CN108300356A - Polarizing coating with adhesive phase and image display device - Google Patents

Polarizing coating with adhesive phase and image display device Download PDF

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Publication number
CN108300356A
CN108300356A CN201710864513.0A CN201710864513A CN108300356A CN 108300356 A CN108300356 A CN 108300356A CN 201710864513 A CN201710864513 A CN 201710864513A CN 108300356 A CN108300356 A CN 108300356A
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China
Prior art keywords
adhesive phase
methyl
weight
mentioned
polarizing coating
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CN201710864513.0A
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Chinese (zh)
Inventor
藤田昌邦
外山雄祐
森本有
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN108300356A publication Critical patent/CN108300356A/en
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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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic acid 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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

The present invention relates to a kind of polarizing coatings with adhesive phase, it is with adhesive phase and polarizing coating, described adhesive layer is fitted on the transparency conducting layer of transparent conductive base and is used, the transparent conductive base has transparency conducting layer over the transparent substrate, wherein, the adhesive composition for being used to form above-mentioned adhesive phase contains (methyl) acrylic polymer and the silane coupling agent containing mercapto.Even if the polarizing coating with adhesive phase of the present invention is in the case where fitting in the transparent conductive base over the transparent substrate with transparency conducting layer, it may have high-durability, the especially excellent in te pins of durability under humidified ambient, and operability is also excellent again.

Description

Polarizing coating with adhesive phase and image display device
Technical field
The present invention relates to the polarizing coating with adhesive phase with adhesive phase and polarizing coating, described adhesive fits in It is used on the transparency conducting layer of bright conductive substrate, the transparent conductive base has transparency conducting layer over the transparent substrate. Moreover, it relates to have the image display panel of transparent conductive base, the transparent conductive base has used above-mentioned Polarizing coating with adhesive phase.In addition, the present invention relates to the image display devices for including above-mentioned image display panel.
Background technology
Image display panel, for example, liquid crystal display panel for liquid crystal display device etc. usually the both sides of liquid crystal cells across Adhesive phase lamination has polarizing coating, the liquid crystal cells to be formed by the liquid crystal layer of a pair of of transparent substrate and configuration between them. High-durability is required to such adhesive phase, for example, being carried out usually as environmental accelerated test using heating and being added In wet equal endurance test, it is desirable that not generation cause in adhesive phase stripping, tilt a problem that.
Various researchs have been carried out to the adhesive composition of such optical applications, such as have proposed a kind of adhesive combination Object, though in the case where being positioned under high wet heat condition after pasting optical film, will not it is peeling-off, foaming (for example, Referring to patent document 1).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-242767 bulletins
Invention content
The subject that the invention solves
Tin indium oxide (ITO) has been used in the presence of being formed on the transparent substrate of liquid crystal cells for constituting liquid crystal display panel The device of the transparent conductive films such as film, the Organic Conductive Films for having used electric conductive polymer, what is contacted with the transparent conductive film is viscous Mixture layer is easy to happen stripping, tilting etc., has the tendency that durability reduction.Moreover, especially under humidified ambient, durability Decline notable.The adhesive phase formed by the adhesive composition of patent document 1 is poor to tin indium oxide (ITO) layer adaptation, makees For the adhesive composition for the liquid crystal display panel with transparency conducting layer, and it is insufficient.
In addition, the adaptation of the adhesive phase and transparency conducting layer that are designed in order to ensure heat resistance is high, then operates and (shell again From rework) when it some times happens that thickener residual, polarizing coating fracture.For above-mentioned adhesive phase, also require without as not The operability again of good situation.
Therefore, the object of the present invention is to provide it is a kind of by adhesive phase be set to polarizing coating with the inclined of adhesive phase Vibrating diaphragm, though the adhesive phase on fitting in transparent base with transparency conducting layer transparent conductive base in the case of, Also there is high-durability, the especially excellent in te pins of durability under humidified ambient, and operability is also excellent again.
In addition, the object of the present invention is to provide a kind of image display panel having transparent conductive base, this is transparent Conductive substrate has used the above-mentioned polarizing coating with adhesive phase.In addition, the present invention also aims to provide a kind of comprising upper State the image display device of image display panel.
Solution to the problem
Further investigation has been repeated in the present invention etc. to solve the above-mentioned problems, finally, it is found that the bonding of following bands The polarizing coating of oxidant layer, so as to complete the present invention.
That is, the present invention relates to a kind of polarizing coatings with adhesive phase, with adhesive phase and polarizing coating, described adhesive Layer, which fits on the transparency conducting layer of transparent conductive base, to be used, and the transparent conductive base has saturating over the transparent substrate Bright conductive layer, wherein
The adhesive composition for being used to form above-mentioned adhesive phase contains (methyl) acrylic polymer and contains mercapto Silane coupling agent.
It is preferred that the above-mentioned silane coupling agent containing mercapto is the silane coupling agent containing mercapto of oligomeric.
It is preferred that the above-mentioned silane coupling agent containing mercapto is in the molecule with 2 or more alkoxysilyls.
Preferably with respect to above-mentioned 100 parts by weight of (methyl) acrylic polymer, the above-mentioned silane coupling agent containing mercapto Use level be 0.01~3 parts by weight.
It is preferred that the mercaptan equivalent of the above-mentioned silane coupling agent containing mercapto is 700g/mol or less.
In addition, the present invention relates to a kind of image display panel, have：It the above-mentioned polarizing coating with adhesive phase and transparent leads Conductive substrate, above-mentioned transparent conductive base have transparency conducting layer over the transparent substrate, wherein
The adhesive phase of the above-mentioned polarizing coating with adhesive phase fits in the above-mentioned electrically conducting transparent of above-mentioned image display panel Layer.
In addition, the present invention relates to a kind of image display device, with above-mentioned image display panel.
The effect of invention
The adhesive composition of the adhesive phase in the polarizing coating with adhesive phase of the present invention is formed due to containing sulfur-bearing The silane coupling agent of alcohol radical, therefore, even if in the case where the adhesive phase fits in transparency conducting layer, it may have high durable Property, the especially excellent in te pins of durability under humidified ambient.In addition, the operability again of above-mentioned adhesive phase is good, can inhibit again Thickener residual, polarizing coating fracture when operation.So, the polarizing coating of the invention with adhesive phase can be taken into account to transparent The durability of conductive layer and again operability.In addition, in accordance with the invention it is possible to providing a kind of with the polarizing coating with adhesive phase Image display panel and image display device with the image display panel.
Description of the drawings
Fig. 1 is an implementation of the liquid crystal display panel of one of image display panel for being shown as to be used in the present invention The schematic cross sectional view of mode.
Symbol description
1 liquid crystal display panel
2 visible side transparent protective films
3 polarizers
4 liquid crystal cell side transparent protective films
5 adhesive phases
6 transparency conducting layers
7 transparent bases
8 liquid crystal layers
9 transparent bases
10 adhesive phases
11 liquid crystal cell side transparent protective films
12 polarizers
13 light source side transparent protective films
Specific implementation mode
1. adhesive composition
The adhesive composition of the present invention is used for the formation of adhesive phase, and above-mentioned adhesive phase fits in transparent conductivity base It is used on the transparency conducting layer of material, above-mentioned transparent conductive base has transparency conducting layer over the transparent substrate, which is characterized in that Above-mentioned adhesive composition contains (methyl) acrylic polymer and the silane coupling agent containing mercapto.Hereinafter, to the present invention The composition of adhesive composition illustrate.
(1) (methyl) acrylic polymer
The adhesive composition of the present invention contains (methyl) acrylic polymer and the silane coupling agent containing mercapto, excellent Choosing contains (methyl) acrylic polymer as principal component.Principal component mentioned here refers to contained in adhesive composition The most ingredient of content ratio in all solids ingredient, for example, referring in all solids ingredient contained by adhesive composition Shared ratio is more than the ingredient of 50 weight %, refers to further the ingredient that shared ratio is more than 70 weight %.
(methyl) acrylic polymer usually contain (methyl) alkyl acrylate as monomeric unit as it is main at Point.It should be noted that (methyl) acrylate refers to acrylate and/or methacrylate, (methyl) with the present invention Meaning is identical.
(methyl) alkyl acrylate of main framing as composition (methyl) acrylic polymer, can example go out straight chain (methyl) alkyl acrylate that the atomic number of alkyl carbon of shape or branched is 1~18.For example, as abovementioned alkyl, can enumerate Methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, amyl, hexyl, cyclohexyl, heptyl, 2- ethylhexyls, iso-octyl, nonyl Base, decyl, isodecyl, dodecyl, different myristyl, lauryl, tridecyl, pentadecyl, cetyl, heptadecane Base, octadecyl etc..They can be used alone or are applied in combination.As the average carbon atom number of these alkyl, preferably 3~ 9。
May be used also in addition to above-mentioned (methyl) alkyl acrylate as the monomer of composition (methyl) acrylic polymer To enumerate carboxyl group-containing monomer, hydroxyl monomer, amide-containing monomer, (methyl) acrylate etc. containing aromatic rings.
