CN107430300A - Liquid crystal panel and image display device - Google Patents

Liquid crystal panel and image display device Download PDF

Info

Publication number
CN107430300A
CN107430300A CN201680018048.2A CN201680018048A CN107430300A CN 107430300 A CN107430300 A CN 107430300A CN 201680018048 A CN201680018048 A CN 201680018048A CN 107430300 A CN107430300 A CN 107430300A
Authority
CN
China
Prior art keywords
liquid crystal
methyl
weight
crystal panel
adhesive phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201680018048.2A
Other languages
Chinese (zh)
Other versions
CN107430300B (en
Inventor
木村智之
藤田昌邦
外山雄祐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of CN107430300A publication Critical patent/CN107430300A/en
Application granted granted Critical
Publication of CN107430300B publication Critical patent/CN107430300B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Adhesive Tapes (AREA)

Abstract

It is an object of the invention to provide a kind of liquid crystal panel, and it, which is included in one side, has the liquid crystal cells of transparency conducting layer, it is possible to increase the overall durability of liquid crystal panel, is further able to suppress panel warpage, light leak.In addition, it is an object of the invention to provide a kind of image display device for having used above-mentioned liquid crystal panel.The present invention liquid crystal panel liquid crystal cells one side formed with transparency conducting layer, the 1st polarizing coating is bonded by the 1st adhesive phase formed by adhesive composition (A1) on the transparency conducting layer, the 2nd polarizing coating is bonded by the 2nd adhesive phase formed by adhesive composition (A2) on the another side of liquid crystal cells, wherein, above-mentioned adhesive composition (A1) includes (methyl) acrylic polymer (a1) and containing epoxy silane coupling, above-mentioned adhesive composition (A2) includes (methyl) acrylic polymer (a2) and silane coupler containing mercapto, the gel fraction of above-mentioned 1st adhesive phase and the 2nd adhesive phase is more than 65% and less than 90%, and meet following formula (1).[mathematical expression 1]

