in Fig. 1 with schematic cross-section.In the example shown in Fig. 1 (A), the diaphragm 3 with surface-treated layer 2, to stick on a face of straight line polarizing coating 1 in the face of opposition side with described surface-treated layer 2, is formed to polarization plates 5.In this embodiment, polarization plates 5 also becomes said blooming 10 in the present invention simultaneously.Straight line polarizing coating 1 with the face of diaphragm 3 in opposition side on the adhesive phase that comprises ionic compound 20 described above is set, form band bonding agent blooming 25.And, using sticking on the liquid crystal cells 30 of glass substrate in the face of opposition side with polarization plates 5 of described adhesive phase 20, form optical laminate 40.
In the example shown in Fig. 1 (B); by first diaphragm 3 with surface-treated layer 2 to stick on a face of straight line polarizing coating 1 in the face of opposition side with described surface-treated layer 2; on the another side of straight line polarizing coating 1, paste the second diaphragm 4, form polarization plates 5.In this embodiment, polarization plates 5 becomes said blooming 10 in the present invention simultaneously.At the arranged outside adhesive phase that comprises ionic compound 20 described above of the second diaphragm 4 that forms polarization plates 5, form band bonding agent blooming 25.And, using sticking on the liquid crystal cells 30 of glass substrate in the face of opposition side with polarization plates 5 of described adhesive phase 20, form optical laminate 40.
In the example shown in Fig. 1 (C), the diaphragm 3 with surface-treated layer 2, to stick on a face of straight line polarizing coating 1 in the face of opposition side with described surface-treated layer 2, is formed to polarization plates 5.Straight line polarizing coating 1 with the face of diaphragm 3 in opposition side on, paste phase retardation film 7 via interlayer adhesive 8, form blooming 10.At the arranged outside adhesive phase that comprises ionic compound 20 described above of phase retardation film 7 that forms blooming 10, form band bonding agent blooming 25.And, using sticking on the liquid crystal cells 30 of glass substrate in the face of opposition side with blooming 10 of described adhesive phase 20, form optical laminate 40.
In addition; in the example shown in Fig. 1 (D); first diaphragm 3 with surface-treated layer 2, to stick on a face of straight line polarizing coating 1 in the face of opposition side with described surface-treated layer 2, is pasted to the second diaphragm 4 at the another side of straight line polarizing coating 1, form polarization plates 5.Phase retardation film 7 is pasted via interlayer adhesive 8 in outside at the second diaphragm 4 that forms polarization plates 5, forms blooming 10.At the arranged outside adhesive phase that comprises ionic compound 20 described above of phase retardation film 7 that forms blooming 10, form band bonding agent blooming 25.And, using sticking on the liquid crystal cells 30 of glass substrate in the face of opposition side with blooming 10 of described adhesive phase 20, form optical laminate 40.
In these examples, conventionally, the first diaphragm 3 and the second diaphragm 4 are made up of three cellulose acetate membrane, in addition, also can be made up of above-described various transparent resin films.In addition, the surperficial surface-treated layer that is formed at the first diaphragm 3 can be hard conating, antiglare layer, anti-reflection layer, antistatic layer etc.Multiple these layers also can be set.
As Fig. 1 (C) and the example (D), in polarization plates 5, when stacked phase retardation film 7, middle-size and small-size liquid crystal indicator if,, as the preferred example of this phase retardation film 7, can enumerate 1/4 wavelength plate.In this situation, conventionally, using the absorption axes of polarization plates 5 with show greatly as the hysteresis phase axle of the phase retardation film 7 of 1/4 wavelength plate the mode that 45 degree report to the leadship after accomplishing a task and be configured, but also can its angle be offset to a certain degree by 45 degree according to the characteristic of liquid crystal cells 30.On the other hand, the large-scale liquid crystal indicator such as televisor, is compensated for as object with phase difference compensation or the field angle of liquid crystal cells 30 if, uses the phase retardation film with various phase difference values according to the characteristic of this liquid crystal cells 30.In this situation, conventionally, be configured with the absorption axes of polarization plates 5 and the hysteresis phase axle of phase retardation film 7 mode substantially vertical or almost parallel.In the time forming phase retardation film 7 by 1/4 wavelength plate, preferably use the stretched film of single shaft or twin shaft.In addition, when being compensated for as object and phase retardation film 7 be set with the phase difference compensation of liquid crystal cells 30 or field angle, except single shaft or biaxially-stretched film, can also use the film of through-thickness orientation on single shaft or biaxial stretch-formed basis, coating of liquid crystalline equiphase is poor on support membrane manifests material and make it be orientated film that fixing film etc. is called as optical compensation films as phase retardation film 7.