Carboxyl group-containing monomer is to contain carbonyl in its structure and contain the polymerisms such as (methyl) acryloyl group, vinyl not It is saturated the compound of double bond.As the concrete example of carboxyl group-containing monomer, it can be mentioned, for example：(methyl) acrylic acid, (methyl) acrylic acid Carboxyethyl, (methyl) acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, fumaric acid, butenoic acid etc..In above-mentioned carboxyl group-containing monomer, From the viewpoint of copolymerizable, price and adhesion characteristic, preferred acrylic acid.
Hydroxyl monomer be in its structure contain hydroxyl and include the polymerisms such as (methyl) acryloyl group, vinyl not It is saturated the compound of double bond.As the concrete example of hydroxyl monomer, it can be mentioned, for example：(methyl) acrylic acid 2- hydroxy methacrylates, (first Base) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) propylene (methyl) acrylic acid such as sour 8- hydroxyls monooctyl ester, (methyl) acrylic acid 10- hydroxyls last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric esters Hydroxyalkyl acrylate, acrylic acid (4- Hydroxymethyl-cyclo-hexyls) methyl esters etc..In above-mentioned hydroxyl monomer, from durability aspect, It is preferred that (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxybutyls, particularly preferred (methyl) acrylic acid 4- hydroxyls Butyl ester.
Amide-containing monomer is to contain amide groups in its structure and containing polymerizations such as (methyl) acryloyl group, vinyl The compound of property unsaturated double-bond.As the concrete example of amide-containing monomer, (methyl) acrylamide, N, N- dimethyl can be enumerated (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, n-isopropyl acrylamide, N- methyl (methyl) acryloyl Amine, N- butyl (methyl) acrylamide, N- hexyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- methylols- N- propyl (methyl) acrylamide, amino methyl (methyl) acrylamide, amino-ethyl (methyl) acrylamide, mercapto methyl The acrylamide monomers such as (methyl) acrylamide, mercaptoethyl (methyl) acrylamide；N- (methyl) acryloyl morpholine, N- The N- acryloyl group heterocyclic monomers such as (methyl) acryloylpiperidine, N- (methyl) acryloyl group pyrrolidines；N- ethenyl pyrrolidones Lactams monomers containing N- vinyl such as ketone, N- vinyl-Epsilon-caprolactams etc..Amide-containing monomer is meeting durability Aspect is preferred, and in amide-containing monomer, the lactams monomer containing N- vinyl is taking into account the durability to transparency conducting layer And operability aspect is particularly preferred again.
Above-mentioned (methyl) acrylate containing aromatic rings is to contain aromatic ring structure in its structure and contain (methyl) The compound of acryloyl group.As aromatic rings, phenyl ring, naphthalene nucleus or cyclohexyl biphenyl can be enumerated.(methyl) acrylic acid containing aromatic rings Ester can meet durability (especially to the durability of transparency conducting layer).
As the concrete example of (methyl) acrylate containing aromatic rings, it can be mentioned, for example：(methyl) benzyl acrylate, (methyl) phenyl acrylate, o-phenyl phenol (methyl) acrylate, (methyl) acrylic acid phenoxy group ester, (methyl) acrylic acid benzene Oxygroup ethyl ester, (methyl) acrylic acid phenoxy-propyl, phenoxy group diethylene glycol (methyl) acrylate, ethylene-oxide-modified nonyl Phenol (methyl) acrylate, ethylene-oxide-modified cresols (methyl) acrylate, phenolethylene oxide are modified (methyl) propylene Acid esters, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, (methyl) methoxyethyl benzyl ester, (methyl) acrylic acid benzyl chloride Base ester, (methyl) toluene toluene, polystyrene (methyl) acrylate etc. have (methyl) acrylate of phenyl ring；Hydroxyl second Base betanaphthol acrylate, (methyl) acrylic acid 2- naphthylethyls ester, acrylic acid 2- naphthoxys ethyl ester, (methyl) acrylic acid 2- (4- methoxyl group -1- naphthoxys) ethyl ester etc. has (methyl) acrylate of naphthalene nucleus；(methyl) biphenyl acrylate etc. has connection (methyl) acrylate of phenyl ring.
Above-mentioned carboxyl group-containing monomer, hydroxyl monomer, amide-containing monomer, (methyl) acrylate containing aromatic rings are viscous Mixture composite becomes the reflecting point with crosslinking agent in the case of containing crosslinking agent.Especially carboxyl group-containing monomer, hydroxyl monomer Due to high with the reactivity of intermolecular cross-linking agent, for the adhesive phase improved coherency, heat resistance when it is excellent Choosing uses.
It is preferred that (methyl) acrylic polymer that the present invention uses is in the weight ratio for all constituting monomer (100 weight %) Contain above-mentioned each monomer as monomeric unit according to amount below in rate.
The weight rate of above-mentioned (methyl) alkyl acrylate can be set as the list in addition to (methyl) alkyl acrylate The remainder of body, specifically, it is preferable that being 70 weight % or more.From the aspect of ensuring cementability, preferably by (methyl) third The weight rate of olefin(e) acid Arrcostab is set as above range.
The weight rate of above-mentioned carboxyl group-containing monomer is preferably 2 weight % hereinafter, more preferably 0.01~2 weight %, into one Step is preferably 0.05~1.5 weight %, is still more preferably 0.05~1 weight %, particularly preferably 0.05~0.5 weight Measure %.When the weight rate of carboxyl group-containing monomer is less than 0.01 weight %, have the tendency that durability and again operability cannot be taken into account.Separately On the one hand, when being more than 2 weight %, transparency conducting layer corrodes sometimes, has the tendency that durability and again operability cannot be taken into account, no It is preferred that.
The weight rate of hydroxyl monomer is preferably 3 weight % hereinafter, more preferably 0.01~3 weight %, further excellent It is selected as 0.1~2 weight %, particularly preferably 0.2~2 weight %.When the weight rate of hydroxyl monomer is less than 0.01 weight %, The crosslinking of adhesive phase is insufficient, have the tendency that cannot taking into account durability and again operability, adhesion characteristic cannot be met.Another party Face when being more than 3 weight %, has the tendency that durability and again operability cannot be taken into account.
The weight rate of amide-containing monomer is preferably 8 weight % hereinafter, more preferably 0.1~8 weight %, further excellent It is selected as 0.3~5 weight %, is still more preferably 0.3~4 weight %, particularly preferably 0.7~2.5 weight %.Amide-containing When the weight rate of monomer is less than 0.1 weight %, the durability to transparency conducting layer cannot be taken into account and operate again by being especially in the presence of The tendency of property.On the other hand, when being more than 8 weight %, have the tendency that durability and again operability cannot be met simultaneously.
The weight rate of (methyl) acrylate containing aromatic rings is preferably 25 weight % hereinafter, more preferably 0~22 Weight %, further preferably 0~18 weight %.The weight rate of (methyl) acrylate containing aromatic rings is more than 25 weights When measuring %, have the tendency that durability and again operability cannot be met simultaneously.
In above-mentioned (methyl) acrylic polymer, other than above-mentioned monomeric unit, it need not particularly contain it Its monomeric unit, but can will include (methyl) acryloyl for improving cementability, taking into account heat resistance and purpose operational again 1 kind or more comonomer of the functional group of the polymerism with unsaturated double-bond such as base or vinyl is imported by being copolymerized.
As the ratio of the above-mentioned comonomer in (methyl) acrylic polymer, in above-mentioned (methyl) acrylic polymer In the whole weight rates for constituting monomer (100 weight %) for closing object, preferably 0~10 weight % or so, more preferably 0~7 Weight % or so, further preferably 0~5 weight % or so.
The polymer that (methyl) acrylic polymer of the present invention is 1,000,000~2,500,000 usually using weight average molecular weight. If it is considered that durability, particularly heat resistance, then preferable weight-average molecular weight is 1,200,000~2,000,000.Weight average molecular weight is less than 100 Wan Shi, in terms of heat resistance not preferably.In addition, when weight average molecular weight is more than 2,500,000, adhesive has the tendency that being easy to be hardened, and becomes Peeling must be easy to happen.In addition, indicating that weight average molecular weight (Mw)/number average molecular weight (Mn) of molecular weight distribution is preferably 1.8 Above and 10 hereinafter, more preferably 1.8~7, further preferably 1.8~5.When molecular weight distribution (Mw/Mn) is more than 10, resistance to It is not preferred in terms of long property.It should be noted that weight average molecular weight, molecular weight distribution (Mw/Mn) are by passing through GPC (gel infiltration colors Spectrometry) it measures and the value of calculating is found out by the way that polystyrene convert by.