Description

Liquid crystal panel and image display device
Technical field
The present invention relates to a kind of liquid crystal panel and the image display device of the liquid crystal panel is used.
Background technology
Liquid crystal panel for liquid crystal display device etc. generally has partially in the both sides of liquid crystal cells across adhesive phase lamination Vibrating diaphragm, the liquid crystal cells are formed by the liquid crystal layer of a pair of transparency carriers and configuration between them.To such adhesive phase It is required that high-durability, for example, in the long duration test using heating and humidification etc. carried out usually as environmental accelerated test, It is required 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 Thing, its after optical film is pasted, even if in the case of being positioned under high wet heat condition, also will not it is peeling-off, foaming (for example, With reference to patent document 1).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-242767 publications
The content of the invention
The invention problem to be solved
It is known to have on the transparency carrier of liquid crystal cells for forming liquid crystal panel formed with tin indium oxide (ITO) film Deng the device of nesa coating, compared to the adhesive phase contacted with transparency carriers such as glass substrates, connect with the nesa coating Tactile adhesive phase is easily peeling-off, tilts etc., there is durability reduction.By the adhesive composition of patent document 1 The adhesive phase of formation is poor to the adaptation of tin indium oxide (ITO) layer, as the liquid crystal panel with transparency conducting layer Adhesive composition, and it is insufficient.
It is another formed with nesa coatings such as ito thin films on a transparency carrier of liquid crystal cells as above described Individual is that transparency carrier, the situations that the property on the two sides of liquid crystal cells is different such as glass substrate are more.In the presence of being difficult in such liquid Durability that the two sides of brilliant unit keeps not foaming, peeling off, the problem of being difficult to keep the durability of liquid crystal panel entirety. In patent document 1, pair there is no any regulation with the relation of the adherend such as liquid crystal cells, the durability overall from liquid crystal panel Viewpoint is set out, and insufficient.
In addition, in recent years, it is desirable to which the slimming of liquid crystal panel, but if liquid crystal panel is thinned, then panel is sent out sometimes Raw warpage.If the warpage of panel becomes big, produce because of liquid crystal panel and display image caused by the contact of the framework of display Become the peeling-off unfavorable condition of two-sided tape that is uneven, fixing liquid crystal panel and backlight.In addition, carry out making liquid The region of the periphery of crystal device narrows and improves the area ratio (narrow edge) of viewing area in a display device, but Due to the narrow width of the periphery by shading in the outside of viewing area, so causing polarizing coating end to be entered by the contraction of polarizing coating Enter the inner side of viewing area, light leak occurs for the periphery in viewing area sometimes.So, liquid crystal panel is being carried out Slimming, narrow edge in recent years in, to preventing the warpage of panel, the requirement level of light leak from improving constantly.
Therefore, it is an object of the invention to provide a kind of liquid crystal panel, it, which is included in one side, has the liquid of transparency conducting layer Brilliant unit, it is possible to increase the overall durability of liquid crystal panel, can further suppress panel warpage, light leak.It is in addition, of the invention Purpose be to provide a kind of image display device for having used above-mentioned liquid crystal panel.
The method solved the problems, such as
Further investigation has been repeated in order to solve the above problems in the present inventor etc., is as a result found that following liquid crystal surfaces Plate, so as to complete the present invention.
That is, the present invention relates to a kind of liquid crystal panel, its liquid crystal cells one side formed with transparency conducting layer, it is transparent at this The 1st polarizing coating is bonded by the 1st adhesive phase formed by adhesive composition (A1) on conductive layer, in the another of liquid crystal cells The 2nd polarizing coating is bonded by the 2nd adhesive phase formed by adhesive composition (A2) on face, wherein,
Above-mentioned adhesive composition (A1) includes (methyl) acrylic polymer (a1) and containing epoxy silane coupling,
Above-mentioned adhesive composition (A2) includes (methyl) acrylic polymer (a2) and silane coupler containing mercapto,
The gel fraction of above-mentioned 1st adhesive phase and the 2nd adhesive phase is more than 65% and less than 90%, and is met following Formula (1),
[mathematical expression 1]
It is preferred that above-mentioned is the oligomer for having more than 2 alkoxysilyls in intramolecular containing epoxy silane coupling Type contains epoxy silane coupling.
It is preferred that above-mentioned silane coupler containing mercapto is the oligomer for having more than 2 alkoxysilyls in intramolecular Type silane coupler containing mercapto.
It is above-mentioned containing epoxy silane coupling relative to the above-mentioned parts by weight of (methyl) acrylic polymer (a1) 100 Use level is preferably 0.001~5 parts by weight.
Relative to the above-mentioned parts by weight of (methyl) acrylic polymer (a2) 100, the above-mentioned silane coupler containing mercapto Use level is preferably 0.001~5 parts by weight.
It is preferred that above-mentioned (methyl) acrylic polymer (a1) and/or (a2) contain the weight % of carboxyl group-containing monomer 0.01~2 As monomeric unit.
It is preferred that above-mentioned (methyl) acrylic polymer (a1) and/or (a2) contain the weight % conducts of amide-containing 0.1~8 Monomeric units.
It is preferred that above-mentioned (methyl) acrylic polymer (a1) and/or (a2) contain the weight % of hydroxyl monomer 0.01~7 As monomeric unit.
It is preferred that above-mentioned adhesive composition (A1) and/or (A2), which contain, is selected from isocyanates crosslinking agent and peroxide At least one of crosslinking agent crosslinking agent.
Moreover, it relates to a kind of image display device, it uses above-mentioned liquid crystal panel.
The effect of invention
In the present invention, by the one side positioned at liquid crystal cells electrically conducting transparent aspect across by specific adhesive group Compound (A1) formed the 1st adhesive phase configure the 1st polarizing coating, liquid crystal cells another side across by specific adhesive group The 2nd adhesive phase that compound (A2) is formed configures the 2nd polarizing coating, and controls the gel of the 1st adhesive phase and the 2nd adhesive phase Rate, so as to improve the overall durability of liquid crystal panel, it can further suppress panel warpage, light leak.
Brief description of the drawings
Fig. 1 is the schematic cross sectional view for an embodiment for showing the liquid crystal panel of the present invention.
Symbol description
1a visible side transparent protective films
1b liquid crystal cell side transparent protective films
2a polarizers
2b polarizers
3a liquid crystal cell side transparent protective films
3b light source side transparent protective films
The polarizing coatings of 4a the 1st
The polarizing coatings of 4b the 2nd
The 1st adhesive phase that 5a is formed by adhesive composition (A1)
The 2nd adhesive phase that 5b is formed by adhesive composition (A2)
6 transparency conducting layers
7 the 1st transparency carriers
8 liquid crystal layers
9 the 2nd transparency carriers
10 liquid crystal cells
11 liquid crystal panels
Embodiment
1. liquid crystal panel
The present invention liquid crystal panel liquid crystal cells one side formed with transparency conducting layer, pass through on the transparency conducting layer The 1st adhesive phase formed by adhesive composition (A1) is bonded the 1st polarizing coating, by by gluing on the another side of liquid crystal cells The 2nd adhesive phase that mixture composite (A2) is formed is bonded the 2nd polarizing coating, wherein,
Above-mentioned adhesive composition (A1) includes (methyl) acrylic polymer (a1) and containing epoxy silane coupling,
Above-mentioned adhesive composition (A2) includes (methyl) acrylic polymer (a2) and silane coupler containing mercapto,
The gel fraction of above-mentioned 1st adhesive phase and the 2nd adhesive phase is more than 65% and less than 90%, and is met following Formula (1),
[mathematical expression 2]
(1) adhesive composition (A1)
Adhesive composition (A1) used in the present invention is containing (methyl) acrylic polymer (a1) and containing epoxy radicals Silane coupler, preferably comprise (methyl) acrylic polymer (a1) and be used as principal component.Principal component mentioned here refers to The most composition of content ratio in contained solid constituent in adhesive composition (A1), for example, referring in adhesive composition (A1) occupy the composition more than 50 weight % in all solids composition contained by, further refer to occupy more than 70 weight % into Point.
(methyl) acrylic polymer (a1) usually contains (methyl) alkyl acrylate conduct as monomeric unit Principal component.It should be noted that (methyl) acrylate refers to acrylate and/or methacrylate, (the first with the present invention Base) meaning is identical.
As form (methyl) acrylic polymer (a1) main framing (methyl) alkyl acrylate, can example go out The atomic number of alkyl carbon of straight-chain or branched is 1~18 (methyl) alkyl acrylate.For example, as abovementioned alkyl, can Enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, amyl group, hexyl, cyclohexyl, heptyl, 2- ethylhexyls, different pungent Base, nonyl, decyl, isodecyl, dodecyl, different myristyl, lauryl, tridecyl, pentadecyl, cetyl, ten Seven alkyl, octadecyl etc..They can be used alone or are applied in combination.As the average carbon atom number of these alkyl, preferably For 3~9.
As form (methyl) acrylic polymer (a1) monomer, in addition to above-mentioned (methyl) alkyl acrylate, Carboxyl group-containing monomer, hydroxyl monomer, amide-containing monomer, (methyl) acrylate containing aromatic rings etc. can also be enumerated.
Carboxyl group-containing monomer is to contain carbonyl in its structure and contain the polymerisms such as (methyl) acryloyl group, vinyl not The compound of saturation double bond.As the concrete example of carboxyl group-containing monomer, can enumerate 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 containing hydroxyl and comprising polymerisms such as (methyl) acryloyl group, vinyl not The compound of saturation double bond.As the concrete example of hydroxyl monomer, can enumerate 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 containing amide groups and containing the polymerization such as (methyl) acryloyl group, vinyl in its structure 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, NIPA, N- methyl (methyl) acryloyl Amine, N- butyl (methyl) acrylamide, N- hexyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- methylols- N- propyl group (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 meeting the durability to transparency conducting layer Aspect is particularly preferred.
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 (particularly to the durability of transparency conducting layer).
As the concrete example of (methyl) acrylate containing aromatic rings, can enumerate for example：(methyl) benzyl acrylate, (methyl) phenyl acrylate, o-phenyl phenol (methyl) acrylate, (methyl) acrylate, (methyl) acrylic acid Phenoxy-propyl, phenoxy group diethylene glycol (methyl) acrylate, ethylene-oxide-modified nonyl phenol (methyl) acrylate, ring Oxidative ethane is modified cresols (methyl) acrylate, phenolethylene oxide is modified (methyl) acrylate, (methyl) acrylic acid 2- hydroxyls Base -3- phenoxy-propyls, (methyl) methoxyethyl benzyl ester, (methyl) acrylic acid benzyl chloride base ester, polystyrene (methyl) third Olefin(e) acid ester etc. has (methyl) acrylate of phenyl ring；Hydroxyethylation betanaphthol acrylate, (methyl) acrylic acid 2- naphthalene ethyls Ester, acrylic acid 2- naphthoxys ethyl ester, (methyl) acrylic acid 2- (4- methoxyl group -1- naphthoxys) ethyl ester etc. have (methyl) of naphthalene nucleus Acrylate；(methyl) biphenyl acrylate etc. has (methyl) acrylate of cyclohexyl biphenyl.
As above-mentioned (methyl) acrylate containing aromatic rings, from the aspect of adhesion characteristic, durability, preferred (first Base) benzyl acrylate, (methyl) acrylate, particularly preferred (methyl) acrylate.
Above-mentioned carboxyl group-containing monomer, hydroxyl monomer, amide-containing monomer, (methyl) acrylate containing aromatic rings are viscous Mixture composite (A1) containing crosslinking agent in the case of turn into reflecting point with crosslinking agent.Particularly carboxyl group-containing monomer, hydroxyl Monomer is due to high with the reactivity of intermolecular cross-linking agent, therefore, in order to improve obtained coherency, the heat resistance of adhesive phase Shi Youxuan is used.
It is preferred that (methyl) acrylic polymer (a1) that the present invention uses all is forming the weight of monomer (100 weight %) Contain above-mentioned each monomer as monomeric unit according to following amount in amount ratio.
