CN102119348B - 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
CN102119348B
CN102119348B CN200980131194.6A CN200980131194A CN102119348B CN 102119348 B CN102119348 B CN 102119348B CN 200980131194 A CN200980131194 A CN 200980131194A CN 102119348 B CN102119348 B CN 102119348B
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Prior art keywords
blooming
methyl
acrylate
bonding agent
adhesive phase
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CN102119348A (en
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竹厚流
金容演
许智惠
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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Physics & Mathematics (AREA)
  • Adhesive Tapes (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to an optical film with an adhesive layer, wherein the optical film (10) is provided with the adhesive layer with the adhesive formed from a composition that contains the 100 wt% of A, 0.3-12 wt% of B, and 0.1-5 wt% of C. The A is an acrylic resin, namely a copolymer of a monomer mixture that contains: 55-94 wt% of(A-1), 5-40 wt% of a (meth)acrylic acid ester having an alkoxyethyl group, such as acrylic acid 2-methoxyethyl, and 0.1-5 wt% of an unsaturated monomer having a polar functional group. The B is an ionic compound that has organic cations and is a solid at room temperature. The C is a crosslinking agent. The A-1 is a (meth)acrylic acid ester with formula (I), wherein R1 is hydrogen or a methyl group, and R2 is a C1-14 alkyl or aralkyl).

Description

Blooming with bonding agent and the optical laminate using it
Technical field
The present invention relates to a kind of blooming being formed with adhesive phase.As the blooming becoming object in the present invention, such as polarization plates and phase retardation film can be enumerated.The invention still further relates to and a kind ofly use this liquid crystal display optical laminate being formed with the blooming of adhesive phase.
Background technology
Polarization plates is mounted on liquid crystal indicator and is widely used, and it is with the two sides laminating transparent diaphragm at polaroid, and the surface of at least one diaphragm formed adhesive phase, and paste on this adhesive phase stripping film state circulation.In addition, stacked phase retardation film in the polarization plates under the state being sometimes also pasted with diaphragm on the two sides of polaroid and make elliptic polarization plate, and at this phase retardation film side adhesive layer/stripping film.And then, sometimes also can at the surface mount adhesive phase/peel ply of phase retardation film.Before liquid crystal cells bonding, stripping film to be peeled from these polarization plates, elliptic polarization plate, phase retardation film etc., and paste on liquid crystal cell by the adhesive phase exposed.Due to electrostatic can be produced when such polarization plates, elliptic polarization plate or phase retardation film paste on liquid crystal cells being peeled off by stripping film, thus wish to develop its Prevent countermeasures.
As one of its countermeasure; the stacked diaphragm in a kind of surface at polarizer membrane is proposed in Japanese Unexamined Patent Publication 6-313807 publication (patent documentation 1); and the polarization plates of adhesive phase is provided with on the surface of diaphragm; wherein, use the composition comprising ionic conductivity composition and the acrylic acid series copolymer be made up of electrolytic salt and organopolysiloxane as bonding agent.By using this bonding agent, although show antistatic behaviour, its performance may not be abundant, and bonding persistence aspect can not say it is reach sufficient performance.
On the other hand, in Japanese Unexamined Patent Application Publication 2004-536940 publication (patent documentation 2), disclose the antistatic agent coordinating organic salt in pressure adhesive (bonding agent), and give antistatic behaviour to this bonding agent.In addition, describing by comprising in bonding agent etc. by total carbon atom number in Japanese Unexamined Patent Publication 2004-114665 publication (patent documentation 3) is that antistatic behaviour given by the salt that the quaternary ammonium cation of 4 ~ 20 and the negative ion containing fluorine atom are formed.And then, describe in Japanese Unexamined Patent Publication 2006-307238 publication (patent documentation 4) and make in bonding agent containing being the ionic liquid of liquid and realize antistatic effect under room temperature (25 DEG C).Describe in Japanese Unexamined Patent Publication 2006-16595 publication (patent documentation 5) a kind of comprise ionic liquid and containing oxirane compound and based on the glass temperature Tg of polymkeric substance be the antistatic behaviour adhesive composition of the polymkeric substance of less than 0 DEG C.But, by be coated with in these documents the disclosed polarization plates being combined with the bonding agent of ionic liquid place for a long time time, because of rheological parameters' change with time sometimes antistatic behaviour be deteriorated.It is 6 months that the circulation of general polarization plates and holding time start the longest from making, so will keep antistatic property in during requiring before client's use.Especially, in the liquid crystal cells of flat plate switch (In-Plane Switching:IPS) pattern, in a lot of situation, all require that blooming has high-antistatic.
In addition, the blooming of band bonding agent as above is pasted with its adhesive phase side and is made liquid crystal indicator on liquid crystal cell, but under being positioned over high temperature or hot and humid condition with this state or when repeatedly carrying out heating and cooling, sometimes along with the change in size of blooming, can foaming be produced at adhesive phase or produce between blooming and adhesive phase or between adhesive phase and liquid crystal cells glass and heave or stripping etc., therefore, seek this undesirable condition not to occur and excellent durability.And then, when exposing at high temperature, owing to acting on the skewness of the residual stress of blooming, stress is concentrated in the peripheral part of blooming, thus the phenomenon being referred to as whiting that peripheral part turns white can be produced when black display or produce color spot, therefore, also seek to suppress this whiting and color spot.And then, on liquid crystal cell laminating band bonding agent blooming time, when not posting, once its blooming is peeled off, then need new film of again fitting, therefore also seek re-workability, that is, when above-mentioned stripping, adhesive phase is stripped together along with blooming and can not residues on unit glass and not produce stain etc.
Disclose in Japanese Unexamined Patent Publication 2005-206776 publication (patent documentation 6) and a kind ofly comprise the antistatic acrylic bonding agent that side chain has the acrylic acid series copolymer of the alkylene oxide such as hydroxyl and ethylene oxide chain chain, glass compound and hardening agent.But the compound used in patent documentation 6 is only the ionic compound with inorganic cations such as Li salt, there is the problem with the intermiscibility difference of the base polymer of bonding agent in such ionic compound.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-313807 publication
Patent documentation 2: Japanese Unexamined Patent Application Publication 2004-536940 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2004-114665 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-307238 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-16595 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2005-206776 publication
Summary of the invention
Problem of the present invention is, provides a kind of and gives high antistatic behaviour, and its antistatic behaviour not The book of Changes time change, the blooming being provided with the band bonding agent of adhesive phase on the surface of blooming that permanance is also excellent.The present inventor etc. have carried out wholwe-hearted research to solve above-mentioned problem, found that, be the ionic compound of solid and crosslinking chemical by being engaged in specific acryl resin under room temperature (25 DEG C), and said composition is arranged at blooming surface and as adhesive phase, the blooming of antistatic behaviour, the rheological parameters' change with time of antistatic behaviour and the band bonding agent of excellent in te pins of durability can be obtained, thus complete the present invention.
Namely, according to the present invention, a kind of blooming with bonding agent can be provided, it is characterized in that, form adhesive phase at least one face of blooming, wherein, described adhesive phase is formed by the adhesive composition of the C containing the A of 100 weight portions and the B of 0.3 ~ 12 weight portion and 0.1 ~ 5 weight portion
Described A is the acryl resin of the multipolymer obtained by the monomer mixture of the A-3 of A-2 and 0.1 ~ 5 % by weight of A-1, the 5-40 % by weight containing 55 ~ 94 % by weight,
Described B has organic cation and is at room temperature the ionic compound of solid,
Described C is crosslinking chemical,
Described A-1 is (methyl) acrylate that following formula (I) represents,
In formula, R 1represent hydrogen atom or methyl, R 2represent that carbon number is alkyl or the aralkyl of 1 ~ 14,
Described A-2 is (methyl) acrylate (following, to be sometimes referred to as " ether type (methyl) acrylate ") that following formula (II) represents,
In formula, R 3represent hydrogen atom or methyl, R 4represent that carbon number is the alkyl of 1 ~ 8, n is the integer of 1 ~ 10,
Described A-3 is the unsaturated monomer with polar functional group.