The manufacture of such (methyl) acrylic polymer can suitably select polymerisation in solution, bulk polymerization, lotion poly- Manufacturing method well known to conjunction, various free radical polymerizations etc..In addition, obtained (methyl) acrylic polymer can be random total The arbitrary copolymer such as polymers, block copolymer, graft copolymer.
In addition, in polymerisation in solution, as polymer solvent, can use such as ethyl acetate, toluene.As specific Polymerisation in solution example is reacted under the nonactive air-flow such as nitrogen, and polymerization initiator is added, usually 50~70 DEG C or so, it is 5~30 small When or so reaction condition under carry out.
For the polymerization initiator, chain-transferring agent, emulsifier etc. used in free radical polymerization, it is not particularly limited, it can be with Appropriate selection uses.In addition, the weight average molecular weight of (methyl) acrylic polymer can be according to polymerization initiator, chain-transferring agent Usage amount, reaction condition and control, its usage amount is suitably adjusted according to its type.
As polymerization initiator, it can be cited for example that：2,2 '-azodiisobutyronitriles, 2,2 '-azos two (2- amidine propanes) Dihydrochloride, 2,2 '-azo two [2- (5- methyl -2- imidazoline -2- bases) propane] dihydrochlorides, 2,2 '-azo, two (2- methyl Third amidine) dithionate, 2,2 '-azos two (N, N '-dimethyleneisobutylamidine), 2,2 '-azo, two [N- (2- carboxy ethyls) -2- Methyl-prop amidine] hydrate (trade name：VA-057, Wako Pure Chemicals Co., Ltd. system) etc. azo-initiators, potassium peroxydisulfate, over cure The persulfates such as sour ammonium, dicetyl peroxydicarbonate two (2- ethylhexyls) ester, dicetyl peroxydicarbonate two (4- tert-butylcyclohexyls) ester, Peroxide-butyl carbonate, new peroxide tert-butyl caprate, talkyl peropivalate, the tertiary fourth of peroxidating pivalic acid Ester, dilauroyl peroxide, two positive decoyl of peroxidating, peroxidating 2 ethyl hexanoic acid 1,1,3,3- tetramethyls butyl ester, peroxidating two (4- methyl benzoyls), di-tololyl peroxide, peroxidating tert-butyl isobutyrate, 1,1- bis- (the tertiary hexyl of peroxidating) hexamethylene The peroxide type initiators such as alkane, tert-butyl hydroperoxide, hydrogen peroxide, the combination of persulfate and sodium hydrogensulfite, peroxide The combination etc. of compound and sodium ascorbate is combined with peroxide and redox type initiators made of reducing agent etc., but not It is defined in these.
Above-mentioned polymerization initiator can be used alone, and in addition can also mix two or more use, total content is relative to list 100 parts by weight of total amount of body ingredient are preferably 0.005~1 parts by weight or so, more preferably 0.02~0.5 parts by weight or so.
It should be noted that using such as 2,2 '-azodiisobutyronitriles manufacture above-mentioned heavy divide equally as polymerization initiator When (methyl) acrylic polymer of son amount, relative to 100 parts by weight of total amount of monomer component, the usage amount of polymerization initiator 0.06~0.2 parts by weight or so are preferably set to, 0.08~0.175 parts by weight or so are more preferably set as.
In addition, chain-transferring agent, emulsifier etc. suitable can use known substance.For its additive amount, Ke Yi It does not damage in the range of effect of the present invention suitable for decision.
(2) silane coupling agent containing mercapto
In the present invention, the silane coupling agent containing mercapto is contained in adhesive composition.By being combined in adhesive Contain the silane coupling agent containing mercapto in object, the durability of the adhesive phase formed by the adhesive composition can be improved, Excellent in te pins of durability especially under humidified ambient, and can take into account again operational.In addition, in the silane coupling agent containing mercapto In, the silane coupling agent containing mercapto of particularly preferred oligomeric.Oligomeric mentioned here refers to 2 polymers of monomer Less than the polymer of 100 polymers or so, the weight average molecular weight of the silane coupling agent as oligomeric, preferably 300 ~30000 or so.
As the silane coupling agent containing mercapto of oligomeric, preferably in the molecule with 2 or more alkoxy first The silane coupling agent containing mercapto of the oligomeric of silylation.Specifically, it can be mentioned, for example SHIN-ETSU HANTOTAI's chemical industry strain formula meetings X-41-1805, X-41-1810, X-41-1818 etc. of society's manufacture.These coupling agents are not volatile, due to multiple alkoxies Silicyl and effectively improve durability and operational again, thus preferably.
As the silane coupling agent containing mercapto other than oligomeric, it can be mentioned, for example 3- mercaptopropyi trimethoxies Silane, γ-mercapto propyl methyl dimethoxy silane etc..Specifically, it can be mentioned, for example Shin-Etsu Chemial Co., Ltd's systems The KBM-803 etc. made.
The quantity of the alkoxysilyl of the above-mentioned silane coupling agent containing mercapto is not particularly limited, is preferably being divided It is 2 or more in sub.In addition, in silane coupling agent, the amount of the alkoxy of the above-mentioned silane coupling agent containing mercapto is preferably 10 ~60 weight %, more preferably 20~50 weight %, further preferably 20~40 weight %.
The type of alkoxy is not particularly limited, it can be mentioned, for example：Methoxyl group, ethyoxyl, propoxyl group, butoxy, penta The alkoxy of the carbon atom numbers such as oxygroup, hexyloxy 1~6.In these, preferably methoxyl group, ethyoxyl, more preferable methoxyl group.Separately Outside, it is also preferred that containing both methoxyl group and ethyoxyl in a molecule.
The mercaptan equivalent (mercapto equivalents) of the above-mentioned silane coupling agent containing mercapto is preferably 1000g/mol hereinafter, more excellent 800g/mol is selected as hereinafter, further preferably 700g/mol is hereinafter, be still more preferably 500g/mol or less.In addition, right The lower limiting value of mercaptan equivalent is not particularly limited, but the above-mentioned silane coupling agent containing mercapto be oligomeric when, preferably for Such as 200g/mol or more.
The above-mentioned silane coupling agent (the especially silane coupling agent containing mercapto of oligomeric) containing mercapto can be single It solely uses, and two or more use can also be mixed, but relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, Total content is preferably 0.01~6 parts by weight, more preferably 0.01~3 parts by weight, further preferably 0.05~1 parts by weight.It is logical It crosses and the silane coupling agent containing mercapto is contained with above range, the durability of adhesive phase, especially humidified ambient can be improved Under excellent in te pins of durability, and can take into account again operational.
In addition, in the adhesive composition of the present invention, can also add other than the above-mentioned silane coupling agent containing mercapto Other silane coupling agents.As other coupling agents, can enumerate：3- TSL 8330s, N-2- (amino-ethyl)- 3- aminopropylmethyldimethoxysilanes, 3- triethoxysilicane alkyl-N- (1,3- dimethylbutylenes) propylamine, N- phenyl- The amino-containing silane coupling agent such as gamma-amino propyl trimethoxy silicane, 3- acryloyloxypropyltrimethoxysilanes, 3- first Base acryloxypropyl triethoxysilane etc. contains the silane coupling agent, 3- isocyanate group propyl three of (methyl) acryloyl group The silane coupling agent etc. containing isocyanate group such as Ethoxysilane.
Other silane coupling agents in addition to the above-mentioned silane coupling agent containing mercapto can not damage effect of the present invention In the range of add, its additive amount is not particularly limited.
(3) crosslinking agent
It is preferred that the adhesive composition that the present invention uses contains crosslinking agent.As crosslinking agent, can be crosslinked using organic Agent, multifunctional metallo-chelate.As organic crosslinking agent, can enumerate isocyanates crosslinking agent, peroxide crosslinking agent, Epoxies crosslinking agent, imines crosslinking agent etc..Multifunctional metallo-chelate be polyvalent metal with organic compound covalent bonding or Chelate made of coordination bonding.As polyvalent metal atom, can enumerate Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc..It, can as the atom in the organic compound of covalent bonding or coordination bonding Oxygen atom etc. is enumerated, as organic compound, Arrcostab, alcoholic compound, carboxylic acid compound, ether compound, assimilation can be enumerated and closed Object etc..
As crosslinking agent, preferred isocyanate class crosslinking agent and/or peroxide crosslinking agent, more preferably by isocyanates Class crosslinking agent and peroxide crosslinking agent are applied in combination.
As isocyanates crosslinking agent, at least compound with 2 isocyanate group can be used.For example, usually It is more that used well known aliphatic polyisocyante, alicyclic polyisocyanates, aromatic series are reacted using urethane Isocyanates etc..
As aliphatic polyisocyante, it can be mentioned, for example：Trimethylene diisocyanate, tetramethylene diisocyanate Ester, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanates, 1,3- butylidenes two are different Cyanate, ten dimethylene diisocyanates, 2,4,4- trimethyl hexamethylene diisocyanates etc..