The weight rate of above-mentioned (methyl) alkyl acrylate can be set to the list in addition to (methyl) alkyl acrylate The remainder of body, specifically, preferably more than 70 weight %.From the aspect of cementability is ensured, 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 below 2 weight %, more preferably 0.01~2 weight %, enters one Step is preferably 0.05~1.5 weight %, particularly preferably 0.05~1 weight %.The weight rate of carboxyl group-containing monomer is less than 0.01 During weight %, there is that durability can not be met, on the other hand, during more than 2 weight %, sometimes result in transparency conducting layer corruption Erosion, have the tendency of that this point of durability can not be met, not preferably.
The weight rate of hydroxyl monomer is preferably 0.01~7 weight %, more preferably 0.01~5 weight %, further Preferably 0.1~3 weight %, particularly preferably 0.2~2 weight %.The weight rate of hydroxyl monomer is less than 0.01 weight % When, the crosslinking of adhesive phase is insufficient, there is that durability, adhesion characteristic can not be met, on the other hand, more than 5 weight % When, have the tendency of that durability can not be met.
The weight rate of amide-containing monomer is preferably more preferably 0.1~8 weight % below 8 weight %, further excellent Elect 0.3~5 weight % as, be 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 tendency that can not meet to the durability of transparency conducting layer is especially in the presence of, separately When on the one hand, more than 8 weight %, there is durability reduction, not preferably.
The weight rate of (methyl) acrylate containing aromatic rings is preferably below 25 weight % more preferably 0~22 Weight %, more preferably 0~18 weight %.The weight rate of (methyl) acrylate containing aromatic rings is more than 25 weights When measuring %, there is durability reduction.
In above-mentioned (methyl) acrylic polymer (a1), in addition to above-mentioned monomeric unit, it is not necessary to especially contain There are other monomeric units, but for improvement cementability, the purpose of heat resistance, can will include (methyl) acryloyl group or vinyl More than a kind comonomer Deng the functional group of the polymerism with unsaturated double-bond is imported by being copolymerized.
As the concrete example of such comonomer, can enumerate：The list containing anhydride group such as maleic anhydride, itaconic anhydride Body；The caprolactone addition product of acrylic acid；Allyl sulphonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, (methyl) acryloyl Amine propane sulfonic acid, (methyl) acrylic acid sulphur propyl ester etc. contain sulfonic monomer；2- hydroxyethyl acryloyl phosphates etc. contain Monomer of phosphate etc..
In addition, the monomer example as modified purpose, can be enumerated：(methyl) acrylate, (methyl) acrylic acid N, (methyl) the acrylic acid alkylaminoalkyl esters such as N- dimethylamino ethyl esters, (methyl) tbutylaminoethylacrylate；(first Base) (methyl) alkoxyalkyl acrylate such as methoxyethyl acrylate, (methyl) ethoxyethyl acrylate；N- (methyl) Acryloyl-oxy methylene succinimide, N- (methyl) acryloyl group -6- epoxide hexa-methylenes succinimide, N- (methyl) The succinimide class monomers such as the methylene succinimide of acryloyl group -8- epoxides eight；N- N-cyclohexylmaleimides, N- isopropyls The maleimide monomers such as base maleimide, N- lauryls maleimide, N-phenylmaleimide；N- methyl clothing health Acid imide, N- ethyl clothing health acid imide, N- butyl clothing health acid imide, N- octyl group clothing health acid imide, N-2- ethylhexyl clothing health acyls Clothing health acid imide monomers such as imines, N- cyclohexyl clothing health acid imide, N- lauryl clothing health acid imides etc..
In addition, as modified monomer, the vinyl monomers such as vinyl acetate, propionate can also be used；Propylene The cyanoacrylate monomer such as nitrile, methacrylonitrile；(methyl) of (methyl) glycidyl acrylate etc. containing epoxy radicals Acrylate；Polyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy ethyl glycol (methyl) propylene Glycols (methyl) acrylate such as acid esters, methoxyl group polypropylene glycol (methyl) acrylate；(methyl) tetrahydrofurfuryl acrylate, (methyl) acrylate monomers such as fluorine (methyl) acrylate, organosilicon (methyl) acrylate, acrylic acid 2- methoxy acrylates Deng.In addition, isoprene, butadiene, isobutene, vinyl ethers etc. can be enumerated.
In addition, as the monomer other than the above that can be copolymerized, silanes monomer containing silicon atom etc. can be enumerated.As Silanes monomer, such as can enumerate：3- acryloxypropyls triethoxysilane, vinyltrimethoxy silane, vinyl Triethoxysilane, 4- vinyl butyls trimethoxy silane, 4- vinyl butyls triethoxysilane, 8- vinyl octyl group three Methoxy silane, 8- vinyl octyltri-ethoxysilane, 10- Methacryloxydecyls trimethoxy silane, 10- propylene Acyloxy decyl trimethoxy silane, 10- Methacryloxydecyls triethoxysilane, 10- acryloxies decyl three Ethoxysilane etc..
In addition, as comonomer, can enumerate：Tripropylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) third Olefin(e) acid ester, 1,6-HD two (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, neopentyl glycol Two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, Ji Wusi Alcohol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, in oneself Carboxylate of (methyl) acrylic acid such as ester modified dipentaerythritol six (methyl) acrylate and polyalcohol etc. has more than 2 The multi-functional monomer of the unsaturated double-bonds such as (methyl) acryloyl group, vinyl；In the bone of polyester, epoxy, carbamate etc. Addition has more than 2 as the unsaturation pair such as (methyl) acryloyl group with monomer component identical functional group, vinyl on frame Polyester (methyl) acrylate of key, epoxy (methyl) acrylate, carbamate (methyl) acrylate etc..
As the ratio of the above-mentioned comonomer in (methyl) acrylic polymer (a1), in above-mentioned (methyl) acrylic acid Birds of the same feather flock together in whole weight rates for forming monomer (100 weight %) of compound (a1), preferably 0~10 weight % or so is more excellent Elect 0~7 weight % or so, more preferably 0~5 weight % or so as.
(methyl) acrylic polymer (a1) of the present invention usually using weight average molecular weight be 1,000,000~2,500,000 it is poly- Compound.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 small It is not preferred in terms of heat resistance when 1,000,000.In addition, when weight average molecular weight is more than 2,500,000, adhesive has what is be easily hardened to incline To becoming easily to peel off.In addition, represent that weight average molecular weight (Mw)/number mean molecule quantity (Mn) of molecular weight distribution is preferred For more than 1.8 and less than 10, more preferably 1.8~7, more preferably 1.8~5.Molecular weight distribution (Mw/Mn) is more than 10 When, it is not preferred in terms of durability.It should be noted that weight average molecular weight, molecular weight distribution (Mw/Mn) are by passing through GPC (gels Permeation chromatography) measure and being converted by polystyrene obtains the value that calculates.
The manufacture of such (methyl) acrylic polymer (a1) can suitably select polymerisation in solution, polymerisation in bulk, breast Manufacture method known to liquid polymerization, various radical polymerizations etc..In addition, obtained (methyl) acrylic polymer can be nothing Advise any copolymers such as copolymer, 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, react under the nonactive air-flow such as nitrogen, add polymerization initiator, generally 50~70 DEG C or so, it is 5~30 small When or so reaction condition under carry out.
For polymerization initiator, chain-transferring agent, emulsifying agent for being used in radical polymerization etc., it is not particularly limited, can be with Appropriate selection uses.In addition, the weight average molecular weight of (methyl) acrylic polymer (a1) can turn according to polymerization initiator, chain Move the usage amount of agent, reaction condition and control, its usage amount is suitably adjusted according to its species.
As polymerization initiator, for example,：2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2- amidine propanes) Dihydrochloride, 2,2 '-azo two [2- (5- methyl -2- imidazoline -2- bases) propane] dihydrochloride, (the 2- methyl of 2,2 '-azo two Third amidine) dithionate, 2,2 '-azo two (N, N '-dimethyleneisobutylamidine), [N- (2- the carboxy ethyls) -2- of 2,2 '-azo two Methyl-prop amidine] hydrate (trade name：VA-057, and the pure medicine Co. Ltd. system of light) etc. azo-initiator, 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, TBHP, hydrogen peroxide, the combination of persulfate and sodium hydrogensulfite, peroxide Combination of compound and sodium ascorbate etc. is combined with redox type initiators that peroxide forms with reducing agent etc., but not It is defined in these.
Above-mentioned polymerization initiator can be used alone, and can also mix two or more use, its total content relative to monomer into The parts by weight of total amount 100 divided 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 for example using 2,2 '-azodiisobutyronitrile as polymerization initiator come manufacture it is above-mentioned it is heavy divide equally During (methyl) acrylic polymer (a1) of son amount, relative to the parts by weight of total amount 100 of monomer component, polymerization initiator makes Dosage is preferably set to 0.06~0.2 parts by weight or so, is more preferably set to 0.08~0.175 parts by weight or so.
In addition, chain-transferring agent, emulsifying agent etc. can suitably use known material.For its addition, Ke Yi Do not damage in the range of effect of the present invention and suitably determine.
A feature of the present invention is, epoxy silane coupling is contained in adhesive composition (A1).Pass through Contain epoxy silane coupling in adhesive composition (A1), the overall durability of liquid crystal panel can be improved, may be used also To suppress panel warpage, light leak.
Contain epoxy silane coupling as above-mentioned, such as can enumerate：3- glycidoxy-propyltrimethoxy silanes, 3- rings The third oxygen of oxygen propyl-triethoxysilicane, 3- glycidoxypropyls diethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl Trimethoxy silane etc..
In addition, in the present invention, as containing epoxy silane coupling, being preferably used in intramolecular has more than 2 alkane The oligomeric of epoxide silicyl contains epoxy silane coupling.Specifically, such as SHIN-ETSU HANTOTAI's chemical industry strain formula can be enumerated X-41-1053, X-41-1059A, X-41-1056 of commercial firm's manufacture etc..These coupling agents are not volatile, due to multiple alkane Epoxide silicyl and effectively improve durability, thus preferably.Oligomeric mentioned here refers to, 2 polymers of monomer with It is upper and less than the polymer of 100 polymers or so, as the weight average molecular weight of oligomeric silane coupler, preferably 300~ 30000 or so.
It is not particularly limited for the quantity of alkoxysilyl of the above-mentioned oligomeric containing epoxy silane coupling, It it is more than 2 in intramolecular.In addition, in silane coupler, the amount of the alkoxy of the above-mentioned silane coupler containing mercapto is excellent Elect 10~60 weight %, more preferably 15~50 weight %, more preferably 15~40 weight % as.
The species of alkoxy is not particularly limited, can be enumerated for example：Methoxyl group, ethyoxyl, propoxyl group, butoxy, penta The alkoxy of the carbon numbers such as epoxide, hexyloxy 1~6.Among these, preferably methoxyl group, ethyoxyl, more preferably methoxyl group.Separately Outside, it is also preferred that containing both methoxyl group and ethyoxyl in a molecule.
The above-mentioned epoxide equivalent containing epoxy silane coupling is preferably below 1000g/mol, more preferably 500g/mol Hereinafter, more preferably below 300g/mol.In addition, being not particularly limited to the lower limit of epoxide equivalent, such as it is preferably More than 200g/mol.
It is above-mentioned to can be used alone containing epoxy silane coupling, two or more use can also be mixed in addition, relative to upper The parts by weight of (methyl) acrylic polymer (a1) 100 are stated, its total content is preferably 0.001~5 parts by weight, more preferably 0.01 ~3 parts by weight, more preferably 0.02~2 parts by weight, particularly preferably 0.05~1 parts by weight.By being contained with above range Have and contain epoxy silane coupling, it is possible to increase the overall durability of liquid crystal panel, additionally it is possible to suppress panel warpage, light leak.
The middle addition of adhesive composition (A1) alternatively, it is also possible to be used in the present invention is coupled except above-mentioned containing epoxy radicals silicone hydride Other silane couplers beyond agent.As other coupling agents, can enumerate：3- TSL 8330s, N-2- (amino Ethyl) -3- amino propyl methyls dimethoxysilane, 3- triethoxysilicane alkyl-N- (1,3- dimethylbutylenes) propylamine, N- Phenyl-gamma-amino propyl trimethoxy silicane etc. containing amino silicane coupling agent, 3- acryloxypropyls trimethoxy silane, 3- methacryloxypropyls etc. contain the silane coupler, 3- NCOs third of (methyl) acryloyl group Silane coupler containing NCO such as ethyl triethoxy silicane alkane etc..Alternatively, it is also possible to add at adhesive composition (A2) The silane coupler containing mercapto of middle addition, but preferably contain mercapto silane coupler without this.
Except it is above-mentioned containing epoxy silane coupling in addition to other silane couplers can not damage effect of the present invention In the range of add, its addition is not particularly limited.