Find thus, as for giving antistatic behaviour to the adhesive phase formed by the adhesive composition comprising the specific acryl resin A that the present invention specifies and suppressing the antistatic agent of the rheological parameters' change with time of this antistatic behaviour, be that the ionic compound B of solid is effective especially under being used in room temperature (25 DEG C).
In addition, according to the present invention, a kind of blooming of described band bonding agent is also provided to be laminated in the optical laminate of glass substrate with its adhesive phase side.
Invention effect
The blooming of band bonding agent of the present invention can effectively suppress the charged of optics.
And then, by adhesive composition containing having organic cation and be at room temperature the ionic compound of solid, preserve even if long-time after making, also can keep the antistatic property at initial stage.
In addition, cause optical defect owing to can prevent uneven by stress distribution, therefore, whiting can be suppressed.And then, the blooming first pass of band bonding agent is being laminated in after on glass substrate, in the ill-considered situation of any laminating of appearance, even if this blooming is peeled off from glass substrate together with bonding agent, the surface of the glass substrate after stripping also seldom produces cull and stain, again can be used as glass substrate, re-workability is excellent.
The blooming of this band bonding agent, by being laminated in the glass substrate of such as liquid crystal cells, can provide a kind of liquid crystal display optical laminate.Due to this optical laminate its adhesive phase Absorbable rod the stress relaxed caused by the change in size of blooming and glass substrate under wet heat condition, therefore, the stress that can alleviate local is concentrated, thus adhesive phase can be suppressed to heave and stripping etc. from glass substrate.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section representing the example that the preferably layer of optical laminate of the present invention is formed.
Embodiment
The present invention is described in detail below.The blooming of band bonding agent of the present invention defines adhesive phase at least one face of blooming, described adhesive phase by comprising A acryl resin, B has organic cation and is that the ionic compound of solid and the composition of C crosslinking chemical are formed in room temperature.First, each composition forming adhesive composition is described.
[acryl resin A]
In the blooming of band bonding agent of the present invention, the structural unit of (methyl) acrylate since the acryl resin A that adhesive phase uses shown in self-ascending type (I) is major component, specifically, except the structural unit be somebody's turn to do from (methyl) acrylate, also comprise the structural unit of ether type (methyl) acrylate represented from above-mentioned formula (II); And from have free carboxy, hydroxyl, amino, with epoxide ring be the heterocyclic radical isopolarity functional group of representative monomer, preferably there is the structural unit of (methyl) acrylic compounds of polar functional group.At this, (methyl) acrylic acid refers to be any one in acrylic or methacrylic acid, and " (methyl) " when in addition, being called (methyl) acrylate etc. also has identical implication.
In the above-mentioned formula (I) of the essential building blocks as acryl resin A, R 1for hydrogen atom or methyl, R 2for alkyl or aralkyl, preferably alkyl that carbon number is 1 ~ 14.
In (methyl) acrylate A-1 shown in formula (I), as R 2for (methyl) acrylate during alkyl, specifically can illustrate: the straight-chain alkyl acrylate of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl, lauryl acrylate and so on; The branched alkyl acrylate of isobutyl acrylate, 2-EHA, Isooctyl acrylate monomer and so on; The straight-chain alkyl methacrylate of methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, n-BMA, n octyl methacrylate, lauryl methacrylate and so on; The branched alkyl methacrylate etc. of isobutyl methacrylate, 2-Ethylhexyl Methacrylate, EHMA and so on.As R 2for (methyl) acrylate shown in the formula (I) during aralkyl, specifically can exemplary propylene acid benzyl ester and benzyl methacrylate etc.These (methyl) acrylate A-1 can individually use, and also can use different multiplely to carry out copolymerization.
Wherein, preferred n-butyl acrylate, specifically, in all monomers forming acryl resin A, is preferably more than 50 % by weight with n-butyl acrylate and the mode meeting the relevant regulations of above-mentioned (methyl) acrylate A-1 uses.
Ether type (methyl) acrylate of A-2 represents by above-mentioned formula (II).As ether type (methyl) the acrylate A-2 shown in formula (II), specifically can illustrate: acrylic acid 2-methoxy acrylate, acrylic acid 2-ethoxy ethyl ester, acrylic acid 2-methoxyl-2-ethoxy ethyl ester, methacrylic acid 2-methoxy acrylate, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid 2-methoxyl-2-ethoxy ethyl ester etc.These ether type (methyl) acrylate A-2 can be used alone, and also can use different multiplely to carry out copolymerization.
Wherein, preferably use acrylic acid 2-methoxy acrylate as the one formed in (methyl) acrylate A-2 of acryl resin A.
As the example of unsaturated monomer A-3 with polar functional group, can enumerate: the monomer with free carboxy of acrylic acid, methacrylic acid, β-propyloic acrylic ester and so on; The 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, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification tetrahydrofurfuryl acrylate, 3, the monomer with heterocyclic radical of 4-epoxycyclohexyl-methyl (methyl) acrylate, (methyl) glycidyl acrylate, DHF and so on; The unsaturated monomer etc. with the amino different from heterocycle of N, N-dimethyl aminoethyl (methyl) acrylate and so on.These unsaturated monomers with polar functional group can individually 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 use the monomer with hydroxyl as the one contained in the monomer A-3 of polar functional group forming acryl resin A.In addition, have except the monomer of hydroxyl except using, and be also effective with the monomer with other polar functional group, the monomer such as with free carboxy.
Acryl resin A for adhesive phase be represented by the above-mentioned formula (I) containing 55 ~ 94 % by weight (methyl) acrylate A-1,5 ~ 40 % by weight the multipolymer that obtains of the monomer mixture with the unsaturated monomer A-3 of polar functional group of ether type (methyl) acrylate A-2 and 0.1 ~ 5 % by weight that represents of above-mentioned formula (II).In this multipolymer, the structural unit of (methyl) acrylate A-1 preferably represented from formula (I) is 70 ~ 94 % by weight and then preferably 72 ~ 94 % by weight; The structural unit of ether type (methyl) the acrylate A-2 represented from formula (II) is 7 ~ 25 % by weight; And be 0.5 ~ 3 % by weight from the structural unit of the unsaturated monomer A-3 with polar functional group.
The acryl resin A that the present invention uses can comprise from (methyl) acrylate of formula described above (I), ether type (methyl) acrylate of formula (II) and the structural unit containing the monomer beyond the unsaturated monomer of polar functional group.As their example, can enumerate: from have in molecule the structural unit of (methyl) acrylate of ester ring type structure, the structural unit from styrenic monomers, the structural unit from vinyl 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 about 5 ~ 7.As the concrete example of acrylate with ester ring type structure, can enumerate: isobornyl acrylate, cyclohexyl acrylate, acrylic acid two ring pentyl ester, acrylic acid cyclo-dodecyl ester, acrylic methyl cyclohexyl, acrylic acid 3-methyl cyclohexanol ester, t-butylcyclohexyl ester, α-ethoxy-c olefin(e) acid cyclohexyl, acrylate base phenyl ester etc., as the concrete example of methacrylate with ester ring type structure, can enumerate: isobornyl methacrylate, cyclohexyl methacrylate, methacrylic acid two ring pentyl ester, methacrylic acid cyclo-dodecyl ester, the own ester of trimethyl cyclohexyl methacrylate, methacrylic acid 3-methyl cyclohexanol ester, t-butyl cyclohexyl ester, methacrylic acid cyclohexyl phenyl ester etc.