As alicyclic polyisocyanates, it can be mentioned, for example：1,3- cyclopentene diisocyanates, two isocyanide of 1,3- hexamethylenes Acid esters, 1,4- cyclohexane diisocyanates, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation of benzene Diformazan group diisocyanate, hydrogenated toluene diisocyanate, hydrogenation tetramethyl xylylene diisocyanate etc..
As aromatic diisocyanate, it can be mentioned, for example：Phenylene diisocyanate, 2,4 toluene diisocyanate, 2,6- Toluene di-isocyanate(TDI), 2,2 '-methyl diphenylene diisocyanates, 4,4 '-methyl diphenylene diisocyanates, 4,4 '-toluene Amine diisocyanate, 4,4 '-diphenyl ether diisocyanates, 4,4 '-biphenyl diisocyanates, 1,5- naphthalene diisocyanates, benzene Diformazan group diisocyanate etc..
In addition, as isocyanates crosslinking agent, can enumerate above-mentioned diisocyanate polymer (dimer, trimer, Pentamer etc.), change with urethane-modified object, urea-modified object, biuret made of the polyol reactions such as trimethylolpropane Property object, allophanate-modified object, isocyanurate-modified object, Carbodiimide-Modified object etc..
As the commercially available product of isocyanates crosslinking agent, it can be mentioned, for example：Nippon Polyurethane Industry Co., Ltd.'s manufacture Trade name " Millionate MT ", " Millionate MTL ", " Millionate MR-200 ", " Millionate MR- 400 ", the trade name that " Coronate L ", " Coronate HL ", " Coronate HX ", Mitsui Chemicals, Inc manufacture “Takenate D-110N”、“Takenate D-120N”、“Takenate D-140N”、“Takenate D-160N”、 “Takenate D-165N”、“Takenate D-170HN”、“Takenate D-178N”、“Takenate 500”、 " Takenate 600 " etc..These compounds can be used alone, and can also mix two or more use.
As isocyanates crosslinking agent, preferred aliphat polyisocyanates compound, i.e. aliphatic polyisocyante And its modifier.Aliphatic polyisocyante class compound is compared with other isocyanates crosslinking agents, and cross-linked structure is rich in soft It is soft, it is easy to mitigate the stress generated along with expansion/contraction of optical film, is not susceptible to peel off in durability test. As aliphatic polyisocyante class compound, particularly preferred hexamethylene diisocyanate and its modifier.
As peroxide, as long as generating free radicals reactive species by heating or illumination and making the base of adhesive composition Plinth polymer ((methyl) acrylic polymer) carries out crosslinked peroxide, so that it may be used with suitable, but in view of operation Property, stability is, it is preferable to use the peroxide that 1 minute half life temperature is 80 DEG C~160 DEG C, was more preferably declined using 1 minute half The peroxide that phase temperature is 90 DEG C~140 DEG C.
As the peroxide that can be used, it can be mentioned, for example：Dicetyl peroxydicarbonate two (2- ethylhexyls) ester (1 minute Half life temperature：90.6 DEG C), dicetyl peroxydicarbonate two (4- tert-butylcyclohexyls) ester (1 minute half life temperature：92.1℃)、 Peroxide-butyl carbonate (1 minute half life temperature：92.4 DEG C), new peroxide tert-butyl caprate (1 minute half-life period temperature Degree：103.5 DEG C), talkyl peropivalate (1 minute half life temperature：109.1 DEG C), the peroxidating pivalic acid tert-butyl ester (1 Minute half life temperature：110.3 DEG C), dilauroyl peroxide (1 minute half life temperature：116.4 DEG C), peroxidating two it is just pungent Acyl (1 minute half life temperature：117.4 DEG C), peroxidating -2 ethyl hexanoic acid 1,1,3,3- tetramethyls butyl ester (1 minute half-life period temperature Degree：124.3 DEG C), peroxidating two (4- toluyls) (1 minute half life temperature：128.2 DEG C), dibenzoyl peroxide (1 Minute half life temperature：130.0 DEG C), peroxidating tert-butyl isobutyrate (1 minute half life temperature：136.1 DEG C), bis- (mistakes of 1,1- The tertiary hexyl of oxidation) hexamethylene (1 minute half life temperature：149.2 DEG C) etc..Wherein, since cross-linking reaction efficiency is especially excellent, because It is preferable to use dicetyl peroxydicarbonate two (4- tert-butylcyclohexyls) ester (1 minute half life temperatures for this：92.1 DEG C), peroxidating February Osmanthus acyl (1 minute half life temperature：116.4 DEG C), dibenzoyl peroxide (1 minute half life temperature：130.0 DEG C) etc..
It should be noted that the half-life period of peroxide is the index for the decomposition rate for indicating peroxide, refer to until The residual volume of peroxide becomes the time until half.About the decomposition temperature for obtaining half-life period with random time, arbitrary temperature The lower half-life of degree, have in manufacturer's catalogue etc. recorded in, for example, being recorded in NOF Corp《It is organic Peroxide catalogue the 9th edition (in May, 2003)》Deng.
Relative to 100 parts by weight of (methyl) acrylic polymer, the usage amount of crosslinking agent is preferably 0.01~3 weight Part, more preferably 0.02~2 parts by weight, further preferably 0.03~1 parts by weight.It should be noted that crosslinking agent is less than When 0.01 parts by weight, there are the crosslinking hidden danger that is insufficient, cannot meeting durability, adhesion characteristic of adhesive phase, on the other hand, When more than 3 parts by weight, there are the tendencies that adhesive phase becomes durability decline really up to the mark.
Above-mentioned isocyanates crosslinking agent can be used alone, two or more use can also be mixed, relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, total content are preferably 0.01~2 parts by weight, more preferably 0.02~2 weight Part, further preferably 0.05~1.5 parts by weight.It is contemplated that in cohesiveness, durability test prevent stripping etc. and it is suitable Contain.
Above-mentioned peroxide can be used alone, and can also mix two or more use, relative to above-mentioned (methyl) third 100 parts by weight of alkene acids polymers, total content are preferably 0.01~2 parts by weight, more preferably 0.04~1.5 parts by weight, into One step is preferably 0.05~1 parts by weight.In order to adjust processability, cross-linked stable etc., in the range suitable for selection.
(4) ionic compound
The adhesive composition of the present invention can further contain ionic compound.As ionic compound, do not have It is preferable to use ionic compounds used in the art for particular determination.It can be mentioned, for example Japanese Unexamined Patent Publications 2015-4861 Ionic compound described in bulletin, wherein preferred (per-fluoroalkyl sulfonyl) imines lithium salts, more preferable bis- (trifluoro methylsulfonyls Imines) lithium.In addition, the ratio of above-mentioned ionic compound is not particularly limited, can be set as not damaging the model of effect of the present invention It encloses, for example, relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, preferably 10 parts by weight are hereinafter, more preferably 5 Parts by weight hereinafter, further preferably 3 parts by weight hereinafter, below particularly preferably 1 parts by weight.
(5) other
In adhesive composition used in the present invention, the polyethers chemical combination with reactive silicyl can be coordinated Object.Polyether compound is preferred in terms of it can improve operability again.Polyether compound can use such as Japanese Unexamined Patent Publication 2010- Polyether compound disclosed in No. 275522 bulletins.In addition, as its additive amount, it can be in the range for not damaging effect of the present invention It is appropriate to determine.
Further, it is also possible to contain other well known additive in adhesive composition used in the present invention, such as can To add polyether compound, colorant, pigment etc. as the polyalkylene glycol such as polypropylene glycol according to usage Powder, dyestuff, surfactant, plasticizer, tackifier, surface lubricant, levelling agent, softening agent, antioxidant, age resister, Light stabilizer, ultra-violet absorber, polymerization inhibitor, inorganic or organic filler, metal powder or granule, foil-like object etc..In addition, also It can be in the range of can control using the redox class of addition reducing agent.Relative to (methyl) acrylic polymer 100 parts by weight, these additives are preferably below 5 parts by weight, further preferably below 3 parts by weight, still more preferably 1 It is used in range below parts by weight.
2. transparency conducting layer adhesive phase
The transparency conducting layer of the present invention is formed with adhesive phase by above-mentioned adhesive composition.When forming adhesive phase, It is preferred that the additive amount of the whole crosslinking agents of adjustment, and fully consider crosslinking Treatment temperature, the influence of crosslinking Treatment time.
Crosslinking Treatment temperature, crosslinking Treatment time can be adjusted according to the crosslinking agent used.Crosslinking Treatment temperature is preferred It is 170 DEG C or less.It, can also be in addition, above-mentioned crosslinking Treatment can carry out at the temperature at which the drying process of adhesive phase In addition crosslinking Treatment process is set after drying process to carry out.In addition, about the crosslinking Treatment time, it may be considered that productivity, behaviour It is set as property, but usually 0.2~20 minute or so, preferably 0.5~10 minute or so.