Equally, as shown in Fig. 1 (C) and example (D), in the time pasting polarization plates 5 and phase retardation film 7 via interlayer adhesive 8, described interlayer adhesive 8 also can collaboration has the such antistatic agent of ionic compound described above, has been endowed the bonding agent of antistatic behaviour, in the common expectation antistatic behaviour within reason of this part, therefore, common use does not comprise the general acrylic adhesive of antistatic agent.In addition, large-scale liquid crystal indicator as previously discussed, to become the absorption axes of polarization plates 5 and when the hysteresis phase axle of phase retardation film 7 is substantially vertical or the mode of the relation of almost parallel is configured, can by polarization plates 5 and phase retardation film 7 volume to volume paste, not requiring in the purposes of releasable between the two, also can replace Fig. 1 (C) and (D) shown in interlayer adhesive 8, once use the gluing tackifier that just engages and can not peel off securely.As such tackifier, for example, can enumerate: formed and by making aqueous solvent evaporation obtain the water system tackifier of adhesive power, being cured the ultraviolet hardening tackifier etc. that obtains adhesive power by irradiation ultraviolet radiation by aqueous solution or aqueous dispersions.
It should be noted that, Fig. 1 (C) and (D) shown in the material self that is formed with the adhesive phase 20 that contains ionic compound on phase retardation film 7 also can circulate with himself, can be used as the band bonding agent blooming described in the present invention.On phase retardation film, be formed with the adhesive phase that contains ionic compound with bonding agent blooming except its adhesive phase being sticked on the liquid crystal cells of glass substrate and makes optical laminate, can also paste polarization plates and make in its phase retardation film side other band bonding agent blooming.
In Fig. 1, will be configured in the example of the situation of the identification side of liquid crystal cells 30 with bonding agent blooming 25 exemplified with supposition, but of the present inventionly also can be configured in the rear side of liquid crystal cells, i.e. backlight side with bonding agent blooming.By of the present invention while being configured in the rear side of liquid crystal cells with bonding agent blooming; can replace the diaphragm with surface-treated layer 23 shown in Fig. 1; adopt and do not have the diaphragm of surface-treated layer, all the other are same formation with Fig. 1 (A)～(D).In addition, in this situation, also can be in the known configurations such as arranged outside brightness improving film, condensing film, diffusion barrier of diaphragm that forms polarization plates at the various bloomings of the rear side of liquid crystal cells.
As described above, optical laminate of the present invention can be preferred for liquid crystal indicator.The liquid crystal indicator being formed by optical laminate of the present invention can be for comprising liquid crystal display, televisor, display, e-dictionary, digital camera, digital camera, electronic desktop computer, the clock and watch etc. for vehicle for notebook computer of notebook type such as, desk-top, PDA (Personal Digital Assistance) etc.
Embodiment
Below, enumerate embodiment and further specifically describe the present invention, but the present invention is not limited by these examples.In example, representing " part " and " % " of use amount or content, unless otherwise specified, is just weight basis.
In following example, nonvolatile component is the value of using the method based on JIS K 5407 to measure.Particularly, the binder solution that weighs any weight is put into glassware, will in explosion-proof baking oven, represent with 115 ℃ of residual nonvolatile component weight ratios of the weight of the relatively initial solution of measuring that are dried after 2 hours.In addition, being determined as follows of weight-average molecular weight carried out, " the TSK gel XL " of the 4 eastern ソ mono-(strain) that connect in GPC device system, " the GPC KF-802 " of 1 Shodex (strain) system amount to 5 as chromatographic column, use tetrahydrofuran as dissolution fluid, under the condition of sample solution concentration 5mg/ml, sample import volume 100 μ l, 40 ℃ of temperature, flow velocity 1ml/ minute, utilize standard styrene to convert and carry out.
First, represent to have manufactured the acryl resin (A) that stipulates in the present invention of the major component that becomes adhesive composition and similar with it but depart from the example of the acryl resin of regulation of the present invention.