As the example of styrenic monomers, except styrene, can also enumerate: the ring-alkylated styrenes of methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl 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 vinyl 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 and bromine ethene and so on; The vinylidene halides 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, there is in the molecule of 6-hexanediol two (methyl) acrylate, 1,9-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 the monomer of 2 (methyl) acryloyl groups; There is in the molecule of trimethylolpropane tris (methyl) acrylate and so on the monomer etc. of 3 (methyl) acryloyl groups.
(methyl) acrylate of formula (I), ether type (methyl) acrylate of formula (II) and there is polar functional group unsaturated monomer beyond monomer can individually use, also can combinationally use two or more.In the acryl resin A that bonding agent uses, from (methyl) acrylate of formula (I), ether type (methyl) acrylate of formula (II) and there is polar functional group monomer beyond the structural unit of monomer, being generally 0 ~ 20 weight portion relative to nonvolatile component 100 weight portion of described resin, being preferably the ratio of 0 ~ 10 weight portion and containing.
The effective constituent of bonding agent can comprise two or more and contain from (methyl) acrylate of formula as above (I), ether type (methyl) acrylate of formula (II) and the acryl resin of structural unit of monomer with polar functional group.And then, in aforesaid propylene acid resin, the acryl resin different from it can be mixed, specifically, such as, can mix the structural unit that has from (methyl) acrylate of formula (I) and acryl resin etc. not containing polar functional group.Be major component with the structural unit of (methyl) acrylate from formula (I) and comprise the acryl resin of the structural unit from the monomer with polar functional group, be preferably more than 60 % by weight and then preferably more than 80 % by weight in whole acryl resin.
As the acryl resin of the multipolymer obtained by (methyl) acrylate of contained (I), ether type (methyl) acrylate of formula (II) and the monomer mixture of monomer with polar functional group, the weight-average molecular weight (Mw) converted with polystyrene standard being preferably based on that gel permeation chromatography (GPC) measures is in the scope of 1,000,000 ~ 2,000,000.When the weight-average molecular weight converted with polystyrene standard is more than 1,000,000, because the cementability under hot and humid increases, the possibility heaved between glass substrate and adhesive phase and peel off has the tendency of reduction, and the tendency that re-workability is improved, thus preferably.In addition, when this weight-average molecular weight is less than 2,000,000, even if the size being pasted on the blooming of described adhesive phase changes, adhesive phase also can not be followed its change in size and change, therefore, there is no difference between the brightness of the edge part of liquid crystal cells and the brightness of central part, have the tendency suppressing whiting and color spot, thus preferably.The molecular weight distribution shown in ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is usually in the scope of about 2 ~ 10.
In addition, in order to present cohesive, aforesaid propylene acid resin A its glass temperature preferred is in the scope of-10 ~-60 DEG C.The glass temperature of resin can utilize differential scanning calorimeter to measure usually.
This acryl resin can be only made up of the resin that molecular weight as above is higher, also can be made up of the potpourri of aforesaid propylene acid resin and the acryl resin different from it.As acryl resin that can be used in combination, such as, can enumerate: to be major component and the acryl resin of weight-average molecular weight in the scope of 50,000 ~ 300,000 from the structural unit of (methyl) acrylate shown in above-mentioned formula (I).
Acryl resin (being the potpourri of the two when combining two or more), solution when to be preferably dissolved in ethyl acetate the concentration making nonvolatile component be 20 % by weight shows the viscosity of below 20Pas and then 0.1 ~ 7Pas at 25 DEG C.When viscosity is now below 20Pas, because the cementability under hot and humid increases, between glass substrate and adhesive phase, produce the tendency that the possibility heaved and peel off has reduction, and the tendency that re-workability is improved, thus preferably.Viscosity can utilize rich power to fly (Brookfield) viscosity meter and measure.
The acryl resin forming adhesive phase can utilize the known various methods such as such as solution polymerization process, emulsion polymerization, mass polymerization, suspension polymerization to manufacture.In the manufacture of this acryl resin, usually use polymerization initiator.About the use amount of polymerization initiator is 0.001 ~ 5 weight portion relative to total 100 weight portion of the whole monomers used in the manufacture of acryl resin.
As polymerization initiator, use thermal polymerization and Photoepolymerizationinitiater initiater etc.As Photoepolymerizationinitiater initiater, such as, can enumerate: 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc.As thermal polymerization, such as can enumerate: 2,2 '-azobis isobutyronitrile, 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 of 2 '-azo two (2-hydroxymethyl propionitrile) and so on; Lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, peroxidized t-butyl perbenzoate, cumene hydroperoxide hydrogen, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, new peroxide tert-butyl caprate, tert-Butyl peroxypivalate, (3,5,5-trimethyl acetyl base) organic peroxide of superoxide and so on; The inorganic peroxide etc. of potassium persulfate, ammonium persulfate, hydrogen peroxide and so on.In addition, and also can be used as polymerization initiator with the redox series initiators etc. of superoxide and reductive agent.
As the manufacture method of acryl resin, the solution polymerization process preferably in above shown method.When the concrete example enumerating solution polymerization process is described, can enumerate: by desired monomer and organic solvent mixing, and under nitrogen atmosphere, add thermal polymerization, at the temperature of about 40 ~ 90 DEG C, preferably about 60 ~ 80 DEG C, stir the method etc. of 3 ~ 10 hours.In addition, in order to control reaction, add monomer or thermal polymerization serially or off and in the course of the polymerization process, or add monomer or thermal polymerization with the state being dissolved in organic solvent.At this, as organic solvent, can use such as: 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 etc. of acetone, methyl ethyl ketone, methyl isobutyl ketone and so on.
[ionic compound B]
In the present invention, except using above-described acryl resin A, be that the ionic compound B of solid is as antistatic agent under being also used in room temperature (25 DEG C).Described ionic compound B has organic cation.In this manual, sometimes also by this at room temperature for the ionic compound of solid is called ionic solid.
As long as the cation constituent forming ionic compound B is meet the organic cation forming ionic solid, be not particularly limited in addition.Can enumerate: such as glyoxaline cation, pyridylium, ammonium cation, sulfonium cation, phosphonium cation etc., during adhesive phase for blooming, not easily charged when peeling off from the viewpoint of the stripping film that will arrange thereon, preferred pyridylium and glyoxaline cation.
On the other hand, in ionic compound B, being just not particularly limited as long as the anion component becoming the counter ion counterionsl gegenions of above-mentioned cation constituent meets the condition forming ionic solid, can be inorganic anion, also can be organic anion, such as, can enumerate following ion.
Cl anion (Cl -),
Bromine anions (Br -),
Iodine negative ion (I -),
Tetrachloro aluminic acid negative ion (AlCl 4 -),
Heptachlor dichloro 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 anions (NO 3 -),
Acetate anion (CH 3cOO -),
Trifluoracetic acid negative ion (CF 3cOO -),
Methane sulfonate anions (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) imide anion ((CF 3sO 2) 2n -),
Three (trifluoromethane sulfonyl group) methane anion ((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 hypophosphorous acid negative ion ((CH 3) 2pOO -),
(gathering) hydrofluorite fluoride anion (F (HF) n -) (n is about 1 ~ 3),
Dicyanamide anion (dca) ((CN) 2n -),
Sulphur cyanogen negative ion (SCN -),
Perfluorobutane negative ion (C 4f 9sO 3 -),
Two (pentafluoroethane sulfonyl) imide anion ((C 2f 5sO 2) 2n -),
Perfluorobutyric acid negative ion (C 3f 7cOO -),
(trifluoromethane sulfonyl group) (fluoroform carbonyl) imide anion ((CF 3sO 2) (CF 3cO) N -) etc.
Wherein, the anion component containing fluorine atom considers it is preferably use from the ionic solid that can obtain antistatic property excellence, particularly preferably hexafluorophosphoric acid negative ion or two (trifluoromethane sulfonyl group) imide anion.
The concrete example of the ionic solid that the present invention uses suitably can 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, following compound can be enumerated.
N-hexyl pyridine hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-butyl-4-picoline hexafluorophosphate,
N-octyl group-4-picoline hexafluorophosphate,
N-butyl-N-crassitude hexafluorophosphate,
1-ethyl-3-methylimidazole hexafluorophosphate,
1-ethyl-3-methylimidazole tosilate,
1-butyl-3-methylimidazole methane sulfonates,
TBuA hexafluorophosphate,
TBuA tosilate,
Two (trifluoromethane sulfonyl group) acid imide of tributyl-methyl phosphonium ammonium,
(2-hydroxyethyl) trimethyl ammonium dimethyl phosphite etc.
Ionic solid like this can individually use, and also can combine two or more and use.The example of ionic solid is not limited to the above material enumerated.
Be the ionic compound B of solid under room temperature, as mentioned above, giving antistatic behaviour to the adhesive phase that formed by the composition comprising acryl resin A and keeping as being effective in the various physical property of bonding agent.Compared with the situation being particularly the ionic compound of liquid at normal temperatures with use, antistatic property can be kept for a long time.From the viewpoint of the long-time stability of such antistatic behaviour, ionic compound B preferably has the fusing point of more than 30 DEG C and then more than 35 DEG C.On the other hand, when its fusing point is too high, be deteriorated with the intermiscibility of acryl resin A, therefore, preferably there is the fusing point of less than 90 DEG C and then less than 80 DEG C.There is no particular limitation for the molecular weight of ionic compound B, and such as preferred molecular weight is less than 700 and then is preferably less than 500.
Ionic compound B is contained with the ratio being 0.3 ~ 12 weight portion relative to nonvolatile component 100 weight portion of aforesaid propylene acid resin A.Relative to nonvolatile component 100 weight portion of acryl resin A, containing more than ionic compound B0.3 weight portion time, antistatic property improve, thus preferably.In addition, when its amount is below 12 weight portions, easily permanance is kept, thus preferably.Relative to nonvolatile component 100 weight portion of acryl resin A, the amount of ionic compound B is preferably more than 0.5 weight portion and below 5 weight portions.
[crosslinking chemical C]
In above-described acryl resin A and ionic compound B, coordinate crosslinking chemical C to make adhesive composition further.Crosslinking chemical C be have in molecule at least 2 can with the compound of the functional group be particularly cross-linked from the structural unit of the unsaturated monomer A-3 with polar functional group in acryl resin A, specifically can illustrate: isocyanates based compound, epoxy compound, metal complex based compound, aziridine based compound etc.
Isocyanates based compound is the compound in molecule with at least 2 isocyanate bases (-NCO), such as, can enumerate: toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate, hydrogenated xylene diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate etc.In addition, the adduct making these isocyanate compounds and the polyol reaction such as glycerine or trimethylolpropane obtain and the dimer, tripolymer etc. of isocyanate compound also can be used as the crosslinking chemical of bonding agent.Two or more isocyanates based compound can also be mixed use.
Epoxy compound is the compound in molecule with at least 2 epoxy radicals, such as can enumerate: bisphenol A type epoxy resin, ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl base 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 epoxy compound can be mixed with two or more.
As metal complex compounds, such as, can enumerate: the compound etc. of coordination diacetone or ethyl acetoacetate on the polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium.
Aziridine based compound is also referred to as aziridine (ethylene imine), it is the compound in molecule with 3 membered ring skeleton that at least 2 are made up of 1 nitrogen-atoms and 2 carbon atoms, such as can enumerate: diphenyl methane-4, 4 '-bis-(1-aziridine formamide), Toluene-2,4-diisocyanate, 4-two (1-aziridine formamide), triethylenemelanin, between the two-1-(2-methylaziridine) of phenyl-diformyl, three-1-aziridine phosphine oxides, hexa-methylene-1, 6-two (1-aziridine acid amides), trimethylolpropane-three-β-'-aziridino propionic ester, tetramethylol methane-three-β-'-aziridino propionic ester etc.
In these crosslinking chemicals, preferably use isocyanates based compound, particularly Xylene Diisocyanate, toluene diisocyanate or hexamethylene diisocyanate; Or the adduct of these isocyanate compounds and the polyol reaction such as glycerine or trimethylolpropane gained; The dimer, tripolymer etc. of isocyanate compound; The potpourri etc. of these isocyanates based compounds.Containing the unsaturated monomer A-3 of polar functional group when having the polar functional group being selected from free carboxy, hydroxyl, amino and epoxide ring, particularly preferably at least one crosslinking chemical C uses 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; And 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, to be that the ratio of 0.1 ~ 5 weight portion coordinates relative to acryl resin A 100 weight portion, is preferably the ratio about 0.2 ~ 3 weight portion.When being more than 0.1 weight portion relative to the amount of the crosslinking chemical C of acryl resin A 100 weight portion, the permanance of adhesive phase is tended to improve, therefore preferably, in addition, when being below 5 weight portions, whitening when the blooming of band bonding agent is applied to liquid crystal indicator and become not obvious, therefore preferably.
[forming other composition of adhesive composition]
Of the present invention for the formation of in the adhesive composition of adhesive phase, in order to improve the adaptation between adhesive phase and glass substrate, preferably containing silane based compound (D), contain silane based compound (D) particularly preferably in the acryl resin coordinated before crosslinking chemical.
As silane based compound (D), can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl group dimethoxymethylsilane, 3-glycidoxypropyl group ethoxy dimethylsilane etc.Two or more silane based compound (D) can be used.
Silane based compound (D) can be the silane based compound of silicone oligomers type.When representing silicone oligomers by the form of multipolymer, such as following compound can be enumerated.
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-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl-tetraethoxy-silicane alkyl copolymer,
3-methacryloyloxypropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-methacryloyloxypropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-methacryloyloxypropyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing methacryloxypropyl of 3-methacryloyloxypropyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer and so on;
3-acryloxypropyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,
3-acryloxypropyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,
3-acryloxypropyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-acryloxypropyl triethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-acryloxypropyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-acryloxypropyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-acryloxypropyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing acryloxypropyl of 3-acryloxypropyl diethoxy silane-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 methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing vinyl of vinyl methyl diethoxy silane-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-amino propyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-amino propyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-amino propyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The multipolymer etc. containing amino of 3-amino propyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer and so on.
These silane based compounds (D) are in most cases liquid.The use level of the silane based compound in adhesive composition is relative to nonvolatile component 100 weight portion (being that it adds up to weight under using situation of more than two kinds) of acryl resin A, about being generally 0.01 ~ 10 weight portion, be preferably 0.03 ~ 1 weight portion.When being more than more than 0.01 weight portion, especially 0.03 weight portion relative to the amount of the silane based compound of nonvolatile component 100 weight portion of acryl resin, the adaptation of adhesive phase and glass substrate can be improved, therefore preferably.In addition, when its amount is below below 10 weight portions, especially 1 weight portion, the tendency suppressing silane based compound to ooze out from adhesive phase is had, therefore preferably.