The forming method of above-mentioned adhesive phase is not particularly limited, and can be following methods：On various base materials in coating Adhesive composition is stated, is dried by driers such as oven heats, the volatilizations such as solvent are made, according further to needing to implement above-mentioned friendship Connection processing and form adhesive phase, the adhesive phase is then transferred to the polarizing coating described below, on transparent conductive base； It can also directly be coated with above-mentioned adhesive composition on above-mentioned polarizing coating, transparent conductive base and form adhesive phase. In the present invention, preferably pre-production is formed with the polarizing coating with adhesive phase of adhesive phase on polarizing coating, then keeps the band viscous The method that the polarizing coating of mixture layer is attached at liquid crystal cells.
As above-mentioned base material, it is not particularly limited, it can be mentioned, for example：Mold release film, describes transparent resin film base material below The various base materials such as polarizing coating.
As the method to above-mentioned base material, polarizing coating coating adhesive composition, various methods can be used.It is specific and Speech, it can be mentioned, for example：Spray coating method, rolling method, roller lick rubbing method, gravure coating process, reversed rubbing method, roller brush method, spray coating method, leaching Stain rolling method, knife coating, air knife coating method, curtain coating, die lip rubbing method, utilizes the extrusion coating methods of die coating machine etc. at stick coating method The methods of.
Drying condition (temperature, time) is not particularly limited, can be suitable according to composition, the concentration of adhesive composition etc. Setting, for example, for 80~200 DEG C or so, preferably 90~170 DEG C, and be 1~60 minute, preferably 2~30 minutes.
Furthermore it is possible to which the crosslinking treatment is carried out as necessary after the drying, condition such as front is described.
Such as preferably 5~100 μm of the thickness (after dry) of adhesive phase, more preferably 7~70 μm, further preferably 10~50 μm.When the thickness of adhesive phase is less than 5 μm, exists and the adaptation of adherend is short of, is under humidified condition resistance to The insufficient tendency of long property.On the other hand, when the thickness of adhesive phase is more than 100 μm, to forming adhesive when adhesive phase When composition is coated, dries, existing fully to dry, entrapped air pockets, and uneven thickness is generated on the face of adhesive phase, Apparent problem is easy to become significantly to be inclined to.As the constituent material of above-mentioned mold release film, it can be mentioned, for example：Polyethylene gathers The porous materials such as the resin films such as propylene, polyethylene terephthalate, polyester film, paper, cloth, non-woven fabrics, net, foamed sheet, The suitable slice substance etc. such as metal foil and their layered product, but from the excellent aspect of surface smoothness, it is preferable to use resin Film.
As resin film, it can be mentioned, for example：Polyethylene film, polypropylene screen, polybutene film, polybutadiene film, poly- methylpent Alkene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate (PBT) film, Polyurethane film, vinyl-vinyl acetate copolymer film etc..
The thickness of above-mentioned mold release film is usually 5~200 μm, preferably 5~100 μm or so.It can also use as needed Organic silicon, fluorine class, chain alkyl class or fatty acid acyl amine releasing agent, silicon dioxide powder etc. above-mentioned mold release film is taken off Mould and antifouling process or the antistatic process for being coated by type, is mixed into type, vapor deposition type for above-mentioned mold release film etc..In particular, can With by the surface to above-mentioned mold release film suitably carry out organosilicon processing, chain alkyl processing, fluorine processing etc. lift-off processings by into One step improves the fissility relative to above-mentioned adhesive phase.
It as above-mentioned transparent resin film base material, is not particularly limited, the various resin films with the transparency can be used.The tree Adipose membrane is formed by 1 layer of film.For example, as its material, polyethylene terephthalate, poly- naphthalenedicarboxylic acid ethylene glycol can be enumerated The polyester resins such as ester, acetate esters resin, polyether sulfone resin, polycarbonate resin, polyamide-based resin, polyimides Resinoid, polyolefin resin, (methyl) acrylic resin, polyvinyl chloride resin, Vingon resinoid, polyphenyl second Vinyl resin, polyvinyl alcohol resin, polyarylate resinoid, polyphenylene sulfide resinoid etc..It is particularly preferably poly- in these Esters resin, polyimide based resin and polyether sulfone resin.
The thickness of above-mentioned film base material is preferably 15~200 μm.
3. the polarizing coating with adhesive phase
The polarizing coating with adhesive phase of the present invention has above-mentioned adhesive phase in at least one side of polarizing coating.The present invention The polarizing coating with adhesive phase so that the adhesive phase of the polarizing coating was contacted with the transparency conducting layer of transparent conductive base Mode is fitted on above-mentioned transparency conducting layer and is used, and above-mentioned transparent conductive base has transparency conducting layer over the transparent substrate.
The forming method of adhesive phase such as front is described.
It as polarizing coating, is not particularly limited, but the one or two sides for being generally used in polarizer has transparent protective film Polarizing coating.
Polarizer is not particularly limited, various polarizers can be used.As polarizer, it can be mentioned, for example：Make iodine, Dichroic substance as dichroic dye is adsorbed in polyvinyl alcohol film, part formalizing polyvinyl alcohol film, ethylene-second The hydrophilic macromolecule films such as the partly-hydrolysed film of vinyl acetate copolymer class simultaneously carry out film, polyvinyl alcohol obtained from simple tension Polyenoid based oriented films such as dehydration treatment, the dehydrochlorinated products of polyvinyl chloride etc..In these, preferably by polyvinyl alcohol film The polarizer formed with dichroic substances such as iodine, further preferably the iodine class polarizer of iodine and/or iodide ion.In addition, for this The thickness of a little polarizers is not particularly limited, usually 5~80 μm or so.
Being dyed to polyvinyl alcohol film with iodine and carry out polarizer made of simple tension for example can be by by polyvinyl alcohol It is impregnated in 3~7 times that former length is dyed and be stretched in the aqueous solution of iodine and makes.Can also be impregnated in as needed boric acid, In the aqueous solution of potassium iodide optionally comprising zinc sulfate, zinc chloride etc. etc..Further, will can also gather before dyeing as needed Vinyl alcohol film immersion is washed in water.By being washed to polyvinyl alcohol film, in addition to polyvinyl alcohol can be washed away Other than the dirt of class film surface, antiblocking agent, also there is the effect for making polyvinyl alcohol membrane swelling and preventing from dyeing unequal unevenness Fruit.Stretching can be carried out being dyed using iodine after, can also Edge Coloring side stretching, in addition it can carry out stretching it It is dyed afterwards using iodine.It can also be stretched in the aqueous solution of boric acid, potassium iodide etc. or water-bath.
In addition, in the present invention, it is 10 μm of slim polarizers below that can also use thickness.With regard to slimming viewpoint and Speech, which is preferably 1~7 μm.The uneven thickness of this slim polarizer is few, visibility is excellent, and change in size It is few, therefore, excellent in te pins of durability, and then the thickness as polarizing coating can also realize slimming, thus preferably.
As slim polarizer, Japanese Unexamined Patent Application 51-069644 bulletins, Japanese Unexamined Patent Publication 2000- can be typically enumerated No. 338329 bulletins, No. 2010/100917 pamphlet of International Publication No. or Japan Patent No. 4751481 specifications, Japanese Unexamined Patent Publications Slim polarizing coating described in 2012-073563 bulletins.These slim polarizing coatings can be by including by polyvinyl alcohol tree The process and carry out that fat (hereinafter also referred to PVA resinoids) layer and stretching are stretched with resin base material with the state of laminated body The preparation method of the process of dyeing and obtain.If it is the preparation method, even if PVA resinoid layers are relatively thin, resin base material is used due to being stretched It is supported, can also be stretched without generating a problem that being broken caused by stretching.
Including the process stretched with the state of laminated body and the work dyed as above-mentioned slim polarizing coating In the preparation method of sequence, from can with high magnification is stretched and from the aspect of improving polarizing properties, preferably by such as International Publication No. 4751481 No. 2010/100917 pamphlet, No. 2010/100917 pamphlet of International Publication No. or Japan Patent explanations It is included in the process stretched in boric acid aqueous solution as described in book, Japanese Unexamined Patent Publication 2012-073563 bulletins Slim polarizer obtained from preparation method, particularly preferably by being recorded in Japan Patent No. 4751481 specifications, Japanese Unexamined Patent Publications Being included in 2012-073563 bulletins secondarily carries out stretching in atmosphere before being stretched in boric acid aqueous solution Process preparation method obtained from slim polarizer.