It is preferred that adhesive composition (A1) used in the present invention contains crosslinking agent.As crosslinking agent, can use organic Class crosslinking agent, multifunctional metallo-chelate.As organic crosslinking agent, isocyanates crosslinking agent, peroxide can be enumerated Crosslinking agent, epoxies crosslinking agent, imines crosslinking agent etc..Multifunctional metallo-chelate is that polyvalent metal and organic compound are covalent The chelate that bonding or coordination bonding form.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..As the original in the organic compound of covalent bonding or coordination bonding Son, oxygen atom etc. can be enumerated, as organic compound, Arrcostab, alcoholic compound, carboxylic acid compound, ether compound, ketone can be enumerated Compound etc..
As crosslinking agent, preferred isocyanate class crosslinking agent and/or peroxide crosslinking agent.
As isocyanates crosslinking agent, the compound at least with 2 NCOs can be used.For example, generally Using urethane react used in known aliphatic polyisocyante, alicyclic polyisocyanates, aromatic series it is more Isocyanates etc..
As aliphatic polyisocyante, can enumerate for example：Trimethylene diisocyanate, the isocyanic acid of tetramethylene two 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 isocyanate, can enumerate for example：1,3- cyclopentene diisocyanates, the isocyanic acid of 1,3- hexamethylenes two Ester, 1,4- cyclohexane diisocyanates, IPDI, hydrogenated diphenyl methane diisocyanate, hydrogenation of benzene two Methyl diisocyanate, hydrogenated toluene diisocyanate, hydrogenation tetramethyl xylylene diisocyanate etc..
As aromatic diisocyanate, can enumerate for example：Phenylene diisocyanate, 2,4 toluene diisocyanate, 2,6- Toluene di-isocyanate(TDI), 2,2 '-methyl diphenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 4,4 '-toluene Amine diisocyanate, 4,4 '-diphenyl ether diisocyanate, 4,4 '-biphenyl diisocyanate, 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.), the urethane-modified thing, urea modifier, the biuret that are formed with polyol reactions such as trimethylolpropanes change Property thing, allophanate-modified thing, isocyanurate-modified thing, Carbodiimide-Modified thing etc..
As the commercially available product of isocyanates crosslinking agent, can enumerate for example：Nippon Polyurethane Industry Co., Ltd.'s manufacture Trade name " Millionate MT ", " Millionate MTL ", " Millionate MR-200 ", " Millionate MR- 400 ", " Coronate L ", " Coronate HL ", " Coronate HX ", the trade name of Mitsui Chemicals, Inc's 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, caused stress is easily relaxed along with expansion/contraction of optical film, is not susceptible to peel off in endurancing. As aliphatic polyisocyante class compound, particularly preferred hexamethylene diisocyanate and its modifier.
As peroxide, as long as free radical spike is produced by heating or illumination and makes the base of adhesive composition The peroxide that plinth polymer ((methyl) acrylic polymer) is crosslinked, it is possible to it is suitable to use, but in view of operation Property, stability, preferably using the peroxide that 1 minute half life temperature is 80 DEG C~160 DEG C, more preferably declined using 1 minute half Phase temperature is 90 DEG C~140 DEG C of peroxide.
As the peroxide that can be used, can enumerate 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), (mistakes of 1,1- bis- The tertiary hexyl of oxidation) hexamethylene (1 minute half life temperature：149.2 DEG C) etc..Wherein, because cross-linking reaction efficiency is especially excellent, because This preferably uses dicetyl peroxydicarbonate two (4- tert-butylcyclohexyls) ester (1 minute half life temperature：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 representing peroxide, refer to until The residual quantity of peroxide turns into the time untill half.On the decomposition temperature that half-life period is obtained with random time, any temperature The lower half-life of degree, have in manufacturer's catalogue etc. described in, for example, being recorded in NOF Corp 《Organic peroxide catalogue the 9th edition (in May, 2003)》Deng.
Relative to the parts by weight of (methyl) acrylic polymer (a1) 100, the usage amount of crosslinking agent is preferably 0.01~2 weight Measure part, more preferably more preferably 0.02~1 parts by weight, 0.03~0.5 parts by weight.It should be noted that crosslinking agent is small When 0.01 parts by weight, exist adhesive phase crosslinking it is insufficient, durability, the hidden danger of adhesion characteristic, the opposing party can not be met Face, during more than 2 parts by weight, adhesive phase be present becomes the tendency that really up to the mark, durability declines.
Above-mentioned isocyanates crosslinking agent can be used alone, and two or more use can also be mixed, relative to above-mentioned The parts by weight of (methyl) acrylic polymer (a1) 100, its total content are preferably to contain 0.01~2 parts by weight, are more preferably contained There are 0.02~1 parts by weight, more preferably containing 0.03~0.5 parts by weight.It is contemplated that in cohesiveness, endurancing Prevent stripping etc. and suitably contain.
Above-mentioned peroxide can be used alone, and can also mix two or more use, relative to above-mentioned (methyl) third The parts by weight of alkene acids polymers (a1) 100, its total content is preferably 0.01~2 parts by weight, more preferably containing 0.04~1.5 weight Part is measured, more preferably containing 0.05~1 parts by weight.In order to adjust processability, operate (rework) property, cross-linked stable again Property, fissility etc., suitable selection within the range.
Adhesive composition (A1) used in the present invention can further contain ionic compound.It is used as ionicization Compound, as its addition, can not damage this hair it is preferable to use ionic compound usually used in this field Suitably determined in the range of obvious results fruit.
In adhesive composition used in the present invention (A1), the polyethers with reactive silicyl can be coordinated Compound.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 publications.
It can also contain other well known additive in adhesive composition used in the present invention (A1), such as can be with The powder of polyether compound, colouring agent, pigment etc. according to as use is properly added the PAGs such as polypropylene glycol Body, 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 thing etc..In addition, may be used also To use the redox class of addition reducing agent in the range of it can control.Relative to (methyl) acrylic polymer (a1) 100 parts by weight, these additives are preferably below 5 parts by weight, further preferably below 3 parts by weight, still more preferably 1 Used in scope below parts by weight.
(2) adhesive composition (A2)
Adhesive composition (A2) used in the present invention is containing (methyl) acrylic polymer (a2) and containing mercapto Silane coupler, preferably comprise (methyl) acrylic polymer (a2) and be used as principal component.Principal component referred to herein such as above institute Narration.
A feature of the present invention is, silane coupler containing mercapto is contained in adhesive composition (A2).Pass through Contain silane coupler containing mercapto in adhesive composition (A2), it is possible to increase the overall durability of liquid crystal panel, moreover it is possible to Enough suppress panel warpage, light leak.
As above-mentioned silane coupler containing mercapto, can enumerate：3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi first Base dimethoxysilane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyis methyldiethoxysilane, β-mercapto methyl benzene Base ethyl trimethoxy silane, mercapto methyl trimethoxy silane, 6- sulfydryl hexyls trimethoxy silane, 10- sulfydryls decyl three Methoxy silane etc. has compound of sulfydryl etc..
In addition, being used as silane coupler containing mercapto, preferably intramolecular is oligomeric with more than 2 alkoxysilyls Thing type silane coupler containing mercapto.Specifically, for example, the X-41- of Shin-Etsu Chemial Co., Ltd's manufacture can be enumerated 1805th, X-41-1818, X-41-1810 etc..These silane couplers containing mercapto are not volatile, due to multiple alkoxies Silicyl, and durability is effectively improved, thus preferably.Oligomeric mentioned here refers to, it is more than 2 polymers of monomer and It is left as the weight average molecular weight of oligomeric silane coupler, preferably 300~30000 less than the polymer of 100 polymers or so It is right.
The quantity of the alkoxysilyl of above-mentioned oligomeric silane coupler containing mercapto is not particularly limited, Intramolecular is more than 2.In addition, in silane coupler, the alkoxy of above-mentioned oligomeric silane coupler containing mercapto Amount be preferably 10~60 weight %, more preferably 20~50 weight %, more preferably 20~40 weight %.
The species of alkoxy is not particularly limited, can be enumerated for example：Methoxyl group, ethyoxyl, propoxyl group, butoxy, penta The alkoxy of the carbon numbers such as epoxide, hexyloxy 1~6.Among these, preferably methoxyl group, ethyoxyl, more preferably methoxyl group.Separately Outside, it is also preferred that containing both methoxyl group and ethyoxyl in a molecule.
For the content of the mercapto of the above-mentioned silane coupler containing mercapto, for example, in the case of sulfydryl, preferably For below mercapto equivalents 1000g/mol, more preferably below 800g/mol, more preferably below 500g/mol.It is in addition, right The lower limit of mercapto equivalents is not particularly limited, for example, it is preferable to be more than 200g/mol.
Above-mentioned silane coupler containing mercapto can be used alone, and two or more use can also be mixed, relative to above-mentioned The parts by weight of (methyl) acrylic polymer (a2) 100, its total content are preferably 0.001~5 parts by weight, more preferably 0.01~ 3 parts by weight, more preferably 0.02~2 parts by weight, particularly preferably 0.05~1 parts by weight.By being contained with above range Silane coupler containing mercapto, it is possible to increase the overall durability of liquid crystal panel, additionally it is possible to suppress panel warpage, light leak.
Alternatively, it is also possible to be added in adhesive composition used in the present invention (A2) except above-mentioned silane containing mercapto is even Join other silane couplers beyond agent.As other coupling agents, can enumerate：3- TSL 8330s, N-2- (ammonia Base ethyl) -3- amino propyl methyls dimethoxysilane, 3- triethoxysilicane alkyl-N- (1,3- dimethylbutylenes) propylamine, N- phenyl-gamma-amino propyl trimethoxy silicane etc. is containing amino silicane coupling agent, 3- acryloxypropyl trimethoxy silicon Alkane, 3- methacryloxypropyls etc. contain the silane coupler, 3- isocyanates of (methyl) acryloyl group Silane coupler containing NCO such as base propyl-triethoxysilicane etc..
Other silane couplers in addition to above-mentioned silane coupler containing mercapto can not damage effect of the present invention In the range of add, its addition is not particularly limited.
As (methyl) acrylic polymer (a2), can also preferably use by above-mentioned adhesive composition (A1) (methyl) acrylic polymer of any composition exemplified by (methyl) acrylic polymer (a1) used.In addition, with Adhesive composition (A1) is likewise it is possible to addition crosslinking agent, polyether compound, other additions in adhesive composition (A2) Agent etc., it is formed, addition is identical with adhesive composition (A1).But combined in adhesive composition (A1) and adhesive In thing (A2), the composition, addition of (methyl) acrylic polymer can be with identical, can also be different, crosslinking agent, polyethers chemical combination The species of thing and other additives, addition can be with identical, can also be different.
(3) adhesive phase
1st, the 2nd adhesive phase is formed by above-mentioned adhesive composition (A1), (A2).
The gel fraction of the 1st adhesive phase formed by adhesive composition (A1) is 65~90%, preferably 70~85%. In order to suppress to require the light leak in the display device of narrow edge, it is necessary to suppress the contraction of polarizing coating, the preferably hard person of adhesive phase. But on the other hand, it is not preferred from the viewpoint of durability when fitting in display unit if adhesive phase is really up to the mark. In the present invention, it is more than 65% by the gel fraction for making the 1st adhesive phase, light leak can be suppressed, and by making gel fraction For less than 90%, to the excellent in te pins of durability of transparency conducting layer, thus preferably.
For the gel fraction of the 2nd adhesive phase formed by adhesive composition (A2), based on the 1st adhesive phase The reasons why identical, it is 65~90%, more preferably 70~85%.By making the gel fraction of the 2nd adhesive phase be more than 65%, energy Enough suppress light leak.Moreover, by making gel fraction be less than 90%, to the excellent in te pins of durability of glass, thus preferably.
In addition, in the present invention, the gel fraction of above-mentioned 1st adhesive phase and the 2nd adhesive phase meets following formula (1)：
[mathematical expression 3]
The 1st adhesive phase of the transparency conducting layer of the one side of liquid crystal cells is formed at being formed at the another of liquid crystal cells The close situation of the hardness of the 2nd adhesive phase simultaneously can suppress the warpage of panel, by making gel fraction meet above range, The warpage of panel can be suppressed.Above range is preferably less than 0.1, and more preferably less than 0.05.