The resin etc. beyond crosslinking catalyst, weathering stabilizers, tackifier, plastifier, softening agent, dyestuff, pigment, inorganic filler, acryl resin A can be coordinated further in adhesive composition described above.In addition, combined with ultraviolet radiation curability compound in adhesive composition, and after being formed in adhesive phase, irradiation ultraviolet radiation makes it solidify and make harder adhesive phase is also effective.Wherein, if coordinate crosslinking chemical and crosslinking catalyst in adhesive composition simultaneously, then adhesive phase can be prepared by the slaking of short time, and produce between resin molding and adhesive phase in can suppressing obtained band adhesive resin film and heave or peel off or foam in adhesive phase, re-workability is also better sometimes.As crosslinking catalyst, can enumerate such as: the aminated compounds etc. of hexamethylene diamine, ethylenediamine, polyethyleneimine, hexamethylene tetramine, diethylene triamine, trien, isophorone diamine, trimethylene diamine, poly-amino resins, melamine resin and so on.When coordinating the aminated compounds as crosslinking catalyst in adhesive composition, as crosslinking chemical, preferred isocyanate compounds.
Form above-mentioned each composition of adhesive composition to be coated under the state being dissolved in solvent on suitable base material and to make it dry, and make adhesive phase.
[blooming of band bonding agent]
The blooming of band bonding agent of the present invention is provided with at least one side of blooming the adhesive phase formed by adhesive composition as above.Blooming used herein is the film with optical characteristics, such as, can enumerate polarization plates, phase retardation film etc.
So-called polarization plates, for having the blooming sending polarized light function relative to incident lights such as natural lights.Polarization plates comprises: linear polarization plate, and it has the feature absorbing and have the linearly polarized photon of the vibration plane in certain direction and the perpendicular linearly polarized photon of transmission vibration plane; Polarized light separation membrane, it has reflection and has the linearly polarized photon of the vibration plane in certain direction, and the feature of the perpendicular linearly polarized photon of transmission vibration plane; With elliptic polarization plate, polarization plates and following phase retardation film are laminated.As the preferred concrete example of polarization plates, particularly linear polarization plate (sometimes referred to as polaroid or polarizer membrane), can be set forth in gas absorption quantity in the polyvinyl alcohol resin film of uniaxial tension has the polarization plates of the dichromatism such as iodine or dichroic dye pigment.
So-called phase retardation film refers to the anisotropic blooming of display optical, such as, can enumerate: by the polymeric membrane formed by 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 to about 1.01 ~ 6 times and the stretched film etc. that obtains.Wherein, the polymeric membrane of preferred uniaxial tension or biaxial stretch-formed polycarbonate membrane or cyclic polyolefin mesentery.Also the film being referred to as uniaxial retardation film, wide viewing angle phase retardation film, low modulus of photoelasticity phase retardation film etc. is had, all applicable.
In addition, utilize the coating of liquid crystal compounds, orientation to present optically anisotropic film or to utilize the coating of inorganic layered compounds also can be used as phase retardation film to present optically anisotropic film.This phase retardation film have be referred to as temperature compensating type phase retardation film by Shin Nihon Oil Co., Ltd with the film of the rod shaped liquid crystal twisted-oriented of the sold of " LC film ", same by Shin Nihon Oil Co., Ltd with the film of the rod shaped liquid crystal tilted alignment of the sold of " NH film ", the film become with the disc-like liquid crystal tilted alignment of the sold of " WV film " by Fuji Photo Film Co., Ltd., by Sumitomo Chemical Co with the film of the complete biaxially oriented version of the sold of " VAC film ", same by Sumitomo Chemical Co with the film etc. of the biaxially oriented version of the sold of " newVAC film ".
And then the film being pasted with diaphragm on these bloomings also can be used as blooming.As diaphragm; adopt transparent resin molding; as this transparent resin, such as, can enumerate with Triafol T or the cellulose diacetate acetate fiber prime system resin that is representative, take polymethylmethacrylate as the methacrylic resin, vibrin, polyolefin-based resins, polycarbonate resin, polyether-ether-ketone resin, polysulfone resin etc. of representative.The ultraviolet light absorbers such as salicylate based compound, benzophenone based compound, benzotriazole based compound, triazine based compound, acrylic acid cyano group ester based compound, nickel complex salt compounds can be coordinated in the resin forming diaphragm.As diaphragm, preferably use the cellulose acetate resin films such as three cellulose acetate membrane.
In blooming described above, linear polarization plate uses mainly with the state being pasted with diaphragm at the polaroid forming linear polarization plate, the one or both sides of polarizer membrane that are such as made up of polyvinyl alcohol resin greatly.In addition, the polarization plates of the above-mentioned elliptic polarization plate linear polarization plate that has been stacked and phase retardation film, the one or both sides that this polarization plates is also in polarizer membrane have mostly pasted the state of diaphragm.When forming adhesive phase of the present invention on this elliptic polarization plate, usually form adhesive phase in its phase retardation film side.
Blooming with bonding agent preferably at the surface mount stripping film of its adhesive phase, until for the protection of the surface of adhesive phase before using.The blooming being provided with the band bonding agent of stripping film like this can be manufactured by such as 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 obtained; On blooming, coating adhesive composition forms adhesive phase, stripping film protection of then fitting on its bonding agent face, thus obtains the method etc. of the blooming being with bonding agent.Stripping film used herein such as can for using the film be made up of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylates as base material, then to this base material and the composition surface of adhesive phase implement the demoulding process of silicone-treated and so on and the film etc. that obtains.
The thickness of adhesive phase is not particularly limited, and is preferably generally less than 30 μm, is also preferably more than 10 μm, is more preferably 10 ~ 20 μm.When the thickness of adhesive phase is below 30 μm, cementability under hot and humid improves, between glass substrate and adhesive phase, produce the possibility heaved or peel off tend to step-down, and re-workability tends to improve, thus preferred, in addition, when its thickness is more than 10 μm, even if the size of pasting blooming thereon changes, bonding coat also can change along with this change in size, therefore, does not have difference between the brightness of the edge part of liquid crystal cells and the brightness of central part, there is the tendency suppressing whiting or color spot, therefore preferably.At present, the Standard General being pasted on the thickness of the adhesive phase of liquid crystal cells glass is 25 μm, in the present invention, even if this thickness is set as less than 20 μm, also can play the performance as adhesive phase fully.
The blooming of band bonding agent of the present invention is pasted on glass substrate and after forming optical laminate, exist any imappropriate and this blooming is peeled off from glass substrate time, adhesive phase is stripped with blooming, stain or cull etc. is produced hardly on the surface of the glass substrate connected with adhesive phase, therefore, the blooming of adhesive band bonding agent again again on the glass substrate easily after stripping.That is, so-called re-workability is excellent.
[optical laminate]
The blooming of band bonding agent of the present invention is laminated on glass substrate with its adhesive phase, can be made into optical laminate.When making optical laminate the blooming of band bonding agent is laminated in glass substrate, such as, as long as peel stripping film from the blooming of band bonding agent obtained above, the adhesive phase exposed is bonded in the surface of glass substrate.At this, as glass substrate, such as, can enumerate: the glass substrate of liquid crystal cells, anti-dazzle glass, sunglasses glass etc.Wherein, the blooming (upper deflection board) of laminated belt bonding agent on the glass substrate of the front face side (identification side) of liquid crystal cells, on the glass substrate of the rear side of liquid crystal cells, the optical laminate of the blooming (lower polarizing plate) of other band bonding agent stacked can be used as the panel (liquid crystal panel) of liquid crystal indicator again, thus preferably.As the material of glass substrate, such as, 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 layer is 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 is pasted onto a face of linear polarization membrane 1 with the face being in opposition side with described surface-treated layer 2, forms polarization plates 5.In this embodiment, polarization plates 5 becomes the blooming 10 described in the present invention simultaneously.The face being in opposition side with diaphragm 3 of linear polarization membrane 1 arranges the above-mentioned adhesive phase 20 comprising ionic compound, forms the blooming 25 of band bonding agent.And, the face being in opposition side with polarization plates 5 of described adhesive phase 20 is pasted onto as on the liquid crystal cells 30 of glass substrate, forms optical laminate 40.
In the example shown in Fig. 1 (B); first diaphragm 3 with surface-treated layer 2 is pasted onto a face of linear polarization membrane 1 with the face being in opposition side with described surface-treated layer 2; the another side of linear polarization membrane 1 is pasted the second diaphragm 4, forms polarization plates 5.In this embodiment, polarization plates 5 becomes the blooming 10 described in the present invention simultaneously.At the arranged outside adhesive phase 20 comprising ionic compound described above of the second diaphragm 4 of formation polarization plates 5, form the blooming 25 of band bonding agent.And, the face being in opposition side with polarization plates 5 of described adhesive phase 20 is pasted onto as on the liquid crystal cells 30 of glass substrate, forms optical laminate 40.
In the example shown in Fig. 1 (C), the diaphragm 3 with surface-treated layer 2 is pasted onto a face of linear polarization membrane 1 with the face being in opposition side with described surface-treated layer 2, forms polarization plates 5.Be on the face of opposition side at linear polarization membrane 1 with diaphragm 3, paste phase retardation film 7 via interlayer adhesive 8, form blooming 10.At the arranged outside adhesive phase 20 comprising ionic compound described above of the phase retardation film 7 of formation blooming 10, form the blooming 25 of band bonding agent.And, the face being in opposition side with blooming 10 of described adhesive phase 20 is pasted onto as on the liquid crystal cells 30 of glass substrate, forms optical laminate 40.
In addition; in the example shown in Fig. 1 (D); first diaphragm 3 with surface-treated layer 2 is pasted onto a face of linear polarization membrane 1 with the face being in opposition side with described surface-treated layer 2, pastes the second diaphragm 4 at the another side of linear polarization membrane 1, form polarization plates 5.Paste phase retardation film 7 in the outside of the second diaphragm 4 forming polarization plates 5 via interlayer adhesive 8, form blooming 10.At the arranged outside adhesive phase 20 comprising ionic compound described above of the phase retardation film 7 of formation blooming 10, form the blooming 25 of band bonding agent.And, the face being in opposition side with blooming 10 of described adhesive phase 20 is pasted onto as on the liquid crystal cells 30 of glass substrate, forms optical laminate 40.
In these examples, usually, 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 film.In addition, the surface-treated layer being formed at the surface of the first diaphragm 3 can be excellent coating, antiglare layer, anti-reflection layer, antistatic layer etc.These layers multiple also can be set.
Example as shown in Fig. 1 (C) and (D), in polarization plates 5 during stacked phase retardation film 7, if be middle-size and small-size liquid crystal indicator, then as the preferred example of this phase retardation film 7, can enumerate 1/4 wavelength plate.In this situation, usually, show greatly 45 degree of modes of reporting to the leadship after accomplishing a task using the absorption axle of polarization plates 5 with the slow axis as the phase retardation film 7 of 1/4 wavelength plate and be configured, but also its angle can be made to depart from 45 degree to a certain extent according to the characteristic of liquid crystal cells 30.On the other hand, if be the large-scale liquid crystal indicators such as televisor, then for the purpose of the phase difference compensation of liquid crystal cells 30 and viewing angle compensation, the characteristic according to this liquid crystal cells 30 uses the phase retardation film with various phase difference value.In this situation, usually, be configured in the mode that the absorption axle of polarization plates 5 is substantially vertical or almost parallel with the slow axis of phase retardation film 7.When forming phase retardation film 7 by 1/4 wavelength plate, preferably use the stretched film of single shaft or twin shaft.In addition, when for the purpose of the phase difference compensation of liquid crystal cells 30 and viewing angle compensation, phase retardation film 7 is set, except single shaft or biaxially-stretched film, can also be used in the film of through-thickness orientation on single shaft or biaxial stretch-formed basis, on support membrane, coating of liquid crystalline equiphase difference finds material the film etc. that its orientation is fixed is called as the film of optical compensation films as phase retardation film 7.
Equally, example as shown in Fig. 1 (C) and (D), when pasting polarization plates 5 and phase retardation film 7 by interlayer adhesive 8, described interlayer adhesive 8 also can the such antistatic agent of collaboration ionic compound described above and be endowed the bonding agent of antistatic behaviour, usually antistatic behaviour is expected not too much in this part, therefore, usual use does not comprise the general acrylic adhesive of antistatic agent.In addition, large-scale liquid crystal indicator is as previously discussed such, when being configured in the mode that the absorption axle of polarization plates 5 is substantially vertical or almost parallel with the slow axis of phase retardation film 7, polarization plates 5 and phase retardation film 7 volume to volume can be pasted, in the purposes not requiring releasable between the two, also can replace Fig. 1 (C) and the interlayer adhesive shown in (D) 8, use once will engage securely after bonding and the bonding agent that can not peel off.As such bonding agent, such as, can enumerate: the water system bonding agent presenting bonding force by making aqueous solvent evaporate be made up of aqueous solution or aqueous dispersions, being cured by irradiation ultraviolet radiation and presenting the ultraviolet hardening bonding agent etc. of bonding force.
It should be noted that, Fig. 1 (C) and the material itself being formed with the adhesive phase 20 containing ionic compound on phase retardation film 7 shown in (D) also can self circulations, and as the blooming of the band bonding agent described in the present invention.The blooming that phase retardation film defines the band bonding agent of the adhesive phase containing ionic compound is made except optical laminate except its adhesive phase being pasted onto on the liquid crystal cells of glass substrate, can also paste the blooming that polarization plates makes other band bonding agent in its phase retardation film side.
Exemplified with supposition, the blooming 25 of band bonding agent is configured in the example of the situation of the identification side of liquid crystal cells 30 in Fig. 1, but the blooming of band bonding agent of the present invention also can be configured in rear side, i.e. the backlight side of liquid crystal cells.When the blooming of band bonding agent of the present invention is configured in the rear side of liquid crystal cells; the diaphragm 3 with surface-treated layer 2 shown in Fig. 1 can be replaced; adopt the diaphragm without surface-treated layer, all the other are formed in the same manner as (A) ~ (D) of Fig. 1.In addition, in this situation, also can at the known various bloomings that can be configured in the rear side of liquid crystal cells such as arranged outside brightness improving film, condensing film, diffusion barrier of the diaphragm of formation polarization plates.
As described above, optical laminate of the present invention can be preferred for liquid crystal indicator.The liquid crystal indicator formed by optical laminate of the present invention may be used for comprising the PC liquid crystal display, televisor, vehicle display, e-dictionary, digital camera, digital camera, electronic desktop computer, clock and watch etc. of such as notebook type, desk-top, PDA (Personal Digital Assistance) etc.
Embodiment
Below, enumerate embodiment and specifically describe the present invention further, but the present invention does not limit by these examples.In example, representing " part " and " % " of use amount or content, unless otherwise specified, is just weight basis.
In the following examples, nonvolatile component is the value measured by the method based on JIS K 5407.Specifically, get the binder solution of any weight in glass dish, in explosion-proof baking oven, at 115 DEG C after dry 2 hours, residual nonvolatile component weight is the value of nonvolatile component relative to the ratio of the weight of the solution recorded at first.In addition, being determined as follows of weight-average molecular weight is carried out, " GPC KF-802 " that " TSK gel XL ", 1 Shodex (Co., Ltd.) that the 4 eastern Cao (Co., Ltd.) connected in GPC device are made are made amounts to 5 as chromatographic column, use tetrahydrofuran as eluent, be under the condition of 5mg/ml, sample size 100 μ l, temperature 40 DEG C, flow velocity 1ml/ minute at sample solution concentration, utilize polystyrene standard to convert and carry out.