As the material being arranged in the transparent protective film of the one or two sides of above-mentioned polarizer is formed, can be used for example transparent The excellent thermoplastic resin such as property, mechanical strength, thermal stability, moisture barrier, isotropism.As such thermoplastic resin The concrete example of fat can enumerate the celluosic resins such as cellulose triacetate, polyester resin, polyethersulfone resin, polysulfone resin, poly- carbonic acid Ester resin, polyamide, polyimide resin, vistanex, (methyl) acrylic resin, cyclic polyolefin resin (drop Borneol vinyl resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin and their mixture.Furthermore it is possible to The side of polarizer is bonded transparent protective film by adhesive layer, and (methyl) acrylic compounds, carbamate are used in the other side The thermosetting resins such as class, propenoic methyl carbamate class, epoxies, organic silicon or ultraviolet curing resin are as transparent guarantor Cuticula.The additive that a kind of any of the above is suitable can also be contained in transparent protective film.As additive, it can be mentioned, for example purples Ultraviolet absorbers, age resister, lubricant, plasticizer, releasing agent, anti-coloring agent, fire retardant, nucleating agent, antistatic agent, face Material, colorant etc..The content of above-mentioned thermoplastic resin in transparent protective film is preferably 50~100 weight %, and more preferably 50 ~99 weight %, further preferably 60~98 weight %, particularly preferably 70~97 weight %.It is above-mentioned in transparent protective film When the content of thermoplastic resin is 50 weight % or less, it is possible to be unable to fully show high possessed by thermoplastic resin script The transparency.
The thickness of transparent protective film can be suitable for determining, but goes out from the operability such as intensity, treatability, film etc. Hair, usually 1~500 μm or so.
Above-mentioned polarizer is usually closely sealed by aqueous adhesive etc. with transparent protective film.It, can example as aqueous adhesive Go out isocyanates bonding agent, polyvinyl alcohol bonding agent, gelatin class bonding agent, ethylene base system latex class, aqueous polyurethane, water Property polyester etc..Than that described above, the bonding agent as polarizer and transparent protective film can enumerate uv-curing type bonding agent, electricity Beamlet curing type bonding agent etc..Electronic beam solidified polarizing coating shows above-mentioned various transparent protective films with bonding agent good Cementability.Alternatively, it is also possible to contain metallic compound filler in the bonding agent that the present invention uses.
In addition, in the present invention, phase difference film etc. can also be formed on polarizer to replace the transparency protected of polarizing coating Film.Furthermore it is also possible to which other transparent protective films or setting phase difference film etc. are further arranged on transparent protective film.
It can also implement hard conating, antireflection process, anti-sticking in the one side for not being bonded polarizer of above-mentioned transparent protective film The processing for connecing processing, being carried out for the purpose of spreading or is anti-dazzle.
Furthermore it is also possible to have adhesion promoting layer between polarizing coating and adhesive phase.Material for forming adhesion promoting layer does not have Particular determination, it can be mentioned, for example：Various polymerization species, the colloidal sol of metal oxide, Ludox etc..In these, particularly preferably Use polymerization species.Above-mentioned polymerization species can be arbitrary in solvent soluble type, water-dispersion type, water soluble type using form Form.
As above-mentioned polymerization species, it can be mentioned, for example：Polyurethane based resin, polyester resin, acrylic resin, polyethers Resinoid, cellulosic resin, polyvinyl alcohol resin, polyvinylpyrrolidone, polystyrene resins etc..In addition, In above-mentioned polymerization species, the conductive polies such as the polythiophene that can be used as the forming material of following organic conductive layers can be used Close object.
In addition, the above-mentioned polarizing coating with adhesive phase adhesive phase expose in the case of, can use mold release film (every Piece) protect adhesive phase until it is for use.As mold release film, the mold release film that front describes can be enumerated.It makes above-mentioned When adhesive phase, in the case where using mold release film as base material, by making the adhesive phase in mold release film be bonded with polarizing coating, The mold release film can be used as the mold release film of the adhesive phase of the polarizing coating with adhesive phase, can be simplified in terms of process.
The polarizing coating with adhesive phase of the present invention, which fits on the transparency conducting layer of transparent conductive base, to be used, above-mentioned Transparent conductive base has transparency conducting layer over the transparent substrate.
The constituent material of transparency conducting layer as transparent conductive base, is not particularly limited, can be used selected from indium, The metal oxide of at least one of tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminium, gold, silver, copper, palladium, tungsten metal.The metal In oxide can also as needed further contain it is above-mentioned shown in metallic atom.For example, it is preferable to using tin oxide is contained Indium oxide (ITO), the tin oxide etc. containing antimony particularly preferably use ITO.As ITO, 80~99 weight of indium oxide is preferably comprised Measure % and 1~20 weight % of tin oxide.
In addition, as above-mentioned ITO, crystalline ITO, amorphism (amorphous) ITO can be enumerated, is suitable for using.
The transparency conducting layer of transparent conductive base can be enumerated is formed as golden made of the pattern of clathrate by metal fine Belong to net, coating metal particle and the transparency conducting layer formed.As the metal material of composition, as long as the metal that electric conductivity is high, Any appropriate metal (including metal alloy substance) can be used.Specifically, it is preferable that for example selected from gold, platinum, silver, aluminium, And one or more of copper metal, from the viewpoint of electric conductivity, preferably aluminium, silver, copper or gold.
The transparency conducting layer of transparent conductive base can be formed by Organic Conductive Films.Formation material as Organic Conductive Films Material, is not particularly limited, the ionic conductivity group that can be enumerated electric conductive polymer, be made of electrolytic salt and organopolysiloxane Close object, ionic compound, various surfactants (cationic, anionic and amphoteric surfactant) etc..These are worked as In, when optical characteristics, appearance, antistatic effect and antistatic effect are in warm, humidification when stability, It is preferable to use conducting polymers.Particularly preferably using electric conductive polymers such as polyaniline, polythiophenes.These can use water-soluble Any one of property, water dispersible, organic solvent-soluble, organic solvent dispersion, for water-soluble conducting polymer, water For dispersed electric conductive polymer, coating fluid when forming antistatic layer can be prepared into aqueous solution or aqueous dispersions, it should Coating fluid need not use Non-aqueous Organic Solvents, can inhibit the rotten of the transparent base caused by the organic solvent.It needs Illustrate, aqueous solution or aqueous dispersions can also contain aqueous solvent other than containing water.It can be mentioned, for example：Methanol, second Alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-pentyl alcohol, 1- second The alcohols such as base -1- propyl alcohol, 2-methyl-1-butene alcohol, n-hexyl alcohol, cyclohexanol.
In addition, the water-soluble conductings such as above-mentioned polyaniline, polythiophene polymer or aqueous-dispersible conductive polymer are preferred There is hydrophilic functional group in the molecule.As hydrophilic functional group, it can be mentioned, for example：Sulfo group, amino, amide groups, imino group, Quaternary ammonium salt base, hydroxyl, sulfydryl, diazanyl, carboxyl, sulfate group, phosphate-based or these groups salt etc..By in the molecule With hydrophilic functional group, to be easy dissolving in water, it is easily dispersed into microgranular, can easily prepares above-mentioned in water Water-soluble conducting polymer or aqueous-dispersible conductive polymer.
The example of commercially available product as water-soluble conducting polymer can enumerate polyaniline sulfonic acid (Mitsubishi Rayon Co., Ltd 150000) etc. system is by the weight average molecular weight that finds out of polystyrene conversion.Commercially available product as aqueous-dispersible conductive polymer Example, polythiophene class electric conductive polymer (Nagase Chemtex corporations, trade name Denatron series) etc. can be enumerated.
In addition, in order to improve the envelope formative of electric conductive polymer and the adaptation etc. of transparent base, above-mentioned electric conductivity Polymer can also add adhesive ingredients.Electric conductive polymer is that water-soluble conducting polymer or aqueous-dispersible conductive are poly- When closing water-based material as object, water-soluble or water dispersible adhesive ingredients is used.As the example of adhesive, can enumerate ContainOxazoline based polyalcohol, polyurethane based resin, polyester resin, acrylic resin, polyethers resinoid, cellulose family tree Fat, polyvinyl alcohol resin, epoxy resin, polyvinylpyrrolidone, polystyrene resins, polyethylene glycol, pentaerythrite etc.. Particularly preferred polyurethane based resin, polyester resin, acrylic resin.These adhesives can suitably make according to its purposes With one kind or two or more.
Electric conductive polymer, adhesive usage amount depend on its type, preferably by the surface of obtained transparent conductive film Resistance value control is 1 × 108~1 × 1012Ω/□。
In addition, other well known additive can also be contained in organic conductive layers used in the present invention, such as can be with It is properly added the powder of colorant, pigment etc., dyestuff, surfactant, plasticizer, tackifier, surface profit according to usage It is lubrication prescription, levelling agent, softening agent, antioxidant, age resister, light stabilizer, ultra-violet absorber, polymerization inhibitor, inorganic or organic Filler, metal powder or granule, foil-like object etc..
In addition, Organic Conductive Films can also pass through the electrolysis polymerization of the monomer of formation electric conductive polymer over the transparent substrate And it is formed.