When forming the 1st, 2 adhesive phase, the overall addition of crosslinking agent is preferably adjusted, and take into full account crosslinking Treatment temperature Degree, 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 For less than 170 DEG C., can also be in addition, above-mentioned crosslinking Treatment can be carried out at the temperature at which the drying process of adhesive phase Crosslinking Treatment process is set to carry out after drying process in addition.
In addition, on the crosslinking Treatment time, it may be considered that productivity, operability and set, but usually 0.2~20 minute Left and right, 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, solvent etc. is volatilized, according further to needing to implement above-mentioned friendship Connection handles and forms adhesive phase, is then transferred to the adhesive phase on the substrate of the polarizing coating described below, liquid crystal cells； Above-mentioned adhesive composition can also be directly coated with above-mentioned polarizing coating, liquid crystal cells and form adhesive phase.In the present invention In, preferably pre-production polarizing coating with adhesive phase formed with adhesive phase on polarizing coating, then make the band adhesive phase Polarizing coating be attached at method on liquid crystal cells.
As above-mentioned base material, it is not particularly limited, can enumerates for example：The various base materials such as mold release film, transparent resin film base material.
As the method to above-mentioned base material, polarizing coating coating adhesive composition, various methods can be used.It is specific and Speech, can be enumerated for example：Spraying process, rolling method, roller lick rubbing method, gravure coating process, reverse rubbing method, roller brush method, spraying process, leaching Stain rolling method, stick coating method, knife coating, air knife coating method, curtain coating, die lip rubbing method, the extrusion coating methods using die coating machine etc. The methods of.
Drying condition (temperature, time) is not particularly limited, can be suitable according to the composition of adhesive composition, concentration etc. Setting, for example, being 80~170 DEG C or so, preferably 90~200 DEG C, and it is 1~60 minute, preferably 2~30 minutes.
Furthermore it is possible to implement crosslinking Treatment as needed after the drying, its condition is as above described.
The thickness (after drying) of adhesive phase is for example preferably 5~100 μm, more preferably 7~70 μm, is more preferably 10~50 μm.When the thickness of adhesive phase is less than 5 μm, the adaptation shortcoming to adherend be present, in high temperature, high temperature and humidity bar The insufficient tendency of durability under part.On the other hand, the thickness of adhesive phase be more than 100 μm when, to formed adhesive phase when Adhesive composition be coated, dry when, existing fully to dry, entrapped air pockets, produced on the face of adhesive phase Uneven thickness, apparent problem easily become significantly to be inclined to.
As the constituent material of above-mentioned mold release film, can enumerate for example：Polyethylene, polypropylene, polyethylene terephthalate The porous materials such as the resin films such as ester, polyester film, paper, cloth, non-woven fabrics, net, foamed sheet, metal foil and their layered product etc. are suitable Suitable slice substance etc., but from the aspect of surface smoothness is excellent, preferably using resin film.
As resin film, can enumerate 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, the releasing agent of chain alkyl class or fatty acid acyl amine, silicon dioxide powder etc. take off to above-mentioned mold release film Mould and antifouling process or type is coated to above-mentioned mold release film, is mixed into the antistatic process of type, evaporation type etc..Particularly, may be used Suitably to carry out the lift-off processings such as organosilicon processing, chain alkyl processing, fluorine processing by the surface to above-mentioned mold release film to enter One step improves the fissility relative to above-mentioned adhesive phase.
As above-mentioned transparent resin film base material, it 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- among these Esters resin, polyimide based resin and polyether sulfone resin.
The thickness of above-mentioned film base material is preferably 15~200 μm.
Furthermore it is also possible to there is tackifier coating between polarizing coating and adhesive phase.Material for forming tackifier coating It is not particularly limited, can enumerates for example：Various polymerization species, the colloidal sol of metal oxide, Ludox etc..Among these, especially It is preferred that use polymerization species.Above-mentioned polymerization species can be in solvent soluble type, water-dispersion type, water soluble type using form Any form.
As above-mentioned polymerization species, can enumerate for example：Polyurethane based resin, polyester resin, acrylic resin, polyethers Resinoid, cellulosic resin, polyvinyl alcohol resin, PVP, polystyrene resins etc..These are worked as In, particularly preferred polyurethane based resin, polyester resin, acrylic resin.Crosslinking can suitably be coordinated in these resins Agent.These other adhesive ingredients can be according to its purposes suitably using one kind or two or more.Do not have to the thickness of tackifier coating There are particular determination, preferably 5~300nm.
As the forming method of above-mentioned tackifier coating, it is not particularly limited, can be carried out by generally well-known method.Separately Outside, when forming tackifier coating, activation process can be implemented to above-mentioned iodine system polarizing coating.Activation process can use various methods, Such as sided corona treatment, low pressure UV processing, corona treatment etc..
As the method that adhesive phase is formed on the tackifier coating on polarizing coating, as above described.
In addition, the feelings that the adhesive phase on adhesive phase, liquid crystal cells in the above-mentioned polarizing coating with adhesive phase exposes Under condition, mold release film (barrier film) can be used to protect adhesive phase untill it is for use.As mold release film, it can enumerate and above chat The mold release film stated.It is viscous in mold release film by making in the case where using mold release film as base material when making above-mentioned adhesive phase Mixture layer is bonded with polarizing coating or liquid crystal cells, the mold release film can as the polarizing coating with adhesive phase, with adhesive phase The mold release film of the adhesive phase of liquid crystal cells uses, and can simplify in terms of process.
In addition, as the 1st polarizing coating, the 2nd polarizing coating, be not particularly limited, but be generally used in polarizer one side or Two sides has the polarizing coating of transparent protective film.
It is not particularly limited for polarizer, various polarizers can be used.As polarizer, can enumerate for example：Make iodine, Dichroic substance as dichroic dye is adsorbed in polyvinyl alcohol film, part formalizing polyvinyl alcohol film, ethene-second The hydrophilic macromolecule films such as the partly-hydrolysed film of vinyl acetate copolymer class and film obtained from carrying out simple tension, polyvinyl alcohol The polyenoid based oriented film such as desalination acid treatment thing etc. of dewater treatment thing, polyvinyl chloride.Among these, preferably by polyvinyl alcohol film The iodine system polarizer of the polarizer, further preferably iodine and/or iodide ion that are formed with dichroic substances such as iodine.In addition, for this The thickness of a little polarizers is not particularly limited, usually 5~80 μm or so.
Polyvinyl alcohol film is dyed and carried out with iodine polarizer that simple tension forms for example can be by by polyvinyl alcohol It is impregnated in the aqueous solution of iodine dyeing and be stretched to former long 3~7 times and makes.Can also be impregnated in as needed boric acid, Or in the aqueous solution of KI optionally comprising zinc sulfate, zinc chloride etc. etc..Further, can also be incited somebody to action as needed before dyeing Polyvinyl alcohol film immersion is washed in water.By being washed to polyvinyl alcohol film, except polyethylene can be washed away Beyond the dirt on alcohols film surface, antiblocking agent, also have that to dye polyvinyl alcohol membrane swelling and preventing unequal uneven Effect.Stretching can be carried out being dyed using iodine after, can also Edge Coloring side stretch, it can in addition contain stretched Dyed afterwards using iodine.It can also be stretched in the aqueous solution of boric acid, KI etc. or water-bath.
As the material for the transparent protective film for forming the one or two sides for being arranged on above-mentioned polarizer, can be used for example transparent The excellent thermoplastic resin such as property, mechanical strength, heat endurance, moisture barrier, isotropism.As such thermoplastic resin The concrete example of fat, the celluosic resins such as cellulose triacetate, polyester resin, polyethersulfone resin, polysulfone resin, poly- carbonic acid can be enumerated 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 bond layer, and (methyl) acrylic compounds, carbamate are used in opposite side The thermosetting resins such as class, propenoic methyl carbamate class, epoxies, organic silicon or ultraviolet curing resin are as transparent guarantor Cuticula.The suitable additive of a kind of any of the above can also be contained in transparent protective film.As additive, can enumerate for example ultraviolet Light absorbers, age resister, lubricant, plasticizer, releasing agent, anti-coloring agent, fire retardant, nucleator, antistatic additive, pigment, Colouring agent etc..The content of above-mentioned thermoplastic resin in transparent protective film is preferably 50~100 weight %, and more preferably 50~99 Weight %, more preferably 60~98 weight %, particularly preferably 70~97 weight %.Above-mentioned thermoplastic in transparent protective film When the content of property resin is below 50 weight %, it is possible to can not fully show high transparency possessed by thermoplastic resin script Property.
The thickness of diaphragm can be determined suitably, but from the operability such as intensity, treatability, film etc., be led to It is often 1~500 μm or so.
Above-mentioned polarizer is closely sealed generally by aqueous adhesive etc. with diaphragm.As aqueous adhesive, can example go out it is different Cyanate bonding agent, polyvinyl alcohol bonding agent, gelatin class bonding agent, ethene base system latex class, aqueous polyurethane, Waterborne polyester etc..Than that described above, as polarizer and the bonding agent of transparent protective film, can enumerate uv-curing type bonding agent, Electronic beam solidified bonding agent etc..Electronic beam solidified polarizing coating is shown well with bonding agent to above-mentioned various transparent protective films Cementability.Alternatively, it is also possible to contain metallic compound filler in the bonding agent of the invention used.
In addition, in the present invention, phase retardation film etc. can also be formed on polarizer to replace the transparency protected of polarizing coating Film.Furthermore it is also possible to other transparent protective films are further set on transparent protective film or phase retardation film etc. is set.
It can also implement in the one side for not being bonded the side opposite with liquid crystal cells (visible side) of above-mentioned transparent protective film Hard conating, antireflection process, the processing of anti-bonding, the processing carried out for the purpose of spreading or be anti-dazzle.
(4) composition of liquid crystal panel
The composition of liquid crystal panel of the present invention is, liquid crystal cells one side formed with transparency conducting layer, transparent led at this The 1st polarizing coating is bonded by the adhesive phase formed by adhesive composition (A1) in electric layer, on the another side of liquid crystal cells 2nd polarizing coating is bonded by the adhesive phase formed by adhesive composition (A2), wherein,
Above-mentioned adhesive composition (A1) includes (methyl) acrylic polymer (a1) and containing epoxy silane coupling,
Above-mentioned adhesive composition (B2) includes (methyl) acrylic polymer (a2) and silane coupler containing mercapto, And the gel fraction of the 1st adhesive phase of control and the 2nd adhesive phase, it is constructed without particular determination to other.Based on Fig. 1 to the present invention The mode of specific composition of liquid crystal panel illustrate, but the present invention is not limited by it
As the mode of the liquid crystal panel 11 of the invention shown in Fig. 1, as described below.
Liquid crystal cells 10 include liquid crystal layer 8, be configured at the liquid crystal layer 8 side the 1st transparency carrier 7 (visible side), with And the 2nd transparency carrier 9 (light source side) of the opposite side of the liquid crystal layer is configured at, led on the 1st transparency carrier 7 formed with transparent Electric layer 6.In the transparency conducting layer side of the liquid crystal cells across the 1st adhesive phase 5a laminations formed by adhesive composition (A1) There is the 1st polarizing coating 4a.1st polarizing coating 4a has between visible side transparent protective film 1a and liquid crystal cell side transparent protective film 3a Polarizer 2a.In addition, in the side opposite with transparency conducting layer of liquid crystal cells, across what is formed by adhesive composition (A2) 2nd adhesive phase 5b laminations have the 2nd polarizing coating 4b.2nd polarizing coating 4b is saturating in light source side transparent protective film 3b and liquid crystal cell side There is polarizer 2b between bright diaphragm 1b.