[polymerization example 1]
In the reaction vessel that possesses cooling tube, nitrogen ingress pipe, temperature and take into account stirring machine, add 81.8 parts of ethyl acetates, as 93.6 parts of the butyl acrylates of (A-1), as 5.0 parts of the acrylic acid 2-phenoxy ethyl of (A-2), as the mixed solution of 0.4 part, 1.0 parts of the acrylic acid 2-hydroxy methacrylates of (A-3) and acrylic acid, make its oxygen-free gas with the air in nitrogen replaceable equipment, meanwhile, by interior temperature rise to 55 ℃.,, add azoisobutyronitrile (polymerization initiator) 0.14 part and be dissolved in the complete soln of gained in 10 parts of ethyl acetates thereafter.Add initiating agent after 1 hour, mode take the concentration of acryl resin that do not comprise monomer as 35% with 17.3 parts/hr of interpolation speed by ethyl acetate continuous adding in reaction vessel, simultaneously, at 54～56 ℃ of interior temperature, be incubated 12 hours, finally add ethyl acetate, regulate take the concentration of acryl resin as 20% mode.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,710,000, Mw/Mn is 4.3.Set it as acryl resin A.The structural unit that derives from hydroxyl unsaturated monomer in acryl resin A and be acrylic acid 2-hydroxy methacrylate is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 2]
Except by more 90.6 parts of the quantitative changes of the butyl acrylate in monomer composition, by the quantitative change of acrylic acid 2-phenoxy ethyl more 8.0 parts, operation same with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,740,000, Mw/Mn is 4.1.Set it as acryl resin B.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in acryl resin B is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 3]
Except by more 88.6 parts of the quantitative changes of the butyl acrylate in monomer composition, by the quantitative change of acrylic acid 2-phenoxy ethyl more 10.0 parts, operation same with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,560,000, Mw/Mn is 4.5.Set it as acryl resin C.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in acryl resin C is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 4: relatively use]
Except by more 78.6 parts of the quantitative changes of the butyl acrylate in monomer composition, by the quantitative change of acrylic acid 2-phenoxy ethyl more 20.0 parts, operation same with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,370,000, Mw/Mn is 4.4.Set it as acryl resin D.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in acryl resin D is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 5: relatively use]
Except by more 58.6 parts of the quantitative changes of the butyl acrylate in monomer composition, by the quantitative change of acrylic acid 2-phenoxy ethyl more 40.0 parts, operation same with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,270,000, Mw/Mn is 4.4.Set it as Eudragit E.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in Eudragit E is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 6: relatively use]
Except by more 38.6 parts of the quantitative changes of the butyl acrylate in monomer composition, by the quantitative change of acrylic acid 2-phenoxy ethyl more 60.0 parts, operation same with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,270,000, Mw/Mn is 5.0.Set it as acryl resin F.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in acryl resin F is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 7: relatively use]
Except the amount of the butyl acrylate in monomer composition being made as to 98.6 parts, not using acrylic acid 2-phenoxy ethyl, operation same with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The acryl resin obtaining utilize GPC measure polystyrene conversion weight-average molecular weight Mw for Isosorbide-5-Nitrae 70,000, Mw/Mn be 4.4.Set it as acryl resin G.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in acryl resin G is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 8]
Except by more 88.4 parts of the quantitative changes of the butyl acrylate in monomer composition, by more 10.0 parts of the quantitative changes of acrylic acid 2-phenoxy ethyl, by acrylic acid quantitative change more 0.6 part, operation same with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,530,000, Mw/Mn is 4.8.Set it as acryl resin H.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in acryl resin H is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.6%.
[polymerization example 9]
Monomer composition is changed to: as 78.4 parts of the butyl acrylates of (A-1) and 10.0 parts of acrylic acid 2-methoxyl ethyl esters, as 10.0 parts of the acrylic acid 2-phenoxy ethyl of (A-2), as 0.6 part, 1.0 parts of the acrylic acid 2-hydroxy methacrylates of (A-3) and acrylic acid, in addition, operation same with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,540,000, Mw/Mn is 4.9.Set it as acryl resin I.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in acryl resin I is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.6%.