The thickness of above-mentioned transparency conducting layer is not particularly limited, preferably 10nm~1000nm, more preferably 50~ 400nm。
It as the forming method of above-mentioned transparency conducting layer, is not particularly limited, known method may be used.Specifically For, can example go out such as vacuum vapour deposition, sputtering method, ion plating method.In addition, in the case where being coated with coating liquid, can enumerate Such as：Micro- gravure coat method, rolling method, dip coating, flow coat method, spin-coating method, die coating method, casting transfer printing, spray coating method etc.. In addition, in the case of metal mesh, such as can be obtained by following methods：Photosensitive composite containing silver salt is (transparent Conductive layer forms composition) it is coated in the adherends such as mold release film, it is then exposed processing and development treatment, by metal Filament is formed as given pattern.In addition, the transparency conducting layer can also be by by the paste (transparency conducting layer containing metal particle Form composition) it is printed as given pattern and obtains.Suitable method is used alternatively, it is also possible to film thickness as needed.
Alternatively, it is also possible to have outer painting (OC) layer (not shown) on above-mentioned transparency conducting layer.As external coating, without spy Different limitation, can be used external coating usually used in this field, it can be mentioned, for example by alkyd resin, acrylic resin, asphalt mixtures modified by epoxy resin The layer of the formation such as fat, carbamate resins, isocyanate resin.As the thickness of external coating, it is not particularly limited, for example, Preferably 0.1~10 μm.
As transparent base, as long as transparent substrate, is not particularly limited its raw material, for example, can enumerate Glass, transparent resin film base material.As transparent resin film base material, the base material that front is described can be enumerated.
In addition, as needed, priming coat, anti-oligomer layer can also be arranged between transparency conducting layer and transparent substrate Deng.
4. image display panel, image display device
The image display panel of the present invention has above-mentioned polarizing coating and transparent conductive base with adhesive phase, above-mentioned Transparent conductive base has transparency conducting layer over the transparent substrate, which is characterized in that
The adhesive phase of the above-mentioned polarizing coating with adhesive phase fits in the above-mentioned electrically conducting transparent of above-mentioned image display panel Layer.
In addition, the image display device of the present invention is characterized in that, with above-mentioned image display panel.
It is described about the polarizing coating with adhesive phase, transparent conductive base, such as front.Image display panel has upper Transparent conductive base is stated, forms a part for image display device together with the above-mentioned polarizing coating with adhesive.
To the representative embodiments of the image display panel as the polarizing coating with adhesive phase for having used the present invention Liquid crystal display panel illustrate.The liquid crystal cells used in liquid crystal display panel have saturating with transparency conducting layer over the transparent substrate Bright conductive substrate usually has the transparent conductive base on the surface of the visible side of liquid crystal cells.Using Fig. 1 to including energy The liquid crystal display panel for the liquid crystal cells being enough used in the present invention illustrates.But the present invention is not limited by Fig. 1.
As an embodiment of the liquid crystal display panel 1 that can be included in the image display panel of the present invention, can enumerate It is led from visible side by 2/ polarizer of visible side transparent protective film, 3/ liquid crystal cell side transparent protective film, 4/ adhesive phase 5/ is transparent 10/ liquid crystal cell side transparent protective film of electric layer 6/ transparent base, 7/ liquid crystal layer, 8/ transparent base, 9/ adhesive phase, 11/ polarizer 12/ The structure that light source side transparent protective film 13 is constituted.In Fig. 1, it is saturating to be equivalent to visible side for the polarizing coating of the invention with adhesive phase 2/ polarizer of bright protective film, 2/ liquid crystal cell side transparent protective film, 3/ adhesive phase 5.In addition, in Fig. 1, it is used in the present invention Transparent conductive base is made of 6/ transparent base 7 of transparency conducting layer.In addition, in Fig. 1, having used in the present invention transparent The liquid crystal cells of conductive substrate are made of 6/ transparent base of transparency conducting layer, 7/ liquid crystal layer, 8/ transparent base 9.
In addition, in addition to above-mentioned composition, phase difference film, compensation film for angular field of view, brightness can be appropriately arranged in liquid crystal display panel 1 Improve the optical films such as film.
It as liquid crystal layer 8, is not particularly limited, can be used for example：The arbitrary classes such as TN types, STN types, π types, VA types, IPS types The liquid crystal layer of type.Transparent substrate 9 (light source side) is not particularly limited its raw material, can arrange as long as transparent substrate Citing is such as：Glass, transparent resin film base material.As transparent resin film base material, the base material that front is described can be enumerated.
In addition, saturating about the adhesive phase 10 of light source side, liquid crystal cell side transparent protective film 11, polarizer 12, light source side The corresponding component used in the past in this field can be used, alternatively, it is also possible to which it is preferable to use remember in this specification in bright protective film 13 The corresponding component carried.
Above-mentioned liquid crystal display panel 1 so that the transparency conducting layer 6 and the polarizing coating with adhesive phase of liquid crystal cells adhesive phase 5 The mode of contact, in the band bonding of the outermost transparency conducting layer 6 superimposed layer present invention for the visible side for being formed in liquid crystal cells The polarizing coating of oxidant layer.
As long as the present invention image display device including the present invention the polarizing coating with adhesive phase and have electrically conducting transparent Property base material image display panel, the transparent conductive base over the transparent substrate have transparency conducting layer, preferably wrap Containing above-mentioned liquid crystal display panel.Hereinafter, as an example, liquid crystal display device is illustrated, but the present invention is not limited by it.
As the concrete example for the image display device that can apply above-mentioned image display panel, can enumerate：Liquid crystal display fills It sets, organic electroluminescent (EL) display, plasma scope (PD), field-emitter display (FED：Field Emission Display) etc..
As long as the present invention image display device including the present invention the polarizing coating with adhesive phase and have electrically conducting transparent The image display panel of property base material, other compositions, above-mentioned transparent conductive base identical as previous image display device There is transparency conducting layer on the transparent base.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited to the examples.It needs Illustrate, not special provision is placed at room temperature for that condition is 23 DEG C all, 65%R.H..
The measurement ＞ of the weight average molecular weight of ＜ (methyl) acrylic polymer
The weight average molecular weight (Mw) of (methyl) acrylic polymer is measured by GPC (gel permeation chromatography).About Mw/Mn is similarly determined.
Analytical equipment：HLC-8120GPC, TOSOH Co., Ltd's system
Column：G7000HXL+GMHXL+GMHXL, TOSOH Co., Ltd's system
Column dimension：Each 7.8mm φ × 30cm amount to 90cm
Column temperature：40℃
Flow：0.8mL/min
Injection rate：100μL
Eluent：Tetrahydrofuran
Detector：Differential refractometer (RI)
Standard sample：Polystyrene
Production Example 1 (making of polarizing coating)
By the polyvinyl alcohol film of 80 μm of thickness in 30 DEG C, the iodine solution of 0.3 weight % concentration in speed than different rollers Between an Edge Coloring be stretched to 3 times on one side within 1 minute.Then, 60 DEG C, the boric acid comprising 4 weight % concentration, 10 weight % concentration It is 6 times to be stretched to total stretching ratio while impregnating 0.5 minute in the aqueous solution of potassium iodide.Next, by 30 DEG C, contain Have in the aqueous solution of the potassium iodide of 1.5 weight % concentration and impregnate 10 seconds and cleaned, is then carried out 4 minutes at 50 DEG C Drying, obtained the polarizer of 30 μm of thickness.It is bonded through saponification by polyvinyl alcohol bonding agent on the two sides of the polarizer The tri cellulose acetate membrane of 80 μm of the thickness of processing, has made polarizing coating.
Production Example 2 (preparation of the solution of acrylic polymer (a-1))
It is added in the 4 neck flasks for having stirring blade, thermometer, nitrogen ingress pipe, condenser and contains butyl acrylate The monomer mixture of 99 parts by weight, 1 parts by weight of acrylic acid 4- hydroxybutyls.Further, relative to above-mentioned monomer mixture (Gu Body ingredient) 100 parts by weight, 2,2 '-azodiisobutyronitriles of the addition as polymerization initiator together with 100 parts by weight of ethyl acetate 0.1 parts by weight, imported while being slowly stirred nitrogen carry out nitrogen displacement after, make the liquid temperature in flask be held in 55 DEG C it is attached Closely, the polymerisation for carrying out 8 hours, it is the acrylic polymer that 1,560,000, Mw/Mn is 3.2 to be prepared for weight average molecular weight (Mw) (a-1) solution.
Production Example 3~5
In addition to change as shown in table 1 the monomer used in Production Example 2 when preparing acrylic polymer type, Other than its use ratio, according to method identical with Production Example 2, it is prepared for the molten of acrylic polymer (a-2)~(a-4) Liquid.
Table 1
Abbreviation difference in table 1 is as described below.