First, the acryl resin manufactured as the major component of adhesive composition be shown and meet the resin of regulation of the present invention and do not meet the example of resin of regulation of the present invention.
[polymerization example 1]
Possessing cooling tube, nitrogen ingress pipe, temperature take into account in the reaction vessel of stirring machine add ethyl acetate 81.8 parts, the butyl acrylate 88.6 parts as A-1, the acrylic acid 2-methoxy acrylate 10 parts as A-2, as the acrylic acid 2-hydroxy methacrylate 1.0 parts of A-3 and the mixed solution of 0.4 part, acrylic acid, its oxygen-free gas is made with the air in nitrogen replaceable equipment, meanwhile, by interior temperature rise to 55 DEG C.Thereafter, add azobis isobutyronitrile (polymerization initiator) 0.14 part is dissolved in the complete soln obtained in ethyl acetate 10 parts.Add initiating agent after 1 hour, with do not comprise the concentration of the acryl resin of monomer be 35% mode, be that ethyl acetate is added in reaction vessel by 17.3 parts/hr continuously to add speed, simultaneously, 12 hours are incubated at interior temperature 54 ~ 56 DEG C, finally add ethyl acetate, carry out regulating and make the concentration of acryl resin be 20%.The weight-average molecular weight Mw of the polystyrene conversion that the acryl resin obtained utilizes GPC to measure is 1,750,000, Mw/Mn is 4.9.It can be used as acryl resin A.The structural unit derived from as the acrylic acid 2-hydroxy methacrylate of hydroxyl monomer in acryl resin A is 1%, in addition, is 0.4% from the acrylic acid structural unit as carboxyl group-containing monomer.
[polymerization example 2]
Except butyl acrylate during monomer is formed quantitative change more 78.6 parts, by except the quantitative change of acrylic acid 2-methoxy acrylate more 20 parts, example 1 is same operates with polymerization, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of the polystyrene conversion utilizing GPC to measure of the acryl resin obtained is 1,660,000, Mw/Mn is 4.4.It can be used as acryl resin B.The structural unit from the acrylic acid 2-hydroxy methacrylate as hydroxyl monomer in acryl resin B is 1%, in addition, is 0.4% from the acrylic acid structural unit as carboxyl group-containing monomer.
[polymerization example 3]
Except butyl acrylate during monomer is formed quantitative change more 58.6 parts, by except the quantitative change of acrylic acid 2-methoxy acrylate more 40 parts, example 1 is same operates with polymerization, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of the polystyrene conversion utilizing GPC to measure of the acryl resin obtained is 1,580,000, Mw/Mn is 4.8.It can be used as acryl resin C.The structural unit from the acrylic acid 2-hydroxy methacrylate as hydroxyl monomer in acryl resin C is 1%, in addition, is 0.4% from the acrylic acid structural unit as carboxyl group-containing monomer.
[polymerization example 4]
Except the quantitative change more 93.6 parts of butyl acrylate in being formed by monomer, by the quantitative change of acrylic acid 2-methoxy acrylate more 5 parts and temperature retention time be set to except 18 hours, example 1 is same operates with polymerization, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of the polystyrene conversion utilizing GPC to measure of the acryl resin obtained is 1,680,000, Mw/Mn is 5.4.It can be used as acryl resin D.The structural unit from the acrylic acid 2-hydroxy methacrylate as hydroxyl monomer in acryl resin D is 1%, in addition, is 0.4% from the acrylic acid structural unit as carboxyl group-containing monomer.
[polymerization example 5]
Except the amount of butyl acrylate in being formed by monomer is set to 98.6 parts and does not use except acrylic acid 2-methoxy acrylate, example 1 is same operates with polymerization, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw of the polystyrene conversion utilizing GPC to measure of the acryl resin obtained is Isosorbide-5-Nitrae 70,000, Mw/Mn is 4.4.It can be used as Eudragit E.The structural unit from the acrylic acid 2-hydroxy methacrylate as hydroxyl monomer in Eudragit E is 1%, in addition, is 0.4% from the acrylic acid structural unit as carboxyl group-containing monomer.
The guide look of the monomer composition of polymerization example 1 ~ 5, weight-average molecular weight, Mw/Mn is shown in table 1.In table, BA refers to butyl acrylate, and MEA refers to acrylic acid 2-methoxy acrylate, and HEA refers to acrylic acid 2-hydroxy methacrylate, and AA refers to acrylic acid.
[table 1]
Then, illustrate that the above acryl resin manufactured of use is prepared adhesive composition and is applied to embodiment and the comparative example of blooming.In following example, as ionic compound, use following ionic compound 1 ~ 3.Following ionic compound 1 and 2 is solid under the room temperature of 25 DEG C, and ionic compound 3 is liquid under the room temperature of 25 DEG C.
Ionic compound 1 (solid): N-octyl group-4-picoline hexafluorophosphate (there is the structure of following formula, fusing point 44 DEG C)
Ionic compound 2 (solid): two (trifluoromethane sulfonyl group) acid imide (there is the structure of following formula, fusing point 28 DEG C) of tributyl-methyl phosphonium ammonium
Ionic compound 3 (liquid): N-hexyl-4-picoline hexafluorophosphate (there is the structure of following formula, fusing point 18 DEG C)
In addition, as crosslinking chemical and silane based compound, use following material (being trade name) respectively.
(crosslinking chemical)
CORONATE L: the ethyl acetate solution (solid component concentration 75%) of the trimethylolpropane adduct of toluene diisocyanate, to obtain from Japanese polyurethane Co., Ltd..
(silane based compound)
KBM-403: glycidoxypropyltrime,hoxysilane (liquid), to obtain from Shin-Etsu Chemial Co., Ltd.
[embodiment 1 ~ 4 and comparative example 1 ~ 2]
The manufacture of (a) adhesive composition
Relative to each 100 parts of the solid constituent of the acryl resin A ~ E obtained in polymerization example 1 ~ 5, each 3 parts of ionic compound respectively shown in mixture table 2, count the crosslinking chemical " CORONATE L " of 0.5 part and the silane based compound " KBM-403 " of 0.5 part with solid constituent, and then add ethyl acetate in the mode that solid component concentration is 13%, make adhesive composition.In ionic compound one hurdle of table 2, show the sequence number of above-mentioned ionic compound 1 ~ 3 and be at room temperature the situation of solid or liquid.
The making of the blooming of (b) band bonding agent
The polyethylene terephthalate film being used by above-mentioned each adhesive composition coater to be coated on demoulding process (trade name " PET 3811 ", to obtain from lintec (Co., Ltd.), be called separation layer (separator)) demoulding treated side on, dried thickness is made to be 20 μm, and at 90 DEG C dry 1 minute, obtain the bonding agent of sheet.Then; having on a face of the polarization plates of the 3-tier architecture on the two sides of the polyvinyl alcohol polarization sheet of iodine with the diaphragm clamping gas absorption quantity be made up of Triafol T; by lamination and sheet bonding agent obtained above of fitting with the face (bonding agent face) of separation layer opposition side after; slaking 7 days under the condition of temperature 23 DEG C, relative humidity 65%, obtains the polarization plates being with bonding agent.