In Fig. 1 liquid crystal panel 11, the 1st polarizing coating 4a and the 2nd polarizing coating 4b are used to be had on the two sides of polarizer The two-sided protection polarizing coating of transparent protective film, but the one side that only there is transparent protective film in the one side of polarizer can also be used to protect Polarizing coating is protected to replace two-sided protection polarizing coating.Alternatively, it is also possible to replace polarizing coating 4a, 4b liquid crystal list using phase separation layer First side transparent protective film (3a, 1b), furthermore it is also possible to across adhesive phase on liquid crystal cell side transparent protective film (3a, 1b) Further form phase separation layer.
In addition, in addition to above-mentioned composition, phase retardation film, compensation film for angular field of view, bright can be appropriately arranged with liquid crystal panel 11 Degree improves the optical films such as film.
As liquid crystal layer 8, it is not particularly limited, can be used for example：Any classes such as TN types, STN types, π types, VA types, IPS types The liquid crystal layer of type.In addition, form the 1st transparency carrier 7 (visible side) of liquid crystal cells 10 and be configured at the opposite side of the liquid crystal layer The 2nd transparency carrier 9 (light source side) as long as its raw material is not particularly limited, can enumerate example by all transparent substrate Such as：Glass, transparent resin film base material.As transparent resin film base material, can enumerate before the base material that is described.
As the 1st, the 2nd bonding formed by the 1st polarizing coating 4a, the 2nd polarizing coating 4b, adhesive composition (A1) or (A2) Oxidant layer, as above described.
As the constituent material of above-mentioned transparency conducting layer 6, be not particularly limited, can be used selected from indium, tin, zinc, gallium, antimony, The metal oxide of at least one of titanium, silicon, zirconium, magnesium, aluminium, gold, silver, copper, palladium, tungsten metal.Also may be used in the metal oxide With as needed further containing above-mentioned shown metallic atom.For example, it is preferable to using the indium oxide (ITO) containing tin oxide, Tin oxide containing antimony etc., particularly preferably using ITO.As ITO, the weight % of indium oxide 80~99 and tin oxide 1 are preferably comprised ~20 weight %.
In addition, as above-mentioned ITO, crystalline ITO, amorphism (amorphous) ITO can be enumerated, is suitable for using.
The thickness of above-mentioned transparency conducting layer 6 is not particularly limited, preferably more than 10nm, more preferably 15~40nm, More preferably 20~30nm.
As the forming method of above-mentioned transparency conducting layer 6, it is not particularly limited, known method can be used.Tool For body, can example go out such as vacuum vapour deposition, sputtering method, ion plating method.Used alternatively, it is also possible to thickness as needed Suitable method.
In addition, as needed, can also be set between the transparency carrier 7 of transparency conducting layer 6 and the 1st priming coat, prevent it is oligomeric Nitride layer etc..
The present invention liquid crystal panel by the transparency conducting layer of the one side positioned at liquid crystal cells across by specifically gluing The 1st adhesive phase that mixture composite is formed configures the 1st polarizing coating and in another side (face of light source side, the glass of liquid crystal cells Face) across the 2nd adhesive phase the 2nd polarizing coating of configuration formed by specific adhesive composition, thereby, it is possible to improve liquid crystal surface The overall durability of plate, additionally it is possible to suppress panel warpage, light leak.
2. image display device
The image display device of the present invention includes the liquid crystal panel of the present invention.Hereinafter, as an example, to liquid crystal display Device illustrates, but the present invention can be applicable to any display device of liquid crystal panel.
As the concrete example of the image display device for the liquid crystal panel that can apply the present invention, can enumerate：Liquid crystal display fills Put, organic electroluminescent (EL) display, plasma scope (PD), field-emitter display (FED：Field Emission Display) etc..
As long as the image display device of the present invention includes the liquid crystal panel of the present invention, other compositions and conventional image Display device is identical.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited to the examples.Need Illustrate, place that condition is all 23 DEG C, 65%R.H. without the room temperature of special provision.
The measure ＞ of the weight average molecular weight of ＜ (methyl) acrylic polymer
The weight average molecular weight (Mw) of (methyl) acrylic polymer is determined by GPC (gel permeation chromatography).On Mw/Mn, similarly it is determined.
Analytical equipment：HLC-8120GPC, TOSOH Co., Ltd's system
Post：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 specimen：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 1 minute one side of an Edge Coloring be stretched to 3 times.Then, 60 DEG C, the boric acid comprising 4 weight % concentration, 10 weight % concentration Impregnated in the aqueous solution of KI 0.5 minute while being stretched to total stretching ratio as 6 times.Next, by 30 DEG C, contain Have in the aqueous solution of the KI of 1.5 weight % concentration and impregnate 10 seconds and cleaned, then carried out 4 minutes at 50 DEG C Drying, obtained the polarizer of 30 μm of thickness.It is bonded on the two sides of the polarizer by polyvinyl alcohol bonding agent through saponification 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))
Added in the 4 neck flasks for possessing stirring vane, thermometer, nitrogen ingress pipe, condenser and contain butyl acrylate The monomer mixture of 99 parts by weight, the parts by weight of acrylic acid 4- hydroxybutyls 1.Further, relative to above-mentioned monomer mixture (Gu Body composition) 100 parts by weight, 2 as polymerization initiator, 2 '-azodiisobutyronitrile are added together with the parts by weight of ethyl acetate 100 0.1 parts by weight, be slowly stirred while import nitrogen carry out nitrogen displacement after, make the liquid temperature in flask be held in 55 DEG C it is attached Closely, the polymerisation of 8 hours is carried out, is prepared for the acrylic polymer that weight average molecular weight (Mw) is 3.2 for 1,560,000, Mw/Mn (a-1) solution.
Production Example 3,4
Except change as shown in table 1 the monomer used in Production Example 2 when preparing acrylic polymer species, Beyond its use ratio, according to the method same with Production Example 2, acrylic polymer (a-2), the solution of (a-3) are prepared for.
[table 1]
Abbreviation difference in table 1 is as described below.
BA：Butyl acrylate
NVP：NVP
AA：Acrylic acid
HBA：Acrylic acid 4- hydroxybutyls
Embodiment 1
(preparations of acrylic pressure-sensitive adhesive compositions (A1))
Relative to the parts by weight of solid constituent 100 of the solution of the acrylic polymer (a-1) obtained in Production Example 2, match somebody with somebody 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 BMT40SV, NOF Corp's system) and γ- Glycidoxy-propyltrimethoxy silane (trade name：KBM-403, Shin-Etsu Chemial Co., Ltd's system) 0.3 part, it is prepared for third The solution of olefin(e) acid class adhesive composition (A1).
(preparations of acrylic pressure-sensitive adhesive compositions (A2))
Relative to the parts by weight of solid constituent 100 of the solution of the acrylic polymer (a-1) obtained in Production Example 2, match somebody with somebody 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 BMT40SV, NOF Corp's system) and 3- mercaptos Base propyl trimethoxy silicane (trade name：KBM-803, Shin-Etsu Chemial Co., Ltd's system) 0.3 part, it is prepared for acrylic compounds The solution of adhesive composition (A2).
(making of the polarizing coating with adhesive phase)
By the solution coating of acrylic pressure-sensitive adhesive compositions (A1) in polyethylene terephthalate film (barrier film, business The name of an article：MRF38, Mitsubishi Plastics Inc's system) through organic silicon remover handle one side on, at 155 DEG C carry out 1 point The drying of clock so that the thickness of dried adhesive phase is 23 μm, and adhesive phase is formd on the surface of barrier film.Next, It will be formed in the adhesive phase on barrier film to be transferred on the polarizing coating of the making of Production Example 1, made the polarizing coating with adhesive phase (A1).In addition, using acrylic pressure-sensitive adhesive compositions (A2) solution, by identical method, band adhesive phase has been made Polarizing coating (A2).
Embodiment 2~12, comparative example 1~10
In embodiment 1, acrylic polymer (a1), the species of (a2), silane coupler are changed as shown in table 2 Species, its addition, in addition, according to method similarly to Example 1 be prepared for acrylic pressure-sensitive adhesive compositions (A1), (A2) solution.Using the solution of obtained acrylic pressure-sensitive adhesive compositions, by method similarly to Example 1, make Polarizing coating with adhesive phase.
Abbreviation difference in table 2 is as described below.
Isocyanates：Trade name：Takenate D160N, trimethylolpropane hexamethylene diisocyanate, three wells KCC's system
Peroxide：Trade name：Nyper BMT 40SV, benzoyl peroxide, NOF Corp's system
KBM403：γ-glycidoxypropyltrimethoxy silane, trade name：KBM-403, SHIN-ETSU HANTOTAI's chemical industry strain formula meeting Society manufactures
KBM803：3-mercaptopropyi trimethoxy silane, trade name：KBM-803, Shin-Etsu Chemial Co., Ltd's manufacture
X-41-1056：Oligomeric contains epoxy silane coupling, alcoxyl base unit weight：17 weight %, epoxide equivalent：280g/ Mol, Shin-Etsu Chemial Co., Ltd's manufacture
X-41-1810：Oligomeric sulfydryl contains silane coupler, alcoxyl base unit weight：30 weight %, mercapto equivalents：450g/ Mol, Shin-Etsu Chemial Co., Ltd's manufacture
KBM-5103：3- acryloxypropyl trimethoxy silanes, Shin-Etsu Chemial Co., Ltd's manufacture
KBE-9007：3- isocyanates propyl-triethoxysilicanes, Shin-Etsu Chemial Co., Ltd's manufacture
Following evaluation has been carried out to the polarizing coating with adhesive phase obtained in above-described embodiment and comparative example, evaluation has been tied Fruit is shown in table 3.
The making ＞ of ＜ liquid crystal panels
The polarizing coating (A1) with adhesive phase and (A2) that embodiment and comparative example are obtained are cut into 109mm × 59mm's Size.In the case of the polarizing coating (A1) with adhesive phase, carry out the absorption axiss of the Polarizer mode parallel with short side Cut, in the case of the polarizing coating (A2) with adhesive phase, make the absorption axiss of Polarizer with the parallel mode of long side carry out Cut.Polarizing coating (A1) with adhesive phase is pasted on to 110mm × 60mm, thick 0.32mm liquid crystal panel using laminating machine Ito surface, and the polarizing coating (A2) with adhesive phase is pasted on glass surface.Next, carried out 15 minutes with 50 DEG C, 0.5MPa Autoclave process, make polarizing coating completely closely sealed with liquid crystal panel, as evaluation liquid crystal panel.In addition, it is pasted on liquid crystal panel Ito surface and the polarizing coating (A1) with adhesive phase of glass surface, (A2) such as each embodiment, comparative example in the band bonding that makes Described in the combination of the polarizing coating (A1), (A2) of oxidant layer.
＜ panel warpages ＞
The evaluation liquid crystal panel of making is exposed 24 hours under 80 DEG C of atmosphere.By the liquid crystal panel after exposure in room After the lower placement of temperature 1 hour, according to the direction of warpage, it is positioned in a manner of upwarping four angles on flat platform, uses laser Displacement meter (ProductName：LK-G35, Keyence company system) determine the height at four angles.Will be to four respective measured values in angle Carry out it is average obtained by value as amount of warpage, judged according to following metewand.
○：Amount of warpage is less than 0.2mm
△：Amount of warpage is 0.2mm less than 0.5mm
×：Amount of warpage is more than 0.5mm
＜ endurancings ＞
(heat run) after 85 DEG C of lower 500 hours of atmosphere is placed in liquid crystal panel to the evaluation of making and is placed in 60 DEG C, 95%R.H. atmosphere is after lower 500 hours (humidification experiment), the foaming for the adhesive phase that detects by an unaided eye, peel off, according to Under metewand evaluated.
(metewand)
◎：Completely without apparent changes such as foaming, strippings.
○：End is slightly peeled off or foamed, but is had no problem in actual use.
△：There are stripping or foaming in end, but if not being special purposes, then has no problem in actual use.
×：There is significant stripping end, problem in actual use be present.
＜ light leaks ＞
Liquid crystal panel after 85 DEG C of endurancing is positioned under the transmitted light from backlight in darkroom, observe from Polarizer end whether there is light leak, is evaluated according to following metewand.
○：Without light leak.
×：There is light leak.
[table 3]