BA：Butyl acrylate
NVP：N-vinyl-2-pyrrolidone
AA：Acrylic acid
HBA：Acrylic acid 4- hydroxybutyls
Embodiment 1
(preparations of acrylic pressure-sensitive adhesive compositions)
100 parts by weight of solid constituent of solution relative to the acrylic polymer (a-1) obtained in Production Example 2, match Close isocyanate crosslinking (trade name：Takenate D160N, trimethylolpropane hexamethylene diisocyanate, three wells Learn Co. Ltd. system) 0.1 part, 0.3 part of benzoyl peroxide (Nyper BMT 40SV, NOF Corp's system) and 3- Mercaptopropyi trimethoxy silane (trade name：KBM-803, alcoxyl base unit weight：47 weight %, mercaptan equivalent：196g/mol, SHIN-ETSU HANTOTAI Chemical industry Co. Ltd. system) 0.3 part, it is prepared for the solution of acrylic pressure-sensitive adhesive compositions.
(making of the polarizing coating with adhesive phase)
By the solution coating of acrylic pressure-sensitive adhesive compositions in polyethylene terephthalate film (diaphragm, trade name： MRF38, Mitsubishi Plastics Inc's system) through organic silicon remover handle one side on, carried out at 155 DEG C 1 minute It is dry so that the thickness of the adhesive phase after dry is 23 μm, and adhesive phase is formd on the surface of diaphragm.Next, by shape At on the polarizing coating that the adhesive phase on diaphragm is transferred to the making of Production Example 1, the polarizing coating with adhesive phase has been made.
Embodiment 2~13, the Comparative Examples 1 to 5
In embodiment 1, change that the type of acrylic polymer, the type of silane coupling agent, it adds as shown in table 2 Dosage is prepared for the solution of acrylic pressure-sensitive adhesive compositions in the same manner as shown in Example 1 in addition to this.It needs It is bright, in embodiment 12, ionic compound is coordinated with ratio shown in table 2.Use obtained acrylic adhesives The solution of composition has made the polarizing coating with adhesive phase in the same manner as shown in Example 1.
Following evaluation, evaluation result have been carried out to the polarizing coating with adhesive phase obtained in above-described embodiment and comparative example It is shown in table 2.
＜ evaluates the preparation ＞ of sample
The polarizing coating with adhesive phase that Examples and Comparative Examples obtain is cut into 15 inches of size, as sample Product.The sample is fitted in into the glass with transparency conducting layer.As the glass with transparency conducting layer, using thickness 0.7mm's Alkali-free glass (trade name：EG-XG, Corning Incorporated's system) on amorphism ITO layer the glass with ITO layer and with above-mentioned phase The glass with Organic Conductive Films with Organic Conductive Films on same alkali-free glass.The sample is pasted on respectively using laminating machine The Organic Conductive Films of the ITO layer of the above-mentioned glass with ITO layer, the glass with Organic Conductive Films.Next, with 50 DEG C, 0.5MPa 15 minutes autoclave process are carried out, keep above-mentioned sample completely close with the glass with ITO layer and the glass with Organic Conductive Films respectively It closes.
It should be noted that ITO layer is formed by sputtering.In the composition of ITO, Sn ratios are 3 weight %, before being bonded sample Implement 140 DEG C × 60 minutes heating processes.It should be noted that weight/(Sn atom of the Sn ratios of ITO by Sn atoms Weight+In atoms weight) calculate.Organic Conductive Films use the coating containing poly- Ethylenedioxy Thiophene/polyvinyl sulfonate Liquid is formed by spin-coating method.
Durability test ＞ after ＜ just coatings
Sample to implementing above-mentioned processing implements (heating after processing in 500 hours under each atmosphere of 60 DEG C/95%RH Experiment), with the naked eye had rated respectively according to following benchmark between polarizing coating and glass with ITO layer and polarizing coating with organic Appearance between the glass of conductive film.
(evaluation criteria)
◎：Completely without apparent variations such as strippings.
○：End is slightly removed, but there is no problem in actual use.
△：There is stripping in end, but if not being special purposes, then there is no problem in actual use.
×：There is significant stripping in end, problematic in actual use.
＜ bonding forces ＞
The polarizing coating with adhesive phase obtained in Examples and Comparative Examples is cut into the size of wide 25mm, as Sample is evaluated, in addition to this, by being operated in the same manner as the preparation ＞ of ＜ evaluation samples, fits in the glass with transparency conducting layer On (glass with ITO layer and the glass with Organic Conductive Films), is similarly handled, make the polarizing coating with adhesive phase and band The glass of transparency conducting layer is completely closely sealed (initial stage).
Then, heat treatment in 48 hours is implemented under 60 DEG C of drying condition (after heating).Measure the viscous of above-mentioned sample Relay.By cupping machine (Autograph SHIMAZU AG-1 1OKN) with 90 ° of peel angle, peeling rate 300mm/ Divide the bonding force (N/25mm) when measuring stripping to above-mentioned sample, so as to find out bonding force.When measurement, between 1 time/0.5 second Every sampling, using its average value as measured value.
＜ operability ＞ again
The polarizing coating with adhesive phase obtained in Examples and Comparative Examples is cut into the ruler of vertical 350mm × horizontal 250mm It is very little, as sample, in addition to this, implement processing identical with the measure object of above-mentioned bonding force.It will using the hand of people Above-mentioned sample is removed from the glass with transparency conducting layer, operational again based on following benchmark evaluations.Operational evaluation again 3 are made in the order described above, are repeated 3 times and are implemented.
◎：3 are all broken without thickener residual, film, can remove well.
○：Film fracture occurs for the part in 3, but is removed by stripping again.
△：3 all occur film fracture, but are removed by stripping again.
×：3 all generation thickener remains or stripping film is all broken and cannot remove several times.
Abbreviation difference in table 2 is as described below.
Isocyanates：Trade name：Takenate D160N, trimethylolpropane hexamethylene diisocyanate, three wells Chemical Co., Ltd. system；
Peroxide：Trade name：Nyper BMT 40SV, benzoyl peroxide, NOF Corp's system
KBM-803：3-mercaptopropyi trimethoxy silane, alcoxyl base unit weight：47 weight %, mercaptan equivalent：196g/mol, letter More chemical industry Co. Ltd. system；
X-41-1805：The silane coupling agent containing mercapto of oligomeric, alcoxyl base unit weight：50 weight %, mercaptan equivalent： 800g/mol, Shin-Etsu Chemial Co., Ltd's system；
X-41-1818：The silane coupling agent containing mercapto of oligomeric, alcoxyl base unit weight：60 weight %, mercaptan equivalent： 850g/mol, Shin-Etsu Chemial Co., Ltd's system；
X-41-1810：The silane coupling agent containing mercapto of oligomeric, alcoxyl base unit weight：30 weight %, mercaptan equivalent： 450g/mol, Shin-Etsu Chemial Co., Ltd's system；
KBM403：γ-glycidoxypropyl group methoxy silane, alcoxyl base unit weight：39 weight %, SHIN-ETSU HANTOTAI's chemical industry strain formula Commercial firm's system；
X-41-1056：The silane coupling agent containing epoxy group of oligomeric, alcoxyl base unit weight：17 weight %, epoxide equivalent： 280g/mol, Shin-Etsu Chemial Co., Ltd's system；
Ionic compound：Bis- (trifluoro methylsulfonimide) lithiums, Mitsubishi Materials Corp's system.

Claims (7)

1. a kind of polarizing coating with adhesive phase, with adhesive phase and polarizing coating, described adhesive layer fits in transparent lead It is used on the transparency conducting layer of conductive substrate, the transparent conductive base has transparency conducting layer over the transparent substrate, wherein
The adhesive composition for being used to form described adhesive layer contains (methyl) acrylic polymer and the silicon containing mercapto Alkane coupling agent.
2. the polarizing coating with adhesive phase as described in claim 1, wherein the silane coupling agent containing mercapto is oligomeric The silane coupling agent containing mercapto of object type.
3. the polarizing coating with adhesive phase as described in claim 1, wherein the silane coupling agent containing mercapto is in molecule Inside there is 2 or more alkoxysilyls.
4. the polarizing coating with adhesive phase as described in claim 1, wherein relative to (methyl) acrylic polymer The use level of 100 parts by weight, the silane coupling agent containing mercapto is 0.01~3 parts by weight.
5. the polarizing coating as described in any one of claims 1 to 4 with adhesive phase, wherein the silane containing mercapto The mercaptan equivalent of coupling agent is 700g/mol or less.
6. a kind of image display panel, has：Polarizing coating according to any one of claims 1 to 5 with adhesive phase and Transparent conductive base, the transparent conductive base have transparency conducting layer over the transparent substrate, wherein
The adhesive phase of the polarizing coating with adhesive phase fits in the transparency conducting layer of described image display panel.
7. a kind of image display device, with the image display panel described in claim 6.
CN201710864513.0A 2016-09-29 2017-09-22 Polarizing coating with adhesive phase and image display device Pending CN108300356A (en)

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