[polymerization example 10: relatively use]
With in the identical reaction vessel of container using in polymerization example 1, add 81.8 parts of ethyl acetates, as 90.6 parts of the butyl acrylates of (A-1), as 8.0 parts of the acrylic acid 2-phenoxy ethyl of (A-2), as the mixed solution of 0.4 part, 1.0 parts of the acrylic acid 2-hydroxy methacrylates of (A-3) and acrylic acid, make its oxygen-free gas with the air in nitrogen replaceable equipment, meanwhile, by interior temperature rise to 55 ℃.,, add azoisobutyronitrile (polymerization initiator) 0.14 part and be dissolved in the complete soln of gained in 10 parts of ethyl acetates thereafter.Add initiating agent after 1 hour, the mode take the concentration of acryl resin that do not comprise monomer as 35% with 17.3 parts/hr of interpolation speed by ethyl acetate continuous adding in reaction vessel, meanwhile, at 54～56 ℃ of interior temperature, be incubated 4 hours.Thereafter, add the complete soln that azoisobutyronitrile (polymerization initiator) 0.2 part is dissolved in gained in 10 parts of ethyl acetates, be incubated at the same temperature 8 hours, finally add ethyl acetate, regulate take the concentration of acryl resin as 20% mode.The weight-average molecular weight Mw of polystyrene conversion that utilizes GPC to measure of the acryl resin obtaining is 1,070,000, Mw/Mn is 8.2.Set it as acryl resin J.The structural unit that is acrylic acid 2-hydroxy methacrylate from the hydroxyl unsaturated monomer in acryl resin J is 1%, and in addition, carrying out self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
The complete list of the monomer composition of polymerization example 1～10, weight-average molecular weight, Mw/Mn is shown in to table 1.In table, BA refers to butyl acrylate, and MEA refers to acrylic acid 2-methoxyl ethyl ester, and PEA refers to acrylic acid 2-phenoxy ethyl, and HEA refers to acrylic acid 2-hydroxy methacrylate, and AA refers to acrylic acid.
[table 1]
Then the acryl resin that, expression is manufactured more than using is prepared bonding agent and is applicable to embodiment and the comparative example of blooming.In following embodiment and comparative example, as ionic compound, use compound shown below.
Ionic compound 1:N-octyl group-4-picoline hexafluorophosphate structure, the fusing point of following formula (have 44 ℃)
[changing 3]
Two (trifluoromethane sulfonyl group) acid imides of ionic compound 2:N-hexyl-4-picoline structure, the fusing point of following formula (have 18 ℃)
[changing 4]
Ionic compound 3: two (trifluoromethane sulfonyl group) acid imides of tricaprylmethylammonium (have the structure of following formula, be liquid at normal temperatures)
[changing 5]
Ionic compound 4: two (trifluoromethane sulfonyl group) acid imides of tributyl-methyl phosphonium ammonium structure, the fusing point of following formula (have 28 ℃)
[changing 6]
In addition, as crosslinking chemical and silane based compound, use respectively material shown below (being trade name).
(crosslinking chemical)
CORONATE L: the ethyl acetate solution (solid component concentration 75%) of the trimethylolpropane adduct of toluene diisocyanate, obtain from Japanese polyurethane Co., Ltd..
(silane compound)
KBM-403: glycidoxypropyltrime,hoxysilane (liquid), obtain from Shin-Etsu Chemial Co., Ltd.
[embodiment 1～8, reference example 5～6 and comparative example 1～6]
(a) manufacture of bonding agent
With respect to the solid constituent of the acryl resin A～J obtaining in polymerization example 1～10 each 100 parts, the crosslinking chemical (CORONATE L) of the various amounts shown in ionic compound, 0.5 part of silane based compound (KBM-403) and the table 2 of the various amounts shown in mixture table 2 mixes, and then add ethyl acetate take solid component concentration as 13% mode, as adhesive composition.Crosslinking chemical (CORONATEL) is the ethyl acetate solution of solid component concentration 75% as mentioned above, and the addition shown in table 2 is its solid constituent amount.
(b) making with bonding agent blooming
Polyethylene terephthalate film that above-mentioned each adhesive composition is used applicator to be coated on the demoulding to process (trade name " PET 3811 ", obtains from lintec Co., Ltd., be called diffusion barrier) demoulding treated side on, making dried thickness is 20 μ m, at 90 ℃, be dried 1 minute, obtain the bonding agent of sheet.Then; on a face of the polarization plates of the 3-tier architecture forming on the two sides of using the diaphragm clamping absorption being formed by Triafol T to be orientated the polyvinyl alcohol (PVA) polaroid of iodine; paste by lamination after the face contrary with diffusion barrier (bonding agent face) of the above sheet bonding agent obtaining; under the condition of 23 ℃ of temperature, relative humidity 65%, health 7 days, obtains being with bonding agent polarization plates.
(c) the antistatic behaviour evaluation with bonding agent blooming
In the time peeling off the obtained diffusion barrier with bonding agent polarization plates, measure the sheet resistance value of bonding agent with surperficial intrinsic resistance determinator [" Hirest-up MCP-HT450 " (trade name) of Mitsubishi chemical Co., Ltd's system], evaluate antistatic behaviour.Sheet resistance value is 10 11when Ω/ level or its are following, obtain good antistatic behaviour.
(d) making of optical laminate and evaluation
The band bonding agent polarization plates of making from above-mentioned (b) peels after diffusion barrier, its bonding agent face is pasted on to the two sides of glass substrate for liquid crystal cells [" 1737 " (trade name) of Corning company system] to form orthogonal polarization microscope, makes optical laminate.To this optical laminate, carry out the keeping heat resistant test of 96 hours under the drying condition of 80 ℃ of temperature.What leakage when thereafter, visualization is from a polarization plates side incident light was white manifests state.By following benchmark classification for result, be shown in " leaking white (80 ℃ dry) " hurdle of table 2.
What < leakage was white manifests state >
1: do not leak white completely.
2: leak at all unobvious in vain.
3: leak slightly obvious in vain.
4: leak in vain clearly.
In addition, respectively to carrying out the situation (being designated as " heat-resisting " in table 2) of the keeping heat resistant test of 300 hours under the drying condition of 80 ℃ of temperature; Carry out the situation (being designated as " wet-heat resisting " in table 2) in temperature 60 C, 90% time keeping of relative humidity hot resistance test of 300 hours; To be cooled to-30 ℃, then be warming up to the process of 70 ℃ as 1 circulation (1 hour) and repeat the situation (being designated as " resistance to HS " table 2) of the heatproof impact test of 100 these circulations, the optical laminate after visualization test from being heated to the state of 70 ℃ with carrying out.By following benchmark classification for result, be summarized in table 2.
(to the metewand of hot, damp and hot and thermal shock (being designated as respectively " heat-resisting ", " wet-heat resisting ", " resistance to HS " in table 2))
1: do not see completely heave, peel off, the appearance change such as foaming.
2: almost do not see heave, peel off, the appearance change such as foaming.
3: heave, peel off, the appearance change such as foaming is obvious a little.
4: see significantly heave, peel off, the appearance change such as foaming.
(e) the re-workability evaluation with bonding agent blooming
The evaluation of re-workability is carried out as follows.First be, the test film of 25mm × 150mm size by the band bonding agent polarization plates severing obtaining in above-mentioned (b).Then, use sticker (" Lamipacker " (trade name) of Fujipla Co., Ltd. system) to stick on liquid crystal cells with on glass substrate with its binder side this test film, at 50 ℃, 5kg/cm 2(490.3kPa) under, carry out autoclave processing in 20 minutes.Then, at 70 ℃, carry out 2 hours heat treated, then in the baking oven of 50 ℃, preserve after 48 hours, in the atmosphere of 23 ℃ of temperature, relative humidity 50%, the speed of polarization plates being divided with 300mm/ from this stickup test film is peeled off along 180 ° of directions, the state on sight glass plate surface, classifies according to following benchmark.Result is together shown in to table 2.
The metewand > of < re-workability
1: glass pane surface does not produce fuzzy etc. completely.
2: glass pane surface does not almost produce fuzzy etc.
3: glass pane surface generation is fuzzy etc.
4: glass pane surface produces adhesive residue.
[table 2]
From table 1 and table 2, in the acryl resin of the present invention regulation, coordinate the ionic compound of ormal weight and crosslinking chemical and form the embodiment 1～8 of bonding agent antistatic behaviour, leak white preventive and re-workability excellence, in addition, thermotolerance, humidity resistance and resistance to sudden heating also obtain roughly gratifying result.Particularly the antistatic behaviour of embodiment 2, to leak white preventive, re-workability, thermotolerance, humidity resistance and resistance to sudden heating all excellent.
With respect to this, use and contain from thering is the comparative example 1～3 of acryl resins more than structural unit 20 weight portions of unsaturated monomer of aromatic rings and using the white preventive deficiency of leakage of comparative example 4 of acryl resin of structural unit of unsaturated monomer not containing from thering is aromatic rings.In addition, do not reach the comparative example 5 of gel fraction of the present invention regulation in heat resistant test, hot resistance test and heatproof impact test, heave, peel off, the appearance change such as foaming is all obvious.On the other hand, use the white preventive deficiency of leakage of the comparative example 6 of the acryl resin that molecular weight distribution is large.
This disclosed embodiment and embodiment illustrate rather than limit.Scope of the present invention is not above-mentioned explanation but is illustrated in claims, comprises all changes in the meaning and the scope being equal to claim.
Utilizability in industry
Of the present inventionly be endowed high antistatic behaviour with bonding agent blooming, meanwhile, keep for a long time this antistatic behaviour, in addition, permanance is also excellent.This band bonding agent blooming is preferred for liquid crystal indicator.
Symbol description
Adhesive phase, 25 band bonding agent bloomings, 30 liquid crystal cells (glass substrate), 40 optical laminates that 1 straight line polarizing coating, 2 surface-treated layers, 3 first diaphragms, 4 second diaphragms, 5 polarization plates, 7 phase retardation films, 8 interlayer adhesives, 10 bloomings, 20 comprise ionic compound.

Claims (8)

1. a band bonding agent blooming, is characterized in that,
Described is to form adhesive phase at least one side of blooming to form with bonding agent blooming,
This adhesive phase by contain 100 weight portions (A) acryl resin, 0.2～8 weight portion (B) have organic cation, fusing point be 80 ℃ following and normal temperature at 25 ℃ for the ionic compound of solid and the adhesive composition of 0.01～5 weight portion (C) crosslinking chemical form, this adhesive phase has the gel fraction of 70～99 % by weight
Described (A) acryl resin is in 80～96 % by weight (A-1) (methyl) acrylate, 3～15 % by weight (A-2) molecule, to have by comprising the multipolymer that monomer mixture that the unsaturated monomer of the two keys of an alkene and at least one aromatic rings and 0.1～5 % by weight (A-3) have the unsaturated monomer of polar functional group obtains, and the acryl resin that weight-average molecular weight (Mw) is 1,000,000～2,000,000, the molecular weight distribution shown in the ratio Mw/Mn of weight-average molecular weight Mw and number-average molecular weight Mn is 3～7;
Described (A-1) (methyl) acrylate is (methyl) acrylate shown in following formula (I),
Change 1]
In formula, R 1represent hydrogen atom or methyl, R 2the alkyl of the carbon number 1～14 that expression can be replaced by the alkoxy of carbon number 1～10;
The unsaturated monomer in described (A-2) molecule with the two keys of 1 alkene and at least one aromatic rings is (methyl) acrylic monomers containing aromatic rings shown in following formula (II),
[changing 2]
In formula, R 3represent hydrogen atom or methyl, the integer that n is 1～8, R 4represent hydrogen atom, alkyl, aralkyl or aryl.
2. band bonding agent blooming according to claim 1, wherein,
The polar functional group that described (A-3) has the unsaturated monomer of polar functional group is selected from free carboxy, hydroxyl, amino and epoxide ring.
3. band bonding agent blooming according to claim 2, wherein,
Described (C) crosslinking chemical contains isocyanates based compound.
4. band bonding agent blooming according to claim 1, wherein,
The fusing point that described (B) has organic cations ionic compound is more than 30 ℃.
5. band bonding agent blooming according to claim 1, wherein,
Adhesive composition also comprises 0.03～1 weight portion (D) silane based compound.
6. band bonding agent blooming according to claim 1, wherein,
Blooming is selected from polarization plates and phase retardation film.
7. band bonding agent blooming according to claim 1, wherein,
Surface at adhesive phase is pasted with stripping film.
8. an optical laminate, is characterized in that,
Band bonding agent blooming claimed in claim 1 is laminated in glass substrate with its adhesive phase side.
CN200980131207.XA 2008-08-11 2009-08-07 Optical film with adhesive and optical laminate using same Active CN102119349B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2008207234 2008-08-11
JP2008-207234 2008-08-11
PCT/JP2009/064038 WO2010018794A1 (en) 2008-08-11 2009-08-07 Optical film with adhesive and optical laminate using same

Publications (2)

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JP2010066755A (en) 2010-03-25

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