Claims (10)

1. a kind of liquid crystal panel, its liquid crystal cells one side formed with transparency conducting layer, on the transparency conducting layer by by The 1st adhesive phase that adhesive composition (A1) is formed is bonded the 1st polarizing coating, by by bonding on the another side of liquid crystal cells The 2nd adhesive phase that agent composition (A2) is formed is bonded the 2nd polarizing coating, wherein,
Described adhesive composition (A1) includes (methyl) acrylic polymer (a1) and containing epoxy silane coupling,
Described adhesive composition (A2) includes (methyl) acrylic polymer (a2) and silane coupler containing mercapto,
The gel fraction of 1st adhesive phase and the 2nd adhesive phase is more than 65% and less than 90%, and meets following formula (1),
[mathematical expression 1]
2. liquid crystal panel as claimed in claim 1, wherein, the epoxy silane coupling that contains is that have 2 in intramolecular The oligomeric of above alkoxysilyl contains epoxy silane coupling.
3. liquid crystal panel as claimed in claim 1 or 2, wherein, the silane coupler containing mercapto is that have 2 in intramolecular The oligomeric silane coupler containing mercapto of individual above alkoxysilyl.
4. such as liquid crystal panel according to any one of claims 1 to 3, wherein, relative to (methyl) acrylic The parts by weight of thing (a1) 100, the use level containing epoxy silane coupling are 0.001~5 parts by weight.
5. such as liquid crystal panel according to any one of claims 1 to 4, wherein, relative to (methyl) acrylic The parts by weight of thing (a2) 100, the use level of the silane coupler containing mercapto is 0.001~5 parts by weight.
6. such as liquid crystal panel according to any one of claims 1 to 5, wherein, (methyl) acrylic polymer (a1) And/or (a2) contains the weight % of carboxyl group-containing monomer 0.01~2 as monomeric unit.
7. such as liquid crystal panel according to any one of claims 1 to 6, wherein, (methyl) acrylic polymer (a1) And/or (a2) contains the weight % of amide-containing monomer 0.1~8 as monomeric unit.
8. such as liquid crystal panel according to any one of claims 1 to 7, wherein, (methyl) acrylic polymer (a1) And/or (a2) contains the weight % of hydroxyl monomer 0.01~7 as monomeric unit.
9. such as liquid crystal panel according to any one of claims 1 to 8, wherein, described adhesive composition (A1) and/or (A2) Containing selected from least one of isocyanates crosslinking agent and peroxide crosslinking agent crosslinking agent.
10. a kind of image display device, it use liquid crystal panel according to any one of claims 1 to 9.
CN201680018048.2A 2015-03-31 2016-03-18 Liquid crystal panel and image display device Active CN107430300B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2015072681A JP6068543B2 (en) 2015-03-31 2015-03-31 Liquid crystal panel and image display device
JP2015-072681 2015-03-31
PCT/JP2016/058794 WO2016158513A1 (en) 2015-03-31 2016-03-18 Liquid crystal panel and image display device