The antistatic behaviour evaluation of the blooming of (c) band bonding agent
When the separation layer of obtained band bonding agent polarization plates is peeled off, measure the sheet resistance value of bonding agent with surperficial intrinsic resistance determinator [the Hirest-up MCP-HT450 (trade name) of Mitsubishi chemical Co., Ltd], evaluate antistatic behaviour.In IPS pattern, need to make sheet resistance value be 10 10Ω/ rank or its following rank, also require long-term this antistatic property of maintenance.The evaluation of antistatic behaviour is directly carried out after the slaking of band bonding agent polarization plates terminates.In addition, in order to observe rheological parameters' change with time during long-term preservation, the keeping in the baking oven of temperature 60 C, relative humidity 70% of the band bonding agent polarization plates after slaking being terminated, after 6 days, peels off separation layer as described above, measures the sheet resistance value of bonding agent.At this, the effect roughly the same with at room temperature taking care of 6 months within 6 days, can be obtained in temperature 60 C, relative humidity 70% time keeping.Show the result in table 2.
The making of (d) optical laminate and evaluation
After the polarization plates of the band bonding agent be made up of above-mentioned (b) peels separation layer, its bonding agent face is pasted on the one side of liquid crystal cells glass substrate [" 1737 " (trade name) of Corning Inc.], makes optical laminate.For each optical laminate, carry out the keeping heat resistant test (being designated as in table 2 " heat-resisting ") of 300 hours under the drying condition of temperature 80 DEG C respectively; Carry out in temperature 60 C, relative humidity 90% time keeping hot resistance test of 300 hours (being designated as in table 2 " wet-heat resisting "); And using be cooled to from the state being heated to 70 DEG C-30 DEG C, the process that is then warming up to 70 DEG C as 1 circulation (1 hour) time, repeat the heatproof impact test (being designated as in table 2 " resistance to HS ") of 100 these circulations, the situation of the optical laminate after visualization test.By result following benchmark classification, be summarized in table 2.
(metewand relative to the permanance (being designated as " heat-resisting ", " wet-heat resisting ", " resistance to HS " in table 2 respectively) of hot, damp and hot and thermal shock)
1: do not observe completely heave, peel off, the cosmetic variation such as foaming.
2: almost do not observe heave, peel off, the cosmetic variation such as foaming.
3: heave, peel off, the cosmetic variation such as foaming is remarkable a little.
4: see significantly heave, peel off, the cosmetic variation such as foaming.
The re-workability evaluation of the blooming of (e) band bonding agent
The evaluation of re-workability is carried out as follows.First, the polarization plates of the band bonding agent obtained in above-mentioned (b) is cut out the test film being slit into 25mm × 150mm size.Then, sticker (" Lamipacker " (trade name) that Fujipla (Co., Ltd.) makes) is used to be pasted onto on liquid crystal cells glass substrate with its binder side by this test film, and at 50 DEG C, 5kg/cm 2(490.3kPa) autoclave process in 20 minutes is carried out under.Then, carry out heating for 2 hours at 70 DEG C, then preserve in the baking oven of 50 DEG C after 48 hours, in the atmosphere of temperature 23 DEG C, relative humidity 50%, from this stickup test film, the speed that polarization plates is divided with 300mm/ is peeled off along 180 ° of directions, the state on sight glass plate surface, classifies according to following benchmark.Table 2 will be the results are shown in.
The metewand > of < re-workability
1: glass pane surface does not produce stain etc. completely.
2: glass pane surface does not almost produce stain etc.
3: glass pane surface produces stain etc.
4: glass pane surface produces the residual of bonding agent.
[table 2]
From table 1 and table 2, in the acryl resin that the present invention specifies, coordinate the ionic solid of ormal weight and form the embodiment 1 ~ 4 of adhesive composition, compared with coordinating the comparative example 2 of ionic liquid, almost identical antistatic behaviour is shown at the making initial stage, simultaneously, even if place antistatic behaviour long-time also almost constant, in addition, thermotolerance, humidity resistance and resistance to sudden heating also obtain roughly gratifying result.
Relative to this, not containing the comparative example 1 from the structural unit of ether type (methyl) acrylate of formula (II) in acryl resin, although obtain good result in thermotolerance, humidity resistance and resistance to sudden heating, show the result of initial stage antistatic property difference.Coordinate the comparative example 2 forming adhesive composition at 25 DEG C for N-hexyl-4-picoline hexafluorophosphate (ionic compound 3) of liquid, although show good antistatic behaviour at the making initial stage, but heat promote test and temperature 60 C, relative humidity 70% time preservation 6 days time, sheet resistance value after separation layer stripping and the value at initial stage are in a ratio of more than 10 times, have the tendency that antistatic behaviour is deteriorated because taking care of for a long time.
Embodiment of disclosure and embodiment in all respects all for illustration and be not limit.Scope of the present invention is not limited to above-mentioned explanation and by shown in the scope of claim, all changes with the scope of claim with the meaning and the scope be equal to include within the scope of the invention.
Utilizability in industry
The blooming of band bonding agent of the present invention is endowed high antistatic behaviour, and keeps this antistatic behaviour for a long time, and in addition, permanance is also excellent.The blooming of this band bonding agent is preferred for liquid crystal indicator.
Symbol description
1 linear polarization membrane, 2 surface-treated layers, 3 first diaphragms, 4 second diaphragms, 5 polarization plates, 7 phase retardation films, 8 interlayer adhesives, 10 bloomings, 20 comprise the adhesive phase of ionic compound, blooming, 30 liquid crystal cells (glass substrate), 40 optical laminates of 25 band bonding agents.

Claims (6)

1. an optical laminate, it is laminated in glass substrate by the blooming of band bonding agent with its adhesive phase side, and the blooming of described band bonding agent forms adhesive phase at least one face of blooming, wherein,
Described adhesive phase is formed by the adhesive composition containing the A of 100 weight portions and the D of the B of 0.3 ~ 12 weight portion, the C of 0.1 ~ 5 weight portion and 0.03 ~ 1 weight portion,
Described A is the acryl resin of the multipolymer obtained by the monomer mixture of the A-3 of A-2 and 0.1 ~ 5 % by weight of A-1, the 5-40 % by weight containing 55 ~ 94 % by weight,
Described B has organic cation and is at room temperature the ionic compound of solid,
Described C is crosslinking chemical,
Described D is silane based compound,
Described A-1 is (methyl) acrylate that following formula (I) represents,
In formula, R 1represent hydrogen atom or methyl, R 2represent that carbon number is alkyl or the aralkyl of 1 ~ 14,
Described A-2 is (methyl) acrylate of at least one be selected from acrylic acid 2-methoxy acrylate, acrylic acid 2-ethoxy ethyl ester, acrylic acid 2-methoxyl-2-ethoxy ethyl ester, methacrylic acid 2-methoxy acrylate, methacrylic acid 2-ethoxy ethyl ester and methacrylic acid 2-methoxyl-2-ethoxy ethyl ester
Described A-3 is the unsaturated monomer with polar functional group.
2. optical laminate as claimed in claim 1, wherein,
Described A-2 is acrylic acid 2-methoxy acrylate.
3. optical laminate as claimed in claim 1, wherein,
The described polar functional group with the unsaturated monomer A-3 of polar functional group is selected from free carboxy, hydroxyl, amino and epoxide ring.
4. optical laminate as claimed in claim 3, wherein,
Described crosslinking chemical C contains isocyanates based compound.
5. optical laminate as claimed in claim 1, wherein,
Described blooming is selected from polarization plates and phase retardation film.
6. optical laminate as claimed in claim 1, wherein,
Stripping film is had at the surface mount of adhesive phase.
CN200980131194.6A 2008-08-11 2009-08-07 Optical film with adhesive and optical laminate using same Active CN102119348B (en)

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