Publications (2)

Publication Number Publication Date
CN107430300A true CN107430300A (en) 2017-12-01
CN107430300B CN107430300B (en) 2020-10-20

Family

ID=57004252

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201680018048.2A Active CN107430300B (en) 2015-03-31 2016-03-18 Liquid crystal panel and image display device

Country Status (5)

Country Link
JP (1) JP6068543B2 (en)
KR (1) KR101948462B1 (en)
CN (1) CN107430300B (en)
TW (2) TWI677736B (en)
WO (1) WO2016158513A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018181479A1 (en) 2017-03-28 2018-10-04 日東電工株式会社 In-cell liquid crystal panel and liquid crystal display device
JP6596533B2 (en) * 2018-03-30 2019-10-23 日東電工株式会社 Polarizing film with adhesive layer and image display device
JP2019215573A (en) * 2019-08-28 2019-12-19 日東電工株式会社 Polarizing film with adhesive layer and image display device
JP6970723B2 (en) * 2019-10-04 2021-11-24 日東電工株式会社 Display device and base material laminate

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000155213A (en) * 1998-11-19 2000-06-06 Nitto Denko Corp Wide view angle polarizing plate and liquid crystal display device
CN1757664A (en) * 2004-09-17 2006-04-12 住友化学株式会社 Optical laminate
CN1862330A (en) * 2005-01-27 2006-11-15 琳得科株式会社 Pressure sensitive adhesive for polarizing plates, polarizing plate with pressure sensitive adhesive and production process for polarizing plate
CN103261350A (en) * 2010-12-13 2013-08-21 日东电工株式会社 Adhesive composition for optical films, adhesive layer for optical films, adhesive optical film and image display device
TW201431997A (en) * 2012-12-28 2014-08-16 Nitto Denko Corp Aqueous dispersion-type adhesive composition for transparent conductive layer, adhesive layer for transparent conductive layer, optical film with adhesive layer, and liquid crystal display device
WO2014208696A1 (en) * 2013-06-28 2014-12-31 日東電工株式会社 Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer for transparent conductive layer, laminate, and image display device
JP2015010195A (en) * 2013-06-28 2015-01-19 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200535517A (en) * 2003-12-26 2005-11-01 Zeon Corp Polarizing plate protective film, polarizing plate with reflection preventing function and optical product
JPWO2006019086A1 (en) * 2004-08-17 2008-05-08 日本ゼオン株式会社 N3204PCT
TW200630226A (en) * 2004-11-09 2006-09-01 Zeon Corp Antireflective film, polarizing plate and display
KR101299025B1 (en) * 2005-05-12 2013-08-27 니폰 가야꾸 가부시끼가이샤 Photosensitive Resin Compositions, Cured Articles of The Compositions, And Films Containing The Compositions
JP4697871B2 (en) * 2005-10-20 2011-06-08 日東電工株式会社 Laminated film
JP5145081B2 (en) * 2008-03-04 2013-02-13 京セラドキュメントソリューションズ株式会社 Error prediction device
JP5517831B2 (en) * 2010-08-19 2014-06-11 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet
JP5967654B2 (en) * 2012-11-28 2016-08-10 日本化薬株式会社 Resin composition and cured product thereof (2)
JP6472172B2 (en) * 2013-06-28 2019-02-20 日東電工株式会社 Optical film pressure-sensitive adhesive composition, optical film pressure-sensitive adhesive layer, optical film with pressure-sensitive adhesive layer, liquid crystal display device, and laminate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000155213A (en) * 1998-11-19 2000-06-06 Nitto Denko Corp Wide view angle polarizing plate and liquid crystal display device
CN1757664A (en) * 2004-09-17 2006-04-12 住友化学株式会社 Optical laminate
CN1862330A (en) * 2005-01-27 2006-11-15 琳得科株式会社 Pressure sensitive adhesive for polarizing plates, polarizing plate with pressure sensitive adhesive and production process for polarizing plate
CN103261350A (en) * 2010-12-13 2013-08-21 日东电工株式会社 Adhesive composition for optical films, adhesive layer for optical films, adhesive optical film and image display device
TW201431997A (en) * 2012-12-28 2014-08-16 Nitto Denko Corp Aqueous dispersion-type adhesive composition for transparent conductive layer, adhesive layer for transparent conductive layer, optical film with adhesive layer, and liquid crystal display device
WO2014208696A1 (en) * 2013-06-28 2014-12-31 日東電工株式会社 Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer for transparent conductive layer, laminate, and image display device
JP2015010195A (en) * 2013-06-28 2015-01-19 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet

Also Published As

Publication number Publication date
TWI645233B (en) 2018-12-21
JP6068543B2 (en) 2017-01-25
TWI677736B (en) 2019-11-21
CN107430300B (en) 2020-10-20
WO2016158513A1 (en) 2016-10-06
JP2016191865A (en) 2016-11-10
KR20170117556A (en) 2017-10-23
KR101948462B1 (en) 2019-02-14
TW201841028A (en) 2018-11-16
TW201702700A (en) 2017-01-16

Similar Documents

Publication Publication Date Title
CN103917617B (en) Adhesive composition, adhesive layer, polarizing film provided with adhesive layer, and image formation device
CN105339455B (en) Pressure-sensitive adhesive for optical films composition, pressure-sensitive adhesive for optical films layer, band adhesive phase optical film, liquid crystal display device and laminated body
CN103571403B (en) Adhesive, adhesive phase and bonding sheet
CN104046286B (en) Polarizing coating and image display device with adhesive phase
TWI518158B (en) Adhesive composition for optical film, adhesive layer for optical film, adhesive type optical film and image display device
CN107636499A (en) The polarizing coating and image display device of the subsidiary adhesive phase in two sides
CN108873139A (en) Band adhesive phase polarizing film and image display device
CN110172311A (en) Adhesive composition, adhesive phase, polarizing coating and image display device with adhesive phase
CN103571354B (en) Pressure-sensitive adhesive sheet, electrically or electronically bulking block laminate and optical member laminate
CN103917618B (en) Adhesive composition, adhesive phase, the polarizing coating of band adhesive phase and image processing system
CN104981529A (en) Adhesive composition for acrylic-based or cycloolefin-based polarizing film, adhesive layer, acrylic-based or cycloolefin-based polarizing film having adhesive layer, and image formation device
CN105954827B (en) Polarizing film with adhesive phase and image display device
CN107922807A (en) Optical component adhesive phase, optical component and image display device with adhesive phase
CN107250309B (en) Adhesive composition, adhesive phase, bonding sheet, optical component and image display device with adhesive phase
CN103562759A (en) Polarizing film with adhesive layer and image display apparatus
CN109423231A (en) Adhesive sheet and display body
CN103917616A (en) Adhesive agent composition, adhesive agent layer, polarizing plate provided with adhesive agent layer, and image formation device
CN109790420A (en) Optics adhesive phase, the manufacturing method of optics adhesive phase, optical film and image display device with adhesive phase
CN106189942A (en) Adhesive composition and adhesive film
CN107430300A (en) Liquid crystal panel and image display device
CN109790422A (en) Optics adhesive phase, the manufacturing method of optics adhesive phase, optical film and image display device with adhesive phase
CN108690519A (en) Pressure-sensitive-adhesive composition, contact adhesive, pressure sensitive adhesion sheet and display body
JP7128945B2 (en) Optical adhesive layer, method for producing optical adhesive layer, optical film with adhesive layer, and image display device
TW201910470A (en) Adhesive layer, optical film with adhesive layer, optical laminate and image display device
CN107429135A (en) Polarizing coating adhesive composition, polarizing coating adhesive phase, polarizing coating and image display device with adhesive phase

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant