CN106010384A

CN106010384A - Optical film with adhesive layer and liquid crystal display device

Info

Publication number: CN106010384A
Application number: CN201610187070.1A
Authority: CN
Inventors: 浅津悠司; 阪上智惠; 韩银九
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2015-03-31
Filing date: 2016-03-29
Publication date: 2016-10-12
Anticipated expiration: 2036-03-29
Also published as: JP6744115B2; JP2016194071A; KR102507237B1; TWI692514B; TW201700688A; CN106010384B; KR20160117296A

Abstract

The invention provides an optical film with an adhesive layer comprising an optical film and an adhesive layer laminated on at least one surface thereof. The adhesive layer is formed by adhesive composition containing a (meth)acrylic resin (A), a silane compound (B), and an ionic compound (C). The silane compound (B) is represented by a formula (I). The anion of the ionic compound is an anion selected from a predetermined group. The invention also provides a liquid crystal display device containing the optical film with the adhesive layer.

Description

Blooming and liquid crystal indicator with adhesive phase

Technical field

The present invention relates to the blooming with adhesive phase and comprise the liquid crystal indicator of this blooming.

Background technology

Make with the fit polarization plates blooming as representative of transparent resin film of the one or both sides stacking at polaroid It is widely used for constituting the optical component of the image display devices such as liquid crystal indicator.The blooming warp of polarization plates etc Often (such as joined with other component (liquid crystal cells etc. in such as liquid crystal indicator) laminating use across adhesive phase by folder According to Japanese Unexamined Patent Publication 2010-229321 publication).Accordingly, as blooming, it is known to be previously provided with binding agent in one face The blooming with adhesive phase of layer.It addition, in order to give anti-static electricity interference, it is also known that have contain within the adhesive layer from The blooming of sub-property compound.

Summary of the invention

In recent years, liquid crystal indicator is extended to smart mobile phone and panel type terminal, vehicle-mounted navigation system as generation The mobile device purposes with touch panel function of table.With adhesive phase in this kind of touch input formula liquid crystal indicator Blooming the most also its adhesive phase is such as pressed from both sides across resin bed or is directly contact configured at such as by metal line On the metal level constituted.But, in the metal level being made up of metal material and the adhesive phase group containing ionic compound In the composition closed, under hot and humid environment, have metal level the situation of corrosion occurs.In the middle of corrosion, owing to spot corrosion is at gold Belong to the thickness of layer thin in the case of or time metal level is metal line in the case of its line width, metal level can be run through, the most especially It becomes problem.

It is an object of the invention to, it is provided that can suppress the metal level of metal wiring layer etc corrosion with binding agent The blooming of layer and comprise the liquid crystal indicator of this blooming.

The present invention provides the blooming with adhesive phase shown below and the liquid crystal display dress comprising this blooming Put and adhesive composition.

[1] a kind of blooming with adhesive phase, its comprise blooming and be laminated on its at least one face viscous Mixture layer,

Described adhesive phase is by containing (methyl) acrylic resin (A), silane compound (B) and ionic chemical combination The adhesive composition of thing (C) is constituted,

Described silane compound (B) is the silane compound represented with following formula (I):

[changing 1]

In formula, A represents the alkane diyl of carbon number 1～20 or the ester ring type alkyl of the divalent of carbon number 3～20, constitutes This alkane diyl and the-CH of this ester ring type alkyl₂-can also be by-O-or-C (=O)-displacement, R¹Represent carbon number 1～ The alkyl of 5, R²、R³、R⁴、R⁵And R⁶Represent alkyl or the alkoxyl of carbon number 1～5 of carbon number 1～5 independently of one another.

The anion of described ionic compound (C) is the anion in following group:

[changing 2]

[2] according to the blooming with adhesive phase described in [1], wherein, the silane chemical combination represented with described formula (I) Thing (B) is the silane compound represented with following formula (II):

[changing 3]

In formula, R¹、R³、R⁴、R⁵And R⁶Represent implication same as described above, R respectively⁷Represent the alkyl of carbon number 1～5, m Represent the integer of 1～20.

[3] according to the blooming with adhesive phase described in [2], wherein, the m in described formula (II) is 4～20 Integer.

[4] according to the blooming with adhesive phase described in [2], wherein, the m in described formula (II) be 6～8 whole Number.

[5] according to the blooming with adhesive phase described in [2], wherein, the m in described formula (II) is 6.

[6] according to the blooming with adhesive phase recorded any one of [1]～[5], wherein, described silane compound (B) it is 1, double (trimethoxysilyl) hexane of 6-.

[7] according to the blooming with adhesive phase recorded any one of [1]～[6], wherein, described ionic chemical combination The cation of thing (C) is the cation with the heterocycle structure containing nitrogen-atoms comprising unsaturated bond.

[8] according to the blooming with adhesive phase recorded any one of [1]～[7], wherein, described ionic chemical combination The cation of thing (C) is the pyridylium represented with following formula (III):

[changing 4]

In formula, R⁸～R¹³Represent hydrogen atom independently of one another, can have the alkyl of substituent group, can have substituent group Thiazolinyl, can have the alkynyl of substituent group, can have the aryl of substituent group, can have the heterocyclic radical of substituent group, hydroxyl, ether Base, carboxyl, carbonyl or halogen atom, it is also possible between adjacent substituent group, form ring.

[9] according to the blooming with adhesive phase recorded any one of [1]～[8], wherein, described binding agent combines The content of the described silane compound (B) in thing relative to described (methyl) acrylic resin (A) 100 weight portion be 0.01～ 10 weight portions.

[10] according to the blooming with adhesive phase recorded any one of [1]～[9], wherein, described (methyl) third Olefin(e) acid system resin (A) is containing the Component units coming from the monomer with hydroxyl.

[11] according to the blooming with adhesive phase recorded any one of [1]～[10], wherein, described (methyl) third Olefin(e) acid system resin (A) is less than the composition of the alkyl acrylate (a1) of 0 DEG C containing the glass transition temperature coming from homopolymer Unit and come from the Component units of the alkyl acrylate that glass transition temperature is more than 0 DEG C (a2) of homopolymer.

[12] according to the blooming with adhesive phase recorded any one of [1]～[11], wherein, described (methyl) third The weight average molecular weight of olefin(e) acid system resin (A) is 500,000～2,500,000.

[13] according to the blooming with adhesive phase recorded any one of [1]～[12], wherein, described binding agent group Compound is possibly together with isocyanates system cross-linking agent (D).

[14] according to the blooming with adhesive phase recorded any one of [1]～[13], wherein, described binding agent group Compound contains substantially no three azole compounds.

[15] a kind of liquid crystal indicator, it comprises the optics with adhesive phase recorded any one of [1]～[14] Film.

[16] a kind of adhesive composition, it contains (methyl) acrylic resin (A), silane compound (B), Yi Jili Sub-property compound (C),

[changing 5]

The anion of described ionic compound (C) is the anion in following group:

[changing 6]

Described adhesive composition is used to form stacking adhesive phase on the metal layer.

According to the present invention it is possible to provide the blooming with adhesive phase and the bag of the corrosion that can suppress metal level Liquid crystal indicator containing this blooming.

Accompanying drawing explanation

Fig. 1 is the constructed profile of an example of the blooming with adhesive phase representing the present invention.

Fig. 2 is the constructed profile of an example of the layer composition representing polarization plates.

Fig. 3 is the constructed profile of another example of the layer composition representing polarization plates.

Fig. 4 is the constructed profile of an example of the layer composition representing optical laminate.

Fig. 5 is the constructed profile of another example of the layer composition representing optical laminate.

Fig. 6 is the constructed profile of another example of the layer composition representing optical laminate.

Fig. 7 is the constructed profile of another example of the layer composition representing optical laminate.

Fig. 8 is the constructed profile of another example of the layer composition representing optical laminate.

Detailed description of the invention

＜ is with the blooming ＞ of adhesive phase

Fig. 1 is the constructed profile of an example of the blooming with adhesive phase representing the present invention.As shown in Figure 1 this The bright blooming 1 with adhesive phase comprises blooming 10 and the adhesive phase 20 being laminated on its at least one face.Bonding Oxidant layer 20 is generally directly laminated in the surface of blooming 10.

Blooming 10 both can be the blooming of single layer structure, it is also possible to be the blooming of multiple structure.Adhesive phase 20 By containing (methyl) acrylic resin (A), silane compound (B) and ionic compound (C), preferably possibly together with isocyanide The adhesive composition of acid esters system cross-linking agent (D) is constituted.This adhesive composition can also be possibly together with other composition.This explanation In book, " (methyl) acrylic acid " refers at least one party in acrylic acid and methacrylic acid.For " (methyl) acrylate " Or " (methyl) acryloyl group " etc. is the most identical.

(1) blooming

The blooming 10 possessed with the blooming 1 of adhesive phase can be to load the images such as liquid crystal indicator The various bloomings (there is the film of optical characteristics) of display device.Blooming 10 both can be the blooming of single layer structure, it is possible to To be the blooming of multiple structure.The concrete example of the blooming of single layer structure, in addition to polaroid, also includes phase retardation film, bright Degree improves the optical functional films such as film, antiglare film, antireflection film, diffusion barrier, condensing film.The concrete example of the blooming of multiple structure Including polarization plates, polarizer.In this specification, so-called polarization plates refers to be laminated with resin molding at least one surface layer of polaroid Or the component of resin bed.So-called polarizer, refers to be laminated with resin molding or resin bed at least one surface layer of phase retardation film Component.Blooming 10 is preferably polarization plates, polaroid, polarizer or phase retardation film, more preferably polarization plates or polaroid.

(1-1) polarization plates

Fig. 2 and Fig. 3 is the constructed profile of the example of the layer composition representing polarization plates.Polarization plates 10a shown in Fig. 2 is A surface layer at polaroid 2 folds the one side protection polarization plates being fitted with the first resin molding 3, and polarization plates 10b shown in Fig. 3 is Also another surface layer at polaroid 2 folds the two-sided protection polarization plates being fitted with the second resin molding 4.First, second resin molding 3,4 Can press from both sides and fit with polaroid 2 across not shown adhesive layer or adhesive phase.Polarization plates 10a, 10b can also include One, other the film beyond the second resin molding 3,4 or layer.

Polaroid 2 be possess absorption have absorb the rectilinearly polarized light of the parallel vibration plane of axle with it, transmission have with inhale Receive the film of the character of the rectilinearly polarized light of orthogonal (parallel with the axis of homology) vibration plane of axle, such as, can use dichromatic color Element is adsorbed in film obtained by polyvinyl alcohol resin film orientation.As dichromatic pigment, it is possible to use iodine, dichromatic have engine dyeing Material.

Polyvinyl alcohol resin can be by obtaining the resin saponification of polyvinyl acetate system.As polyvinyl acetate It is resin, in addition to the polyvinyl acetate as the homopolymer of vinyl acetate, it is also possible to enumerating can be with vinyl acetate The monomer of ester copolymerization and the copolymer etc. of vinyl acetate.As can enumerating not with the monomer of vinyl acetate copolymerization Saturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid, there is (methyl) acrylamide etc. of ammonium.

The saponification degree of polyvinyl alcohol resin is usually 85～100 moles of %, preferably 98 moles more than %.Polyvinyl alcohol It is that resin can also be modified, the polyvinyl formal that such as can also use by aldehydes modification or polyvinyl acetal Deng.The average degree of polymerization of polyvinyl alcohol resin is usually 1000～10000, preferably 1500～5000.Polyethenol series tree The average degree of polymerization of fat can be obtained according to JIS K 6726.

Generally so that film obtained by polyvinyl alcohol resin masking is used as the raw material film of polaroid 2.Polyvinyl alcohol It is that resin can utilize known method masking.The thickness of raw material film is usually 1～150 μm, if further contemplating the appearance of stretching Yi Du etc., more than the most preferably 10 μm.

Polaroid 2 such as can manufacture as follows, i.e. raw material film is implemented the operation of uniaxial tension, uses dichromatic pigment It is allowed to adsorb the operation of this dichromatic pigment, process the operation of film with boric acid aqueous solution and film is carried out water by film dyeing The operation washed, is finally dried and is manufactured.The thickness of polaroid 2 is usually 1～30 μm, from the blooming with adhesive phase From the viewpoint of the filming of 1, below preferably 20 μm, below more preferably 15 μm, more preferably below 10 μm.

The polaroid 2 making dichromatic pigment be adsorbed in polyvinyl alcohol resin film orientation can utilize following side Method 1 obtains, i.e. use the independent film of polyvinyl alcohol resin film as raw material film, and this film is implemented uniaxial tension process And the dyeing of dichromatic pigment processes, in addition, it is also possible to Application way 2 obtains, i.e. to base material film coating containing polyethylene The coating fluid (aqueous solution etc.) of alcohol system resin, be allowed to be dried and after obtaining having the base material film of polyvinyl alcohol resin layer, by it Carrying out uniaxial tension together with base material film, the dyeing that the polyvinyl alcohol resin layer after stretching is implemented dichromatic pigment processes, Then peel off and remove base material film.As base material film, it is possible to use comprise and first, second resin molding 3,4 described later can be constituted The film of the identical thermoplastic resin of thermoplastic resin, preferably comprise the polyester based resins such as polyethylene terephthalate, The cyclic polyolefin hydrocarbon system resins such as the cellulose-based resin such as polycarbonate-based resin, triacetyl cellulose, norbornene resin, poly- The film of phenylethylene resin series etc..According to said method 2, easily make the polaroid 2 of thin film, the most easily make such as thickness 7 μm Following polaroid 2.

First, second resin molding 3,4 can be each independently comprise have light transmission, the most transparent Thermoplastic resin, such as chain polyolefin-based resins (polyethylene-based resin, polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin The polyolefin-based resins of (norbornene resin etc.) etc；Cellulose-based resin (cellulose esters system resin etc.)；Polyester tree Fat (polyethylene terephthalate, PEN, polybutylene terephthalate (PBT) etc.)；Polycarbonate-based Resin；(methyl) acrylic resin；Polystyrene resin；Polyether-ether-ketone system resin；Polysulfones system resin or their mixing The film of thing, copolymer etc..Wherein, first, second resin molding 3,4 is the most respectively by selected from cyclic polyolefin hydrocarbon system resin, poly-carbonic acid Resin in ester system resin, cellulose-based resin, polyester based resin and (methyl) acrylic resin is constituted, more preferably by Resin in cellulose-based resin and cyclic polyolefin hydrocarbon system resin is constituted.

As chain polyolefin-based resins, in addition to the homopolymer of the chain olefin such as polyvinyl resin, acrylic resin, The copolymer comprising chain olefin of more than two kinds can also be enumerated.

Cyclic polyolefin hydrocarbon system resin is to comprise as polymerized unit with norborene, tetracyclododecen (another name: dimethano eight Hydrogen naphthalene) or their general name of resin of the cyclic olefin that derivant is typical example.If cyclic polyolefin hydrocarbon system resin to be enumerated Concrete example, then be open loop (co) polymer and hydride, the addition polymer of cyclic olefin, the cyclic olefin of cyclic olefin With the chain olefin of ethylene, propylene etc or the copolymer of the aromatic compound with vinyl and they are used insatiable hunger Modified with carboxylic acid or derivatives thereof modified (co) polymer etc..Wherein, it is preferably used as cyclic olefin and employs fall ice The norbornene resin of the norborneol alkene monomers such as sheet alkene or condensed ring norborneol alkene monomer.

Cellulose-based resin is preferably the partially or completely carboxylate etc. of cellulose esters system resin, i.e. cellulose, such as may be used To enumerate the acetas of cellulose, propionic ester, butyrate, their mixed ester etc..Wherein, be preferably used triacetyl cellulose, Diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc..

Polyester based resin is to have the resin beyond ester bond, above-mentioned cellulose esters system resin, usually comprises polynary carboxylic The resin of the condensation polymer of acid or derivatives thereof and polyhydric alcohol.The concrete example of polyester based resin includes polyethylene terephthalate Ester, polybutylene terephthalate (PBT), PEN, PBN, poly terephthalic acid third Diol ester, polytrimethylene naphthalate, polycyclohexylene's diformazan alcohol ester, poly-naphthalenedicarboxylic acid cyclohexanedimethanol Ester.

Polycarbonate-based resin is the polyester formed by carbonic acid and glycol or bis-phenol.Wherein, from thermostability, weatherability and resistance to From the viewpoint of acidity, it is preferably used in strand the aromatic copolycarbonate with diphenyl alkane.As Merlon, Can exemplify by 2, double (4-hydroxy phenyl) propane (another name bisphenol-A) of 2-, 2, double (4-hydroxy phenyl) butane of 2-, 1, 1-bis(4-hydroxyphenyl)cyclohexane, 1, double (4-hydroxy phenyl) iso-butane of 1-, 1, double (4-hydroxy phenyl) ethane of 1- Etc the derivative Merlon of bis-phenol.

(methyl) acrylic resin that can constitute first, second resin molding 3,4 can be to come from metering system The Component units of acid esters, as (such as containing this Component units of more than 50 weight %) polymer of main body, is preferably at it Upper copolymerization has the copolymer of other copolymer compositions.(methyl) acrylic resin can also comprise and of more than two kinds come from methyl The Component units of acrylate.As methacrylate, methyl methacrylate, ethyl methacrylate, first can be enumerated The C of the methacrylic acids such as base butyl acrylate₁～C₄Arrcostab.

As can enumerating acrylate with the copolymer composition of methacrylate copolymers.Acrylate is preferably Acrylic acid C such as acrylic acid methyl ester., ethyl acrylate, butyl acrylate, 2-EHA₁～C₈Arrcostab.Other The concrete example of copolymer composition can enumerate the unsaturated acids such as (methyl) acrylic acid；Styrene, halogenated styrenes, Alpha-Methyl benzene The aromatic ethenyl compound such as ethylene, vinyltoluene；The vinyl cyanide compounds such as (methyl) acrylonitrile；Maleic anhydride, lemon The unsaturated acid anhydrides such as health anhydride；The unsaturated acyl imines such as phenyl maleimide, N-cyclohexylmaleimide etc. have in intramolecular There is the compound beyond 1 polymerism carbon-to-carbon double bond, acrylate.More than 2 poly-can also will be had in intramolecular The compound of conjunction property carbon-to-carbon double bond uses as copolymer composition.Copolymer composition both can only use a kind, it is also possible to and with 2 kinds Above.

From the standpoint of the durability that can improve film, (methyl) acrylic resin can also be in high polymer main chain There is ring structure.Ring structure is preferably the heterocycle structures such as cyclic acid anhydride structure, cyclic imide structure, lactonic ring structure.As The concrete example of cyclic acid anhydride structure, can enumerate glutaric anhydride structure, succinic anhydride structure, as the tool of cyclic imide structure Style, can enumerate glutarimide structure, succimide structure, as the concrete example of lactonic ring structure, can enumerate fourth Lactonic ring structure, valerolactone ring structure.

Considering from the viewpoint such as impact resistance making the masking of film, film, (methyl) acrylic resin can also contain Acrylic rubber particle.So-called acrylic rubber particle, is the particle using elastomeric polymer as required composition, described bullet Property polymer using acrylate as main body, can enumerate the single layer structure the most only comprising this elastomeric polymer particle, Using elastomeric polymer as the particle of the multiple structure of 1 layer.As the example of elastomeric polymer, can enumerate with alkyl acrylate Base ester as main constituent copolymerization can be copolymerized therewith other vinyl monomers and the crosslinking elastomeric copolymer of cross-linkable monomer Thing.As the alkyl acrylate of the main constituent becoming elastomeric polymer, such as, can enumerate acrylic acid methyl ester., acrylic acid second Acrylic acid C such as ester, butyl acrylate, 2-EHA₁～C₈Arrcostab.The carbon number of alkyl be preferably 4 with On.

As can with other vinyl monomers of alkyl acrylate copolymer, can enumerate intramolecular have 1 gather The compound of conjunction property carbon-to-carbon double bond, more specifically, can enumerate the methacrylate of methyl methacrylate etc, benzene The vinyl cyanide compound etc. of the aromatic ethenyl compound of ethylene etc, (methyl) acrylonitrile etc.As bridging property list Body, can enumerate the compound of bridging property in intramolecular with at least 2 polymerism carbon-to-carbon double bonds, more specifically, and can With enumerate the polyhydric alcohol such as ethylene glycol bisthioglycolate (methyl) acrylate, butanediol two (methyl) acrylate (methyl) acrylate, (methyl) allyl acrylate etc. (methyl) acrylic acid alkenyl esters, divinylbenzene etc..

The content of acrylic rubber particle is relative to (methyl) acrylic resin 100 weight portion, preferably 5 weight portions Above, more than more preferably 10 weight portions.If the content of acrylic rubber particle is too many, then the case hardness of film reduces, It addition, the solvent resistance of the organic solvent in surface conditioning agent may be reduced in the case of film is implemented surface process.Cause And, the content of acrylic rubber particle relative to (methyl) acrylic resin 100 weight portion, usually 80 weight portions with Under, below preferably 60 weight portions.

First, second resin molding 3,4 can be containing the common additive in the technical field of the present invention.The tool of additive Style such as includes UV absorbent, infrared absorbent, organic system dyestuff, pigment, inorganic system pigment, antioxidant, prevents Static interference agent, surfactant, lubricant, dispersant, heat stabilizer etc..

As UV absorbent, salicylate compounds, benzophenone cpd, benzotriazole chemical combination can be enumerated Thing, triaizine compounds, (methyl) acrylic acid cyano ester compound, nickel complex etc..

First, second resin molding 3,4 can be the film being not stretched or appointing by single shaft or biaxial stretch-formed film respectively Meaning one.Biaxial stretch-formed both can be stretch along 2 draw directions simultaneously while biaxial stretch-formed, it is also possible to along regulation It is the most biaxial stretch-formed that the other direction of stretching tailing edge, direction carries out stretching.First resin molding 3 and/or the second resin molding 4 are permissible It is the protecting film of the effect undertaking protection polaroid 2, it is also possible to as phase retardation film described later, have optical function concurrently Protecting film.Phase retardation film is to demonstrate optically anisotropic blooming.For example, it is possible to by comprising above-mentioned thermoplastic resin Film carry out stretching (being stretched uniaxially or biaxially) or on this thermoplastic resin film, form liquid crystal layer etc. and make and composed Give the phase retardation film of arbitrary phase difference value.

First resin molding 3 and the second resin molding 4 both can be the films being made up of identical thermoplastic resin, it is also possible to be by The film that thermoplastic resin different from each other is constituted.First resin molding 3 and the second resin molding 4 thickness, the presence or absence of additive or its The aspect such as kind, phase difference characteristics both can be identical, it is also possible to different.

First resin molding 3 and/or the second resin molding 4 can also be its outer surface (with the surface of polaroid 2 opposite side) Possess the surface-treated layers such as hard conating, antiglare layer, anti-reflection layer, light diffusion layer, anti-static electricity interference layer, stain-proofing layer, conductive layer (to be coated with Coating).

The thickness of the first resin molding 3 and the second resin molding 4 respectively be usually 1～150 μm, preferably 5～100 μm, more excellent Elect 5～60 μm as.This thickness can also be below 50 μm, below even 30 μm.Reduce the thickness of first, second resin molding 3,4 Degree, is conducive to the blooming 1 with adhesive phase and comprises the filming of optical laminate of this blooming 1, and then being conducive to Comprise the filming of the liquid crystal indicator of the blooming 1 with adhesive phase or optical laminate.

Especially for for smart mobile phone, the such middle-size and small-size polarization plates of panel type terminal, from filming Require to consider, as the thin resin molding below the first resin molding 3 and/or the second resin molding 4 commonly used thickness 30 μm, and this The power of the contractility planting polarization plates suppression polaroid 2 is weak, and durability is the most insufficient.According to the present invention, even if by this kind partially In the case of vibration plate uses as blooming 10, it is also possible to the blooming with adhesive phase with good durability is provided 1 and comprise the optical laminate of this blooming 1.The so-called blooming 1 with adhesive phase and the durability of optical laminate Refer to following character, i.e. the most in high temperature environments, under hot and humid environment, repeatedly in the environment of high temperature and low temperature etc., can With tilting or coming off in the interface of suppression adhesive phase 20 and optical component adjacent thereto, the foaming of adhesive phase 20 etc. no Good situation.

It addition, from the viewpoint of the filming of polarization plates, only at polaroid 2 as polarization plates 10a shown in Fig. 2 The composition of one side configuration resin molding is favourable composition.Usual bonding of directly fitting in another face of polaroid 2 in the case of Gai Oxidant layer 20 and become the blooming 1 (with reference to Fig. 4) with adhesive phase.In the case of the polarization plates that this kind is constituted, because of bonding Ionic compound contained in oxidant layer 20 and the problem that makes the optical property of polarization plates reduce under hot and humid environment becomes It is especially apparent.According to the present invention, even if in the case of this kind of polarization plates is used as blooming 10, it is also possible to provide and have The blooming 1 with adhesive phase of good optical durability (character of the deterioration of optical characteristics can be suppressed) and bag Optical laminate containing this blooming 1.

First, second resin molding 3,4 can press from both sides fits with polaroid 2 across adhesive layer or adhesive phase.As formation The adhesive of adhesive layer, it is possible to use water system adhesive or active energy ray-curable adhesive.

As water system adhesive, can enumerate and comprise the adhesive of polyvinyl alcohol resin aqueous solution, water system two-liquid type ammonia Carbamate system emulsion adhesive etc..Wherein, applicable use comprises the water system adhesive of polyvinyl alcohol resin aqueous solution.As Polyvinyl alcohol resin, except using the polyvinyl acetate to the homopolymer as vinyl acetate to carry out saponification process Obtained by beyond alcotex, it is also possible to use to vinyl acetate and can be copolymerized therewith the copolymer of other monomers Carry out polyvinyl alcohol based copolymer obtained by saponification process or by modified for their hydroxylic moiety ground modified polyvinylalcohol system Polymer etc..Water system adhesive can contain aldehyde compound, epoxy compounds, tripolycyanamide based compound, methylol chemical combination The cross-linking agent such as thing, isocyanate compound, amines, multivalent metal salt.

In the case of using water system adhesive, after polaroid 2 and first, second resin molding 3,4 are fitted, in order to remove Water contained by going in water system adhesive is preferable to carry out being allowed to dry operation.Can also arrange such as 20 after drying process ～the temperature of about 45 DEG C carries out the curing step of ripening.

Above-mentioned so-called active energy ray-curable adhesive, refers to because irradiation ultraviolet radiation or electron beam isoreactivity energy are penetrated Line and the adhesive that solidifies, such as, can enumerate containing polymerizable compound and the solidification compound of Photoepolymerizationinitiater initiater, contain There is the solidification compound of light reactive resin, containing resin glue and the solidification compound etc. of photoreactivity cross-linking agent. It is preferably ultra-violet solidified adhesive.As polymerizable compound, photo-curable epoxy monomer, photo-curable can be enumerated Photopolymerization monomers such as (methyl) acrylic monomer, photo-curable carbamate system monomer or come from optical polymerism list The oligomer of body.As Photoepolymerizationinitiater initiater, can enumerate produce containing the irradiation because of active energy beam Neutral radical, Radical anion, the Photoepolymerizationinitiater initiater of material at radical cation isoreactivity center.As containing polymerizable compound And the active energy ray-curable adhesive of Photoepolymerizationinitiater initiater, it may be preferred to use containing photo-curable epoxy monomer and The solidification compound of light cationic polymerization initiators, it is polymerized containing photo-curable (methyl) acrylic monomer and optical free radical The solidification compound of initiator or the mixture of these solidification compounds.

Using in the case of active energy ray-curable adhesive, by polaroid 2 and first, second resin molding 3, After 4 laminatings, it is dried operation as required, then carries out making active energy ray-curable by irradiating active energy beam Property adhesive solidification curing process.The light source of active energy beam is not particularly limited, but preferably at below wavelength 400nm Have and send out ultraviolet photodistributed, specifically, it is possible to use low pressure mercury lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, supertension Finsen lamp, chemical lamp, black light lamp, microwave-excitation finsen lamp, metal halide lamp etc..

When polaroid 2 and first, second resin molding 3,4 are fitted, can be to the laminating of their at least any one party Face is implemented the surface activations such as saponification process, sided corona treatment, Cement Composite Treated by Plasma and is processed.At the two sides of polaroid 2 laminating resin In the case of film, the adhesive for being fitted by these resin moldings both can be adhesive of the same race, it is also possible to be glue the most of the same race Stick.

Polarization plates 10a, 10b can also comprise other film or layer.Its concrete example is in addition to phase retardation film described later, also Can be that brightness improves the adhesive phase beyond film, antiglare film, antireflection film, diffusion barrier, condensing film, adhesive phase 20, coating Layer, protecting film etc..Protecting film is in order at the surface of the bloomings 10 such as protection polarization plates from the purpose use damaged or pollute Film, it is common practice to after being fitted on such as metal level 30 by the blooming 1 with adhesive phase, be stripped removing.

Protecting film is generally by base material film be laminated in adhesive phase thereon and constitute.Base material film can by thermoplastic resin, The such as polyolefin-based resins such as polyethylene-based resin, polypropylene-based resin；Polyethylene terephthalate or poly-naphthalenedicarboxylic acid The polyester based resins such as glycol ester；Polycarbonate-based resin；(methyl) acrylic resins etc. are constituted.

(1-2) polarizer

Phase retardation film contained in polarizer is as it has been described above, be to demonstrate optically anisotropic blooming, as can For the phase retardation film in first, second resin molding 3,4, can be to comprising the thermoplastic resin and example being illustrated above Such as polyvinyl alcohol resin, polyarylate system resin, polyimides system resin, polyether sulfone system resin, polyvinylidene fluoride/poly-methyl Acrylic acid methyl ester. system resin, liquid crystal polyester system resin, ethylene-acetidin copolymer saponification material, polyvinyl chloride resin etc. Resin molding be stretched as stretched film obtained by about 1.01～6 times.Wherein, it is preferably Merlon resin film or ring-type alkene Hydrocarbon system resin molding, (methyl) acrylic resin film or cellulose-based resin molding draw obtained by being stretched uniaxially or biaxially Stretch film.It addition, in this manual, zero-lag film be also contained in phase retardation film (but can also use as protecting film.). In addition, it is also possible to uniaxiality phase retardation film, wide viewing angle phase retardation film, low modulus of photoelasticity phase retardation film etc. will be referred to as Film uses as phase retardation film.

So-called zero-lag film, refers to phase difference value R in face_eAnd thickness direction phase difference value R_thIt is all-15～15nm Film.This phase retardation film goes for the liquid crystal indicator of IPS pattern.Phase difference value R in face_eAnd thickness direction phase difference value R_thIt is the most all-10～10nm, is the most all-5～5nm.Phase difference value R in face described herein_eAnd thickness direction phase Potential difference value R_thIt it is value during wavelength 590nm.

Phase difference value R in face_eAnd thickness direction phase difference value R_thIt is defined by the formula respectively:

R_e=(n_x-n_y)×d

R_th=((n_x+n_y)/2-n_z〕×d

In formula, n_xIt is the refractive index of slow-axis direction (x-axis direction) in face, n_yIt is that the quick shaft direction in face is (in face The y-axis direction orthogonal with x-axis) refractive index, n_zBeing the refractive index of film thickness direction (being perpendicular to the z-axis direction of face), d is film Thickness.

As zero-lag film, it is possible to use such as comprise cellulose-based resin, chain polyolefin-based resins and cyclic polyolefin Polyolefin-based resins, PET series resin or the resins of (methyl) acrylic resin such as hydrocarbon system resin Film.Especially because the control of phase difference value is easy, it is also easy to obtain, cellulose-based resin, polyolefin are therefore preferably used Resin or (methyl) acrylic resin.

It addition, utilize the coating of liquid crystal compounds, orientation embody optically anisotropic film, utilize inorganic laminated The coating of compound embodies optically anisotropic film and can also use as phase retardation film.As this kind of phase retardation film, There is the phase retardation film being referred to as temperature compensating type phase retardation film, it addition, also have by the JX day ore deposit day stone energy (strain) with " NH film " Trade name sell by film obtained by rod shaped liquid crystal tilted alignment, by Fujiphoto (strain) with the trade name of " WV film " sell will Film obtained by disc-like liquid crystal tilted alignment, the complete biaxial orientation sold with the trade name of " VAC film " by Sumitomo Chemical (strain) The film of type, the film etc. of the same biaxially oriented version sold with the trade name of " new VAC film " by Sumitomo Chemical (strain).

The resin molding at least one face being laminated in phase retardation film can be such as above-mentioned protecting film.

(2) adhesive phase

It is laminated in the adhesive phase 20 at least one face of blooming 10 by containing (methyl) acrylic resin (A), silicon The adhesive composition of hydride compounds (B) and ionic compound (C) is constituted, preferably possibly together with isocyanates system cross-linking agent (D).In this adhesive composition, silane compound (B) is the silane compound represented with following formula (I):

[changing 7]

It addition, be the chemical combination being made up of cation and anion above-mentioned adhesive composition ionic compound (C) Thing, this anion is the anion in following group:

[changing 8]

According to the adhesive phase 20 being made up of above-mentioned adhesive composition, even if comprising adhesive phase 20 is configured at In the case of in the substrate of the composition of metal level, it is also possible to suppress the corrosion of this metal level, furthermore it is possible to improve with binding agent The blooming 1 of layer and comprise the durability of optical laminate of this blooming 1.Additionally, according to by above-mentioned binding agent combination The adhesive phase 20 that thing is constituted, even with the blooming 1 of adhesive phase and comprise the optical laminate of this blooming 1 Adhesive phase 20 is mounted directly on the composition on polaroid 2, it is also possible to demonstrate good optical durability.Hereinafter, Also the character that can suppress the corrosion of metal level is referred to as " resistance to metal protection ".

The thickness of adhesive phase 20 is usually 2～40 μm, from the blooming 1 of adhesive phase and comprise this optics The viewpoints such as the re-workability (リワ Network) of the durability of the optical laminate of film 1 and the blooming 1 with adhesive phase are examined Consider, preferably 5～30 μm, more preferably 10～25 μm.If it addition, the thickness of adhesive phase 20 is more than 10 μm, then bonded Oxidant layer 20 becomes good for the tracing ability of the change in size of blooming 10, and below 25 μm, then re-workability becomes good Good.

Adhesive phase 20 preferably demonstrates the storage elastic modulus of 0.1～5MPa in the temperature range of 23～80 DEG C Layer.Thus, it is possible to more efficiently improve the blooming 1 with adhesive phase and comprise the optics stacking of this blooming 1 The durability of body.So-called " demonstrating the storage elastic modulus of 0.1～5MPa in the temperature range of 23～80 DEG C ", refers at this At the arbitrary temperature of scope, storage elastic modulus is all the value in above-mentioned scope.Due to storage elastic modulus generally along with temperature Degree raises and is gradually reduced, if therefore the storage elastic modulus of 23 DEG C and 80 DEG C both falls within above-mentioned scope, then and can be at this model The storage elastic modulus in above-mentioned scope is demonstrated at a temperature of enclosing.The storage elastic modulus of adhesive phase 20 can use commercially available Determination of viscoelasticity device, the determination of viscoelasticity device " DYNAMIC ANALYZER RDA II " of such as REOMETRIC company Measure.

(2-1) (methyl) acrylic resin (A)

(methyl) acrylic resin (A) is that the Component units to come from (methyl) acrylic monomer is as main constituent (preferably comprising more than 50 weight %) polymer or copolymer.(methyl) acrylic monomer such as contains and has (methyl) The monomer of acryloyl group, preferably comprises (methyl) alkyl acrylate.The carbon of the alkyl that (methyl) alkyl acrylate is had Atomic number is preferably 1～14, more preferably 1～12, and more preferably 1～8, can be straight-chain, branched or ring-type.Make For (methyl) alkyl acrylate, it is possible to use the acrylic acid containing substituent group having imported substituent group in alkyl described later (methyl) alkyl acrylate containing substituent group of Arrcostab etc.(methyl) alkyl acrylate both can only use a kind, And can also be used two or more.

The concrete example of (methyl) alkyl acrylate includes (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (first Base) acrylic acid just and isopropyl ester, (methyl) acrylic acid just, different and the tert-butyl ester, acrylic acid just and isopentyl ester, (methyl) acrylic acid just And dissident's ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid just and isocyanate, (methyl) acrylic acid just and different monooctyl ester, (first Base) 2-EHA, (methyl) acrylic acid just and different nonyl ester, (methyl) acrylic acid just and isodecyl ester, (methyl) propylene Acid isobornyl thiocyanoacetate, (methyl) acrylic acid are just and Fancol ID base ester, (methyl) stearyl acrylate base ester etc..

(methyl) acrylic resin (A) preferably comprises the glass transition temperature Tg coming from homopolymer less than 0 DEG C The Component units of alkyl acrylate (a1) and come from the alkyl acrylate that Tg is more than 0 DEG C (a2) of homopolymer Component units.This is arranged on improve with the blooming 1 of adhesive phase and the optical laminate that comprises this blooming 1 resistance to The aspect of metal protection and durability is favourable.The Tg of the homopolymer of alkyl acrylate such as can use POLYMER The literature value of HANDBOOK (Wiley-Interscience) etc..

The concrete example of alkyl acrylate (a1) include ethyl acrylate, acrylic acid just and isopropyl ester, acrylic acid just and different Butyl ester, acrylic acid n-pentyl ester, acrylic acid just and dissident's ester, the positive heptyl ester of acrylic acid, acrylic acid just and different monooctyl ester, acrylic acid 2-second The own ester of base, acrylic acid just and different nonyl ester, acrylic acid just and the carbon number of the alkyl such as isodecyl ester, acrylic acid dodecyl ester is The alkyl acrylate of 2～about 12.Other concrete examples as alkyl acrylate (a1), it is also possible to enumerate the carbon to alkyl Atomic number be the alkyl acrylate of 2～about 12 alkyl in imported the acrylic acid alkyl containing substituent group of substituent group Ester.The substituent group of the alkyl acrylate containing substituent group is to replace the group of hydrogen atom of alkyl, its concrete example include phenyl, Alkoxyl, phenoxy group.As the alkyl acrylate containing substituent group, specifically, acrylic acid 2-methoxyl group second can be enumerated Ester, ethioxy methyl ester, acrylate, phenoxy group diethylene glycol acrylate etc..Although acrylic acid alkyl The alkyl of ester (a1) can also have an ester ring type structure, but preferably straight-chain or the alkyl of branched.

Alkyl acrylate (a1) both can only use a kind, it is also possible to and use two or more.Wherein, alkyl acrylate (a1) preferably comprise in ethyl acrylate, n-butyl acrylate, 2-EHA is one kind or two or more.From From the viewpoint of the adhesive phase 20 being had with the blooming 1 of adhesive phase is to the tracing ability of blooming 10, re-workability, Alkyl acrylate (a1) preferably comprises n-butyl acrylate.

Alkyl acrylate (a2) is the alkyl acrylate beyond alkyl acrylate (a1).Alkyl acrylate (a2) Concrete example include acrylic acid methyl ester., cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate base ester, the tertiary fourth of acrylic acid Ester etc..

Alkyl acrylate (a2) both can only use a kind, it is also possible to and use two or more.Wherein, from resistance to metal protection And from the viewpoint of durability, alkyl acrylate (a2) preferably comprises acrylic acid methyl ester., cyclohexyl acrylate, the different ice of acrylic acid Sheet esters etc., more preferably contain acrylic acid methyl ester..

For the content of the Component units coming from alkyl acrylate (a2) in (methyl) acrylic resin (A), From with the blooming 1 of adhesive phase and comprise the resistance to metal protection of optical laminate of this blooming 1 and durability Viewpoint considers, in whole Component units 100 weight portion constituting (methyl) acrylic resin (A), and preferably 10 weight portions Above, more than more preferably 15 weight portions, more preferably more than 20 weight portions, more than particularly preferably 25 weight portions.Separately Outward from the viewpoint of adhesive phase 20 is to the tracing ability of blooming 10 and re-workability, come from alkyl acrylate (a2) The content of Component units is preferably below 70 weight portions, below more preferably 60 weight portions, more preferably 50 weight portions with Under.

(methyl) acrylic resin (A) can be containing other lists come from beyond alkyl acrylate (a1) and (a2) The Component units of body.(methyl) acrylic resin (A) both can contain only a kind of Component units coming from these other monomers, Can also be contained two or more.The concrete example of other monomers is expressed as follows.

1) there is the monomer of polar functional group.

As having the monomer of polar functional group, can enumerate and there is hydroxyl, carboxyl, replacement or unsubstituted amino, epoxy (methyl) acrylate of the substituent groups such as heterocyclic radical such as base.Specifically, can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 2-(2-'-hydroxyethoxy Base) ethyl ester, (methyl) acrylic acid 2-chlorine-2-hydroxyl propyl ester, (methyl) acrylic acid 3-chlorine-2-hydroxyl propyl ester, diethyl two Alcohol list (methyl) acrylate etc. has the monomer of hydroxyl；Acryloyl morpholine, caprolactam, N-vinyl-2- Ketopyrrolidine, vinylpyridine, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification tetrahydrofurfuryl acrylate, 3,4-epoxy radicals Cyclohexyl methyl (methyl) acrylate, (methyl) glycidyl acrylate, DHF etc. have the list of heterocyclic radical Body；(methyl) acrylate, (methyl) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid dimethylamino Base propyl ester etc. has replacement or the monomer of unsubstituted amino；(methyl) acrylic acid, (methyl) carboxyethyl acrylates etc. have carboxylic The monomer of base.Wherein, preferably there is the monomer of hydroxyl, from the side of (methyl) acrylic resin (A) with the reactivity of cross-linking agent Face considers, more preferably has (methyl) acrylate of hydroxyl.

Can also be combined with (methyl) acrylate with hydroxyl comprise above-mentioned other there is polar functional group Monomer, from the viewpoint of excessively increasing from preventing the peeling force that can be laminated in the barrier film of the outer surface of adhesive phase 20, preferably Contain substantially no the monomer with amino.It addition, from the viewpoint of improving for the corrosion resistance of ITO, the most substantially Do not contain the monomer with carboxyl.Containing substantially no described in herein, refers to constituting (methyl) acrylic resin (A) All Component units 100 weight portion is below 0.1 weight portion.

2) acrylamide monomer

For example, N hydroxymethyl acrylamide, N-(2-hydroxyethyl) acrylamide, N-(3-hydroxypropyl) propylene Amide, N-(4-hydroxybutyl) acrylamide, N-(5-Hydroxy pentyl) acrylamide, N-(6-hydroxyl hexyl) acryloyl Amine, N,N-DMAA, N, N-acrylamide, NIPA, N-(3-dimethylamino Base propyl group) acrylamide, N-(1,1-dimethyl-3-oxo butyl) acrylamide, N-(2-(2-oxo-1-miaow Oxazolidinyl) ethyl) acrylamide, 2-Acryloyl amino-2-methyl isophthalic acid-propane sulfonic acid, N-(methoxy) third Acrylamide, N-(ethoxyl methyl) acrylamide, N-(propoxy methyl) acrylamide, N-(1-methylethoxy ylmethyl) Acrylamide, N-(1-methyl propoxy methyl) acrylamide, N-(2-methyl propoxy methyl) acrylamide (another name: N-(isobutoxymethyl) acrylamide), N-(butoxymethyl) acrylamide, N-(1,1-dimethylethoxy ylmethyl) Acrylamide, N-(2-methoxy ethyl) acrylamide, N-(2-ethoxyethyl group) acrylamide, N-(2-propoxyl group Ethyl) acrylamide, N-(2-(1-methyl ethoxy) ethyl) acrylamide, N-(2-(1-methyl-prop epoxide) ethyl) Acrylamide, N-(2-(2-methyl-prop epoxide) ethyl) acrylamide (another name: N-(2-isobutoxyethy) acryloyl Amine), N-(2-butoxyethyl group) acrylamide, N-(2-(1,1-dimethylethyloxy) ethyl) acrylamide etc..Its In, N-(methoxy) acrylamide, N-(ethoxyl methyl) acrylamide, N-(propoxy methyl) third are preferably used Acrylamide, N-(butoxymethyl) acrylamide, N-(2-methyl propoxy methyl) acrylamide.

3) methacrylate (i.e. metacrylate)

For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, The straight-chain Arrcostab of the methacrylic acid such as n octyl methacrylate, lauryl methacrylate；Isobutyl methacrylate, The branched-chain alkyl ester of the methacrylic acid such as 2-Ethylhexyl Methacrylate, 2-Propenoic acid, 2-methyl-, isooctyl ester；Methacrylic acid is different Norbornene ester, cyclohexyl methacrylate, methacrylic acid Bicvclopentyl ester, methacrylic acid cyclo-dodecyl ester, metering system Acid methyl cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, t-butyl cyclohexyl ester, methacrylic acid cyclohexyl benzene The ester ring type Arrcostab of the methacrylic acids such as ester；The first such as methacrylic acid 2-methoxy acrylate, methacrylic acid ethyoxyl methyl ester The acrylic acid alkoxy alkyl of base；The methacrylic acid aralkyl esters such as benzyl methacrylate；Methacrylic acid 2-hydroxyl second Ester, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxybutyl, methacrylic acid 2-(2-hydroxyl-oxethyl) second Ester, methacrylic acid 2-chlorine-2-hydroxyl propyl ester, methacrylic acid 3-chlorine-2-hydroxyl propyl ester, diethylene glycol monomethyl third Olefin(e) acid ester etc. has the Arrcostab of the methacrylic acid of hydroxyl；Aminoethyl methacrylate, methacrylic acid N, N-dimethyl Amino ethyl ester, dimethylamine propyl ester etc. have the Arrcostab of the methacrylic acid of replacement or unsubstituted amino； Methacrylic acid 2-phenoxy ethyl, methacrylic acid 2-(2-phenoxy group) ethyl ester, (methyl) acrylic acid epoxy Oxide-modified nonyl benzene phenolic ester, methacrylic acid 2-(adjacent phenylphenoxy) ethyl ester etc. have the metering system of Phenoxyethyl The ester etc. of acid.

4) Methacrylamide system monomer

For example, with above-mentioned 1) described in Methacrylamide system monomer corresponding to acrylamide monomer.

5) styrenic monomers

For example, styrene；Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethylbenzene The alkane such as ethylene, triethylbenzene ethylene, propylstyrene, butylstyrene, hexyl benzene ethylene, heptyl benzene ethylene, octyl styrene Base styrene；The halogenated styrenes such as fluorobenzene ethylene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene ethylene；Nitrobenzol second Alkene；Acetylbenzene ethylene；Methoxy styrene；Divinylbenzene etc..

6) ethylene base system monomer

For example, vinyl acetate, propionate, vinyl butyrate, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate Deng fatty acid vinyl ester；The vinyl halides such as vinyl chloride, bromine ethylene；The vinylidene halides such as vinylidene chloride；Vinylpyridine, second The nitrogenous aromatic vinyl monomer such as vinyl pyrrolidone, VCz；Butadiene, isoprene, chlorobutadiene equiconjugate Diene monomers；The unsaturated nitrile such as acrylonitrile, methacrylonitrile etc..

7) there is the monomer of multiple (methyl) acryloyl group in intramolecular

For example, BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonyl Glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG Two (methyl) acrylate, tripropylene glycol two (methyl) acrylate etc. have the list of 2 (methyl) acryloyl groups in intramolecular Body；Trimethylolpropane tris (methyl) acrylate etc. have the monomer etc. of 3 (methyl) acryloyl groups in intramolecular.

As it has been described above, (methyl) acrylic resin (A) is from the blooming 1 of adhesive phase and comprise this optics From the viewpoint of the durability of the optical laminate of film 1 and resistance to metal protection, preferably except coming from (methyl) alkyl acrylate Beyond the Component units of base ester, possibly together with the Component units coming from the monomer with polar functional group.There is polar functional group Monomer preferably there is (methyl) acrylic ester monomer of polar functional group, more preferably there is the monomer of hydroxyl.From Content in the Component units of the monomer with polar functional group constitutes list the whole of composition (methyl) acrylic resin (A) In unit's 100 weight portions, preferably 0.1～10 weight portions, more preferably 0.25～5 weight portions, more preferably 0.5～5 weight Amount part.

It addition, from the viewpoint of the re-workability with the blooming 1 of adhesive phase, (methyl) acrylic resin (A) the structure coming from the methacrylic monomers such as methacrylate (metacrylate), Methacrylamide system monomer The content becoming unit is the smaller the better, and specifically, the content of this Component units is constituting the complete of (methyl) acrylic resin (A) In portion's Component units 100 weight portion, below preferably 10 weight portions, below more preferably 5 weight portions, the most substantially Do not contain this Component units (below 0.1 weight portion).

(methyl) acrylic resin (A) preferably weight average molecular weight on the elution curve of gel permeation chromatography (GPC) The scope of Mw1000～2,500,000 has single peak, more preferably have in the scope of Mw1000～2,500,000 single peak, And containing coming from alkyl acrylate (a1) and the Component units of (a2).Using this (methyl) acrylic resin (A) as The adhesive phase 20 of base polymer is improving the blooming 1 with adhesive phase and is comprising the optics stacking of this blooming 1 The aspect of the durability of body is favourable.In the case of peak number in the scope of above-mentioned Mw is more than 2, has and cannot obtain sufficiently The trend of durability.

During the peak number of GPC elution curve in seeking the scope calculating Mw1000～2,500,000, remember according in embodiment one The GPC condition determination carried obtains elution curve.In the above-mentioned scope of the elution curve of gained, so-called " having single peak " is Refer to, the scope of Mw1000～2,500,000 only has 1 maximum.In this specification, in GPC elution curve, by S/N ratio Be more than 30 curve definitions be peak.

The Mw of polystyrene standard based on the GPC conversion of (methyl) acrylic resin (A) is preferably in 500,000～250 The scope of ten thousand, is more preferably in the scope of 600,000～2,000,000.If Mw is more than 500,000, be then conducive to adhesive phase Blooming 1 and comprise the resistance to metal protection of optical laminate and the raising of durability of this blooming 1, with binding agent The trend that the re-workability of the blooming 1 of layer is also improved.It addition, if Mw is less than 2,500,000, then adhesive phase 20 is for light The tracing ability of the change in size learning film 10 becomes good.Represent with the ratio Mw/Mn of weight average molecular weight Mw and number-average molecular weight Mn Molecular weight distribution is usually 2～10.Mw and Mn of (methyl) acrylic resin (A) is according to described in embodiment one GPC condition determination is obtained.

When making (methyl) acrylic resin (A) be dissolved in ethyl acetate to make the solution of concentration 20 weight %, The viscosity of 25 DEG C is preferably below 20Pa s, more preferably 0.1～7Pa s.The viscosity of this scope is conducive to binding agent The blooming 1 of layer and comprise this blooming 1 optical laminate durability raising, with the blooming 1 of adhesive phase Re-workability.Above-mentioned viscosity can utilize Brookfield viscometer to measure.

(methyl) acrylic resin (A) utilize the glass transition temperature Tg that differential scanning calorimeter (DSC) measures It is preferably-60～-10 DEG C, more preferably-55～-15 DEG C.The Tg of this scope is conducive to the blooming with adhesive phase 1 and comprise the resistance to metal protection of optical laminate and the raising of durability of this blooming 1.

Adhesive composition can also contain (methyl) propylene belonging to (methyl) acrylic resin (A) of more than two kinds Acid is resin.It addition, adhesive composition can also be containing other (methyl) different from (methyl) acrylic resin (A) Acrylic resin.Wherein, from the blooming 1 of adhesive phase and comprise the resistance to gold of optical laminate of this blooming 1 From the viewpoint of belonging to corrosivity and durability, the content of (methyl) acrylic resin (A) is at whole (methyl) acrylic acid seriess In the total of resin, more than preferably 70 weight %, more than more preferably 80 weight %, more preferably 90 weight % with On, adhesive composition contains only (methyl) acrylic resin (A) particularly preferable as base polymer.

(methyl) acrylic resin (A) or can other (methyl) acrylic resin as required such as The known method manufacture such as solution polymerization process, mass polymerization, suspension polymerization, emulsion polymerization can be utilized.At (methyl) The manufacture of acrylic resin generally uses polymerization initiator.Used relative in the manufacture of (methyl) acrylic resin All total 100 weight portions of monomer, use the polymerization initiator about 0.001～5 weight portions.It addition, (methyl) acrylic acid It is that resin can also utilize the method such as making polymerization carry out with ultraviolet isoreactivity energy-ray to manufacture.

As polymerization initiator, use thermal polymerization, Photoepolymerizationinitiater initiater etc..As Photoepolymerizationinitiater initiater, such as 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc. can be enumerated.As thermal polymerization, such as may be used To enumerate 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexamethylene-1-first Nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-methoxyl-valeronitrile), two Methyl-2,2 '-azo double (2 Methylpropionic acid ester), 2, the azo system of 2 '-azo two (2-hydroxymethyl propionitrile) etc Compound；Lauroyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, peroxidized t-butyl perbenzoate, hydroperoxidation are withered Alkene, di-isopropyl peroxydicarbonate, dipropyl peroxydicarbonate, new peroxide tert-butyl caprate, peroxidating neopentanoic acid uncle The organic peroxide of butyl ester, peroxidating (3,5,5-trimethyl acetyl) etc；Potassium peroxydisulfate, Ammonium persulfate., hydrogen peroxide it The inorganic peroxide etc. of class.Alternatively, it is also possible to by and used the oxidoreduction series initiators etc. of peroxide and reducing agent to make Use for polymerization initiator.

As the manufacture method of (methyl) acrylic resin, preferred solution polymerization process in method indicated above.Molten One example of liquid polymerization is monomer used and organic solvent to be mixed, and in a nitrogen atmosphere, adds thermal polymerization, 40 ～about 90 DEG C, preferably about 50～80 DEG C stir about 3～15 hours.In order to control reaction, it is also possible to connect in polymerization Add monomer or thermal polymerization continuously or off and on or add monomer or thermal polymerization with the state being dissolved in organic solvent Initiator.As organic solvent, such as, can use the aromatic hydrocarbon of toluene, dimethylbenzene etc；Ethyl acetate, butyl acetate Deng esters；The aliphatic alcohols such as propanol, isopropanol；The ketones etc. such as acetone, butanone, methyl iso-butyl ketone (MIBK).

(2-2) silane compound (B)

Adhesive composition contains silane compound (B).Silane compound (B) is the silanization represented with following formula (I) Compound:

[changing 9]

According to containing the adhesive phase 20 of silane compound (B) represented with above-mentioned formula (I), and use other silanization The situation of compound is compared, and can improve the blooming 1 with adhesive phase and the optical laminate that comprises this blooming 1 Resistance to metal protection and durability, it addition, thus can improve the closely sealed of adhesive phase 20 and metal level 30, glass substrate etc. Property.Silane compound of more than two kinds (B) can also be used.

The concrete example of the alkane diyl that can constitute the carbon number 1～20 of the A in above-mentioned formula (I) include methylene, 1,2- Ethane diyl, 1,3-propane diyl, Isosorbide-5-Nitrae-butane diyl, 1,5-pentane diyl, 1,6-hexane diyl, 1,7-heptane two Base, 1,8-octane diyl, 1,9-nonane diyl, 1,10-decane diyl, 1,12-dodecane diyl, 1, the 14-tetradecane two Base, 1,16-hexadecane diyl, 1,18-octadecane diyl, 1,20-eicosane diyl.The fat of the divalent of carbon number 3～20 The concrete example of ring type alkyl includes 1,3-chloro-pentane diyl, Isosorbide-5-Nitrae-hexamethylene diyl.Constitute this alkane diyl and this ester ring type -the CH of alkyl₂-included-CH by the concrete example of the group after-O-or-C (=O)-replacement₂CH₂-O- CH₂CH₂-,-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-,-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-O- CH₂CH₂-,-CH₂CH₂-C (=O)-O-CH₂CH₂-,-CH₂CH₂-O-CH₂CH₂-C (=O)-O- CH₂CH₂-,-CH₂CH₂CH₂CH₂-O-CH₂CH₂-,-CH₂CH₂CH₂CH₂-O-CH₂CH₂CH₂CH₂-.

As the R that can constitute in above-mentioned formula (I)¹、R²、R³、R⁴、R⁵And R⁶The alkyl of carbon number 1～5, Ke Yiju Go out methyl, ethyl, just and isopropyl, just, the different and tert-butyl group, just, the various amyl groups such as different and tertiary pentyl, above-mentioned as constituting R in formula (I)²、R³、R⁴、R⁵And R⁶The alkoxyl of carbon number 1～5, can enumerate methoxyl group, ethyoxyl, positive propoxy, Isopropoxy, n-butoxy, isobutoxy, tert-butoxy, just, the various amoxys such as different and tertiary amoxy.This alkyl and alcoxyl The carbon number of base is each independent, preferably 1～4, more preferably 1～3, and more preferably 1 or 2.

The concrete example of the silane compound represented with above-mentioned formula (I) is expressed as follows.

Double (trimethoxysilyl) methane,

Double (triethoxysilyl) methane,

Double (tripropoxy-silicane base) methane,

Double (three butoxy silicyls) methane,

Double (three amoxy silicyls) methane,

Double (dimethoxy-methyl silicyl) methane,

Double (dimethoxy-ethyl silicyl) methane,

Double (dimethoxypropyl silicyl) methane,

Double (diethoxymethyl silicyl) methane,

Double (dipropoxy methyl silicane base) methane,

Double (methoxyl group dimetylsilyl) methane,

1-(trimethyl silyl)-1-(methoxyl group dimetylsilyl) methane,

1-(trimethyl silyl)-1-(dimethoxy-methyl silicyl) methane,

1-(trimethoxysilyl)-1-(triethoxysilyl) methane,

Double (dimethoxyethoxy silicyl) methane,

1,2-double (trimethoxysilyl) ethane,

1,2-double (triethoxysilyl) ethane,

1,2-double (tripropoxy-silicane base) ethane,

1,2-double (three butoxy silicyls) ethane,

1,2-double (three amoxy silicyls) ethane,

1,2-double (dimethoxy-methyl silicyl) ethane,

1,2-double (dimethoxy-ethyl silicyl) ethane,

1,2-double (dimethoxypropyl silicyl) ethane,

1,2-double (dimethoxy-ethyl silicyl) ethane,

1,2-double (dimethoxypropyl silicyl) ethane,

1,2-double (diethoxymethyl silicyl) ethane,

1,2-double (dipropoxy methyl silicane base) ethane,

1,2-double (methoxyl group dimetylsilyl) ethane,

1-(trimethyl silyl)-2-(methoxyl group dimetylsilyl) ethane,

1-(trimethyl silyl)-2-(dimethoxy-methyl silicyl) ethane,

1-(trimethoxysilyl)-2-(triethoxysilyl) ethane,

1,2-double (dimethoxyethoxy silicyl) ethane,

1,3-double (trimethoxysilyl) propane,

1,3-double (triethoxysilyl) propane,

1,3-double (tripropoxy-silicane base) propane,

Isosorbide-5-Nitrae-bis-(trimethoxysilyl) butane,

Isosorbide-5-Nitrae-bis-(triethoxysilyl) butane,

Isosorbide-5-Nitrae-bis-(tripropoxy-silicane base) butane,

Isosorbide-5-Nitrae-bis-(three butoxy silicyls) butane,

Isosorbide-5-Nitrae-bis-(three amoxy silicyls) butane,

Isosorbide-5-Nitrae-bis-(dimethoxy-methyl silicyl) butane,

Isosorbide-5-Nitrae-bis-(dimethoxy-ethyl silicyl) butane,

Isosorbide-5-Nitrae-bis-(dimethoxypropyl silicyl) butane,

Isosorbide-5-Nitrae-bis-(diethoxymethyl silicyl) butane,

Isosorbide-5-Nitrae-bis-(dipropoxy methyl silicane base) butane,

Isosorbide-5-Nitrae-bis-(methoxyl group dimetylsilyl) butane,

1-(trimethyl silyl)-4-(methoxyl group dimetylsilyl) butane,

1-(trimethyl silyl)-4-(dimethoxy-methyl silicyl) butane,

1-(trimethoxysilyl)-4-(triethoxysilyl) butane,

Isosorbide-5-Nitrae-bis-(dimethoxyethoxy silicyl) butane,

1,5-double (trimethoxysilyl) pentanes,

1,5-double (triethoxysilyl) pentanes,

1,5-double (tripropoxy-silicane base) pentanes,

1,6-double (trimethoxysilyl) hexanes,

1,6-double (triethoxysilyl) hexanes,

1,6-double (tripropoxy-silicane base) hexanes,

1,6-double (three butoxy silicyls) hexanes,

1,6-double (three amoxy silicyls) hexanes,

1,6-double (dimethoxy-methyl silicyl) hexanes,

1,6-double (dimethoxy-ethyl silicyl) hexanes,

1,6-double (dimethoxypropyl silicyl) hexanes,

1,6-double (dimethoxy-ethyl silicyl) hexanes,

1,6-double (dimethoxypropyl silicyl) hexanes,

1,6-double (diethoxymethyl silicyl) hexanes,

1,6-double (dipropoxy methyl silicane base) hexanes,

1,6-double (methoxyl group dimetylsilyl) hexanes,

1-(trimethyl silyl)-6-(methoxyl group dimetylsilyl) hexane,

1-(trimethyl silyl)-6-(dimethoxy-methyl silicyl) hexane,

1-(trimethoxysilyl)-6-(triethoxysilyl) hexane,

1,6-double (dimethoxyethoxy silicyl) hexanes,

1,8-double (trimethoxysilyl) octanes,

1,8-double (triethoxysilyl) octanes,

1,8-double (tripropoxy-silicane base) octanes,

1,8-double (three butoxy silicyls) octanes,

1,8-double (three amoxy silicyls) octanes,

1,8-double (dimethoxy-methyl silicyl) octanes,

1,8-double (dimethoxy-ethyl silicyl) octanes,

1,8-double (dimethoxypropyl silicyl) octanes,

1,8-double (dimethoxy-ethyl silicyl) octanes,

1,8-double (dimethoxypropyl silicyl) octanes,

1,8-double (diethoxymethyl silicyl) octanes,

1,8-double (dipropoxy methyl silicane base) octanes,

1,8-double (methoxyl group dimetylsilyl) octanes,

1-(trimethyl silyl)-8-(methoxyl group dimetylsilyl) octane,

1-(trimethyl silyl)-8-(dimethoxy-methyl silicyl) octane,

1-(trimethoxysilyl)-8-(triethoxysilyl) octane,

1,8-double (dimethoxyethoxy silicyl) octanes,

1,10-double (trimethoxysilyl) decane,

1,12-double (trimethoxysilyl) dodecanes,

1,14-double (trimethoxysilyl) tetradecanes,

1,16-double (trimethoxysilyl) hexadecanes,

1,18-double (trimethoxysilyl) octadecanes,

1,20-double (trimethoxysilyl) eicosanes etc..

Wherein, rotten from the resistance to metal with the blooming 1 of adhesive phase and the optical laminate that comprises this blooming 1 From the viewpoint of erosion property, adhesive phase 20 and the adaptation of metal level 30 or glass substrate etc., silane compound (B) be preferably with The silane compound that following formula (II) represents:

[changing 10]

In formula, R¹、R³、R⁴、R⁵And R⁶Represent implication same as described above, R respectively⁷Represent the alkyl of carbon number 1～5, m Represent the integer of 1～20.R can be constituted⁷The concrete example of alkyl of carbon number 1～5 same as described above.From same as described above From the viewpoint of, the silane compound that silane compound (B) more preferably represents with the above-mentioned formula (II) of the integer that m is 4～20, The silane compound more preferably represented with the above-mentioned formula (II) of the integer that m is 6～8, particularly preferably 1,6-double (three Methoxysilyl) hexane, 1, double (triethoxysilyl) hexane of 6-, 1,8-double (trimethoxysilyl) is pungent Alkane, 1, double (triethoxysilyl) octanes of 8-etc., with integer that m is 6～8 and OR¹、R²、R³、R⁴、R⁵、R⁶And OR⁷Respectively The silane compound represented from the above-mentioned formula (II) that independently be carbon number 1～3 (such as carbon number 1 or 2).Suitably m Example be 6 or 8.

Adhesive composition can together with the silane compound (B) represented with above-mentioned formula (I) possibly together with a kind or 2 kinds with On silane compound (B) beyond other silane compounds.As other silane compounds, such as, can enumerate vinyl three Methoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, 3-glycidoxypropyl group Trimethoxy silane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl group ethyoxyl dimethylsilane, 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, 3- Chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silicon Alkane, 3-mercaptopropyi trimethoxy silane etc..

Other silane compounds can include the compound of silicone oligomers type.If by the concrete example of silicone oligomers with The form of the combination between monomer is stated, the most as follows.

3-mercaptopropyi trimethoxy silane-tetramethoxy-silicane oligomer,

3-mercaptopropyi trimethoxy silane-tetraethoxysilane oligomer,

3-Mercaptopropyltriethoxysilane-tetramethoxy-silicane oligomer,

The oligomer containing mercaptopropyi such as 3-Mercaptopropyltriethoxysilane-tetraethoxysilane oligomer；

Mercapto methyl trimethoxy silane-tetramethoxy-silicane oligomer,

Mercapto methyl trimethoxy silane-tetraethoxysilane oligomer,

Mercapto methyl triethoxysilane-tetramethoxy-silicane oligomer,

The oligomer containing mercapto methyl such as mercapto methyl triethoxysilane-tetraethoxysilane oligomer；

3-glycidoxypropyltrime,hoxysilane-tetramethoxy-silicane alkyl copolymer,

3-glycidoxypropyltrime,hoxysilane-tetraethoxy-silicane alkyl copolymer,

3-glycidoxypropyl group triethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-glycidoxypropyl group triethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-glycidoxypropyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-glycidoxypropyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-glycidoxypropyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,

3-glycidoxypropyl diethoxy silane-tetraethoxy-silicane alkyl copolymers etc. are containing 3-epoxy third The copolymer of epoxide propyl group；

3-methacryloxypropyl trimethoxy silane-tetramethoxy-silicane oligomer,

3-methacryloxypropyl trimethoxy silane-tetraethoxysilane oligomer,

3-methacryloxypropyl-tetramethoxy-silicane oligomer,

3-methacryloxypropyl-tetraethoxysilane oligomer,

3-methacryloyloxypropyl methyl dimethoxysilane-tetramethoxy-silicane oligomer,

3-methacryloyloxypropyl methyl dimethoxysilane-tetraethoxysilane oligomer,

3-methacryloyloxypropyl methyl diethoxy silane-tetramethoxy-silicane oligomer,

3-methacryloyloxypropyl methyl diethoxy silane-tetraethoxysilane oligomer etc. are containing methyl-prop The oligomer of alkene acryloxypropylethoxysilane；

3-acryloxypropyl trimethoxy silane-tetramethoxy-silicane oligomer,

3-acryloxypropyl trimethoxy silane-tetraethoxysilane oligomer,

3-acryloxypropyl triethoxysilane-tetramethoxy-silicane oligomer,

3-acryloxypropyl triethoxysilane-tetraethoxysilane oligomer,

3-acryloxypropyl dimethoxysilane-tetramethoxy-silicane oligomer,

3-acryloxypropyl dimethoxysilane-tetraethoxysilane oligomer,

3-acryloxypropyl diethoxy silane-tetramethoxy-silicane oligomer,

3-acryloxypropyl diethoxy silane-tetraethoxysilane oligomer etc. are containing acryloxy The oligomer of propyl group；

Vinyltrimethoxy silane-tetramethoxy-silicane oligomer,

Vinyltrimethoxy silane-tetraethoxysilane oligomer,

VTES-tetramethoxy-silicane oligomer,

VTES-tetraethoxysilane oligomer,

Vinyl methyl dimethoxysilane-tetramethoxy-silicane oligomer,

Vinyl methyl dimethoxysilane-tetraethoxysilane oligomer,

Vinyl methyl diethoxy silane-tetramethoxy-silicane oligomer,

The oligomer containing vinyl such as vinyl methyl diethoxy silane-tetraethoxysilane oligomer；

3-TSL 8330-tetramethoxy-silicane alkyl copolymer,

3-TSL 8330-tetraethoxy-silicane alkyl copolymer,

APTES-tetramethoxy-silicane alkyl copolymer,

APTES-tetraethoxy-silicane alkyl copolymer,

3-amino propyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-amino propyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-amino propyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,

The copolymer etc. containing amino such as 3-amino propyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer.

Wherein, rotten from the resistance to metal with the blooming 1 of adhesive phase and the optical laminate that comprises this blooming 1 From the viewpoint of the adaptation of erosion property, adhesive phase 20 and metal level 30 or glass substrate etc., the silane represented with above-mentioned formula (I) The content of compound (B) is in the total of whole silane compounds, and more than preferably 70 weight %, more preferably 80 weight % Above, more preferably more than 90 weight %, particularly preferred adhesive composition contains only silanization as silane compound Compound (B).

The content of the silane compound (B) in adhesive composition is relative to (methyl) acrylic resin (A) 100 weight Part, usually 0.01～10 weight portion, preferably 0.03～5 weight portions, more preferably 0.05～2 weight portions, further preferably It it is 0.1～1 weight portion.If the content of silane compound (B) is more than 0.01 weight portion, then it is readily available with adhesive phase Blooming 1 and the resistance to metal protection of the optical laminate that comprises this blooming 1 improve effect and adhesive phase 20 Effect is improved with the adaptation of metal level 30 or glass substrate etc..If additionally content is below 10 weight portions, then can suppress Silane compound (B) oozing out from adhesive phase 20.

(2-3) ionic compound (C)

Adhesive composition contains ionic compound (C).Ionic compound (C) is to be made up of cation and anion Compound, its anion is the anion in following group:

[changing 11]

Cation can be organic cation, inorganic cation any one.By using ionic compound (C), It is possible not only to adhesive phase 20 is given good anti-static electricity interference performance, it is also possible to give excellent resistance to metal protection and light Learn durability.Adhesive composition can be containing one kind or two or more ionic compound (C).Contain at adhesive composition In the case of ionic compound of more than two kinds (C), as long as these aniones are in above-mentioned group, the most both can be identical, also Can be different.

The concrete example of organic cation includes pyridylium, glyoxaline cation, piperidines cation, pyrrolidine Cation, tetrahydropyridine cation, dihydropyridine cation, tetrahydropyrimidine cation, dihydro-pyrimidin cation, pyrrole Azoles cation, pyrazoline cation, ammonium cation, sulfonium cation, cation etc..Organic cation can also have and takes Dai Ji.The concrete example of inorganic cation includes lithium cation (Li⁺), sodium cation (Na⁺), potassium cationic (K⁺), caesium cation 〔Cs⁺) etc. alkali metal ion；Beryllium cation (Be²⁺), magnesium cation (Mg²⁺), calcium cation (Ca²⁺) etc. alkaline-earth metal ion Deng.

Wherein from the compatibility of (methyl) acrylic resin (A) from the viewpoint of, cation be preferably organic sun from Son, from the viewpoint of anti-static electricity interference performance, more preferably pyridylium, glyoxaline cation, piperidines cation, Pyrrolidine cation, tetrahydropyridine cation, dihydropyridine cation, tetrahydropyrimidine cation, dihydro-pyrimidin The organic cation containing nitrogen-atoms such as cation, pyrazoles cation, pyrazoline cation, ammonium cation (can also have Substituted base.), more preferably there is the cation of the heterocycle structure containing nitrogen-atoms comprising unsaturated bond.

Belong to a kind of the cation with the heterocycle structure containing nitrogen-atoms comprising unsaturated bond, can have replacement The suitable concrete example of the pyridylium of base is the pyridylium represented with following formula (III):

[changing 12]

In above-mentioned formula (III), R⁸～R¹³Represent hydrogen atom independently of one another, can have the alkyl of substituent group, can have The thiazolinyl of substituted base, can have the alkynyl of substituent group, can have the aryl of substituent group, can have the heterocycle of substituent group Base, hydroxyl, ether, carboxyl, carbonyl or halogen atom, it is also possible between adjacent substituent group, form ring.

As having the alkyl of substituent group, the preferably alkyl of carbon number 1～30, its concrete example such as includes first Base, ethyl, propyl group, butyl, hexyl, octyl group, decyl, dodecyl, octadecyl, isopropyl, isobutyl group, sec-butyl, tertiary fourth Base, 1-ethyl pentyl group, cyclopenta, cyclohexyl, trifluoromethyl, 2-ethylhexyl, phenacyl, 1-naphthoyl methyl, 2- Naphthoyl methyl, 4-methylsulfany phenacyl, 4-phenylsulfartyl phenacyl, 4-dimethylaminobenzoyl methyl, 4-cyanophenacyl, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorobenzoyl methyl, 3-trifluoro Methylphenacyl group, 3-nitrophenacyl.

As having the thiazolinyl of substituent group, the preferably thiazolinyl of carbon number 2～10, its concrete example such as includes ethylene Base, pi-allyl, styryl.As having the alkynyl of substituent group, the preferably alkynyl of carbon number 2～10, its concrete example Such as include acetenyl, propinyl, propargyl.

As having the aryl of substituent group, the preferably aryl of carbon number 6～30, its concrete example such as includes benzene Base, xenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 9-phenanthryl, 1-pyrenyl, 5-naphthacenyl, 1-indenyl, 2- Base, 9-fluorenyl, terphenyl, tetrad phenyl, o-, m-and p-methylphenyl, xylyl, o-, m-and to isopropylbenzene Base,Base, pentalene base, binaphthyl, three binaphthyl, four binaphthyl cycloheptatriene base (heptalenyl), stretch biphenyl Base, bicyclopentadiene phenyl (indacenyl), fluoranthene base, acenaphthenyl, ethylene close anthryl (アセア Application トリレニ Le base), Base (phenalenyl), fluorenyl, anthryl, dianthranide base, three dianthranide bases, tetrad anthryl, anthraquinoline base, phenanthryl, benzo phenanthryl, pyrene Base,Base, naphthacenyl, seven days of the week thiazolinyl (pleiadenyl), base, base, pentapheneyl, thick pentapheneyl, quarter phenyl, six benzene Three naphthyls stretched by base, thick hexaphenyl, Ru Ji (Le PVC セニ Le base), coronenyl (U ロネニ Le base), connection (trinaphthylenyl), seven phenyl, thick seven phenyl, pyrene anthryl (ピラ Application トレニ Le base), ovalene base (cowherb Base) (ovalenyl).

As having the heterocyclic radical of substituent group, preferably comprise the fragrance of nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms Race or aliphatic heterocycle, its concrete example such as includes thienyl, benzo [b] thienyl, naphtho-[2,3-b] thienyl, thianthrene Base, furyl, pyranose, isobenzofuran-base, chromenyl, ton base, phenazinyl, 2H-pyrrole radicals, pyrrole radicals, imidazoles Base, pyrazolyl, pyridine radicals, pyrazinyl, pyrimidine radicals, pyridazinyl, indolizine base, isoindolyl, 3H-indyl, indyl, 1H- Indazolyl, purine radicals, 4H-quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinolyl, quinazolyl, cinnolines Base, pteridine radicals, 4aH-carbazyl, carbazyl, B-carboline base, phenanthridinyl, acridinyl, pah piperidinyl, phenanthroline base, phenazinyl, Phenarsazine base (phenarsazinyl), isothiazolyl, phenothiazinyl, isoxazolyl, furan a word used for translation base, phenazinyl, different Chromanyl, Chromanyl, pyrroles's piperidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, Yin Diindyl quinoline base, isoindoline base, quinoline are given repeated exhortations ring group, morpholinyl, thioxanthryl.

Can replace above-mentioned can have a substituent group alkyl, can have the thiazolinyl of substituent group, can have substituent group Alkynyl, can have the aryl of substituent group and can have substituent group concrete of hydrogen atom of heterocyclic radical of substituent group Example such as includes the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine；The alcoxyls such as methoxyl group, ethyoxyl, tert-butoxy Base；Phenoxy group, to the aryloxy group such as toloxyl, methoxycarbonyl, butoxy carbonyl, phenyloxycarbonyl, vinyl epoxide carbonyl, The alkoxy carbonyls such as aryloxycarbonyl；The acyloxy such as acetoxyl group, propionyloxy, benzoyloxy；Acetyl group, benzoyl, The acyl groups such as isobutyryl, acryloyl group, methylacryloyl, methoxalyl；The alkylthio group such as methyl mercapto, tertiary butylthio；Thiophenyl, To arylthios such as Tolylsulfanvl；The alkyl amino such as methylamino, Cyclohexylamino；Dimethylamino, diethylamino, morpholine The dialkyl amido such as base, piperidyl；The arylaminos such as phenyl amino, p-methylphenyl amino；Methyl, ethyl, the tert-butyl group, dodecane The alkyl such as base；The aryl such as phenyl, p-methylphenyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl；Hydroxyl, carboxyl, sulphonyl Amido, formoxyl, sulfydryl, sulfo group, mesyl, p-toluenesulfonyl, amino, nitro, nitroso-group, cyano group, trifluoromethyl, three Chloromethyl, trimethyl silyl, phosphinico (phosphinico), phosphonate group, alkyl sulphonyl, aryl sulfonyl, three alkane Base ammonium, dimethyl sulfonium base, triphenylbenzene formyl methyl base.

The pyridylium represented with above-mentioned formula (III) is preferably N-substituted pyridines cation.In the case of Gai, R⁸ Preferably can have the alkyl of substituent group, the more preferably straight-chain of carbon number 1～20, branched or ring-type alkyl. Carbon number is preferably 1～16.R⁹～R¹³Each independent, preferably hydrogen atom, the straight-chain of carbon number 1～20, side chain or The alkyl of the straight-chain of ring-type alkyl, hydroxyl or halogen atom, more preferably hydrogen atom or carbon number 1～20.

If to enumerate ionicization from the viewpoint of anti-static electricity interference performance, resistance to metal protection and optical durability The suitable example of compound (C), the most as follows.

1) following ionic compound, its cation is the pyridylium represented with following formula (III):

[changing 13]

(in formula, preferably R⁸Straight-chain, branched or ring-type alkyl, R for carbon number 1～16⁹～R¹³The most independent Ground is the alkyl of straight-chain of hydrogen atom or carbon number 1～20), anion be any one the moon in above-mentioned group from Son.

2) following ionic compound, its cation is lithium cation (Li⁺), sodium cation (Na⁺), potassium cationic (K⁺) etc. inorganic cation, anion is any one anion in above-mentioned group.

The content of the ionic compound (C) in adhesive composition is relative to (methyl) acrylic resin (A) 100 weight Amount part, preferably 0.1～10 weight portions, more preferably 0.2～8 weight portions, more preferably 0.3～5 weight portion, the most excellent Elect 0.5～3 weight portions as.If the content of ionic compound (C) is more than 0.1 weight portion, the most beneficially anti-static electricity interference The raising of performance, below 10 weight portions, is then conducive to the blooming 1 with adhesive phase and comprises this blooming 1 The resistance to metal protection of optical laminate and durability.

Adhesive composition can be gone back and use it together with the ionic compound (C) of the above-mentioned anion with regulation Anti-static electricity interference agent in addition, from the blooming 1 of adhesive phase and comprise optical laminate resistance to of this blooming 1 The viewpoint such as metal protection considers, adhesive composition preferably as anti-static electricity interference agent contain only above-mentioned the moon with regulation from The ionic compound (C) of son.

(2-4) isocyanates system's cross-linking agent (D)

Adhesive composition preferably comprises isocyanates system cross-linking agent (D).By using isocyanates system cross-linking agent (D) as Cross-linking agent uses, it is possible to improves the blooming 1 with adhesive phase and comprises optical laminate resistance to of this blooming 1 Metal protection and durability.Isocyanates system cross-linking agent (D) may be used alone or in combination of two or more kinds.

Isocyanates system cross-linking agent (D) is the compound in intramolecular with at least 2 NCOs (-NCO), tool For body, toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone diisocyanate, dimethylbenzene two can be enumerated Isocyanates, hydrogenated xylene diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, Naphthalene diisocyanate, triphenylmethane triisocyanate etc..Additionally isocyanates system cross-linking agent (D) can also be these Carbimide .s The polyol compound adduct (adduct of such as glycerol or trimethylolpropane) of ester compounds, isocyanuric acid are esterified Thing, biuret form compound and with polyether polyol or PEPA, acrylic polyol, polybutadiene polyol, Polyisoprene polyol etc. occur the isocyanate compound of carbamate prepolymer type obtained by additive reaction etc. to derive Thing.In the middle of above-mentioned, particularly preferred toluene di-isocyanate(TDI), hexamethylene diisocyanate, XDI or this The polyol compound adduct of a little isocyanate compounds, from the blooming 1 of adhesive phase and comprise this blooming From the viewpoint of the durability of the optical laminate of 1, more preferably XDI or its polyol compound adduct.

The content of isocyanates system cross-linking agent (D), relative to (methyl) acrylic resin (A) 100 weight portion, is preferably 0.08～2.5 weight portions, more preferably 0.1～2 weight portions (below such as 1 weight portion).If isocyanates system cross-linking agent (D) Content be in this scope, then taking into account the blooming 1 with adhesive phase and comprising the optics stacking of this blooming 1 The resistance to metal protection of body and the aspect of durability are favourable.

Adhesive composition can be together with isocyanates system cross-linking agent (D), and with the cross-linking agent beyond it, such as epoxy Compound, aziridine cpd, meal chelate compounds, peroxide etc., however from adhesive phase blooming 1, And from the viewpoint of comprising resistance to metal protection and the durability of the optical laminate of this blooming 1, adhesive composition is excellent It is elected to be and contains only isocyanates system cross-linking agent (D) for cross-linking agent, particularly preferably contain substantially no peroxide.Described in herein Contain substantially no, refer to that relative to the content of (methyl) acrylic resin (A) 100 weight portion be below 0.01 weight portion.

(2-5) other compositions

Adhesive composition can containing one kind or two or more solvent, crosslinking catalyst, UV absorbent, weather-proof surely Determine the additives such as agent, viscosifier, plasticizer, softening agent, dyestuff, pigment, inorganic filler, light scattering microgranule.In addition, to Combined with ultraviolet radiation curable compound in adhesive composition, is allowed to solidify, shape forming irradiation ultraviolet radiation after adhesive phase The adhesive phase becoming harder is also useful way.As crosslinking catalyst, such as, can enumerate hexamethylene diamine, second two Amine, polyethylene imine, hexamethylenetetramine, diethylenetriamines, trien, isophorone diamine, trimethylene The amine compounds such as diamidogen, poly-amino resins and melmac.

Adhesive composition can be containing can improving the blooming 1 with adhesive phase and comprising this blooming 1 The antirust agent of the resistance to metal protection of optical laminate.As antirust agent, can enumerate benzotriazole based compound, other three Azole compounds etc. three azole compounds；Benzothiazole based compound, other the thiazole compound such as thiazole compound；Benzyl Base imidazole compound, other the imidazole compound such as imidazole compound；Imidazoline based compound；Quinoline based compound； Pyridine based compound；Pyrimidine compound；Indole based compound；Amine compound；Urea based compound；Sodium benzoate；Benzyl mercapto Base system compound；Di-sec-butyl thioether；And diphenyl sulfoxide.

But, according to the present invention, even if not containing antirust agent can also obtain sufficient resistance to metal protection, the most antirust The content of agent is the smaller the better.Particularly, adhesive composition preferably contains substantially no three azole compounds as antirust agent, More preferably contain substantially no the antirust agent in above-mentioned compound group.Containing substantially no described in herein, refers to phase Content for (methyl) acrylic resin (A) 100 weight portion is below 0.01 weight portion.

(3) with the composition of blooming and the manufacture method of adhesive phase

Blooming 1 with adhesive phase comprises blooming 10 and is laminated in the adhesive phase 20 (figure in its at least one face 1).Can also be in the two sides laminate adhesive oxidant layer 20 of blooming 10.Generally, adhesive phase 20 is directly laminated in blooming 10 Surface.When adhesive phase 20 being located at the surface of blooming 10, preferably binding face and/or the adhesive phase 20 to blooming 10 Binding face implement the formation of prime coat or surface activation processes, such as Cement Composite Treated by Plasma, sided corona treatment etc., more preferably Implement sided corona treatment.

It is that in the case of one side as shown in Figure 2 protects polarization plates, adhesive phase 20 is generally preferably by directly at blooming 10 Connect be laminated in polarization unilateral, i.e. the face with the first resin molding 3 opposite side of polaroid 2.It is as shown in Figure 3 at blooming 10 In the case of two-sided protection polarization plates, adhesive phase 20 both can be laminated in outside any one party of first, second resin molding 3,4 Surface, it is also possible to be laminated in the outer surface of two sides.

Although anti-static electricity interference layer can also additionally be arranged between blooming 10 and adhesive phase 20, yet with this Bright adhesive phase 20 can utilize single adhesive phase to give excellent anti-static electricity interference, therefore from optical laminate Filming, duplexer manufacturing process simplification from the standpoint of, preferably do not have anti-between blooming 10 and adhesive phase 20 Static interference layer.

Blooming 1 with adhesive phase can also comprise the barrier film (stripping of the outer surface being laminated in adhesive phase 20 Film).This barrier film is generally stripped removing when the use of adhesive phase 20 (such as during stacking on metal level 30).Barrier film is such as Can be to by various resins such as polyethylene terephthalate, polybutylene terephthalate (PBT), Merlon, polyarylates The face being formed with adhesive phase 20 of the film constituted implements the film that the demouldings such as silicone-treated process.

Blooming 1 with adhesive phase can be obtained as below, i.e. by molten for each composition of the above-mentioned adhesive composition of composition Solve or be scattered in solvent and make the adhesive composition containing solvent, then, coated the surface of blooming 10 also It is dried and forms adhesive phase 20.It addition, the blooming 1 with adhesive phase can also be obtained as below, i.e. in the demoulding of barrier film Process face landform same as above composite adhesives layer 20, by this adhesive phase 20 stacking (transfer) in the surface of blooming 10.

＜ optical laminate ＞

Fig. 4 and Fig. 5 is the constructed profile of the example of the layer composition of the optical laminate representing the present invention.1 enforcement In mode, the optical laminate of the present invention is as shown in Figures 4 and 5, comprise the blooming 1 with adhesive phase and be laminated in its glue The metal level 30 of mixture layer 20 side.Optical laminate 5 shown in Fig. 4 is as blooming using polarization plates 10a shown in Fig. 2 10 examples used, the optical laminate 6 shown in Fig. 5 is polarization plates 10b shown in Fig. 3 to be used as blooming 10 Example.In optical laminate 5,6 shown in Fig. 4 and Fig. 5, with the blooming 1 of adhesive phase by so that its adhesive phase 20 modes directly contacted with metal level 30 are laminated on metal level 30.According to the present invention, make like this adhesive phase 20 with In the optical laminate of the composition that metal level 30 directly contacts, it is also possible to effectively suppress the corrosion of metal level 30.

Fig. 6 is the constructed profile of another example of the layer composition of the optical laminate representing the present invention.Implement this another In mode the optical laminate of present invention optical laminate 7 shown in Fig. 6, with the blooming 1 of adhesive phase Adhesive phase 20 is pressed from both sides across resin bed 50 and metal level 30 stacking.Adhesive phase 20 directly contacts with resin bed 50.At this light Learn in duplexer 7, it is also possible to effectively suppress the corrosion of metal level 30.It is configured at the tree between adhesive phase 20 and metal level 30 Lipid layer 50 can also be such as the solidification nitride layer of curable resin.Can make as the curable resin that can form resin bed 50 Use known curable resin, such as, can enumerate the curable resin described in Japanese Unexamined Patent Publication 2009-217037 publication.

Fig. 7 is the constructed profile of another example of the layer composition of the optical laminate representing the present invention.Implement this another In mode the optical laminate of present invention optical laminate 8 shown in Fig. 7, it is also possible to not there is metal level 30.Should In the case of, with adhesive phase blooming 1 adhesive phase 20 such as by with substrate 40 stacking.Substrate 40 as described later, example As for glass substrate.

Metal level 30 can be such as containing selected from aluminum, copper, silver, gold, ferrum, stannum, zinc, nickel, molybdenum, chromium, tungsten, lead and containing choosing The layer of more than a kind in the alloy of the metal of more than two kinds in them, from the viewpoint of electric conductivity, is preferably containing choosing The layer of the metallic element in aluminum, copper, silver and gold, from the viewpoint of electric conductivity and cost, more preferably containing aluminium element Layer, more preferably contains the layer of aluminium element as main constituent.What is called contains as main constituent, refers to constitute metal level 30 Metal ingredient is more than 30 weight % of whole metal ingredient, is more than 50 weight % further.

Metal level 30 can also be such as the metal oxide layers such as ITO, yet with the present invention with adhesive phase Blooming 1 is good particularly with the corrosion resistance of metal simple-substance or alloy, and therefore metal level 30 preferably comprises by above-mentioned metal The metal simple-substance that element is constituted and/or the alloy of more than two kinds containing above-mentioned metallic element.But, optical laminate also may be used , together with this kind of metal level 30, also there is the transparent electrode layer being made up of metal-oxides such as ITO.

The form (such as thickness etc.) of metal level 30, preparation method are not particularly limited, in addition to can being metal forming, Can also is that the metal level utilizing vacuum vapour deposition, sputtering method, ion plating method, ink jet printing method, woodburytype to be formed, preferably For the metal level utilizing sputtering method, ink jet printing method, woodburytype to be formed, more preferably utilize the metal level that sputtering is formed. In the metal level utilizing sputtering to be formed and metal forming, the former side has the trend of corrosion-resistant, but according to the present invention Optical laminate, for utilize sputtering formed metal level also there is good resistance to metal protection.The thickness of metal level 30 Usually below 3 μm, below preferably 1 μm, below more preferably 0.8 μm.Additionally the thickness of metal level 30 is usually 0.01 μm Above.Additionally, in the case of metal level 30 is metal wiring layer, the live width of the metal line that its metal wiring layer is had is led to It is often below 10 μm, below preferably 5 μm, more preferably below 3 μm.It addition, the live width of metal line is usually 0.01 μ More than m, it is preferably more than 0.1 μm, more preferably more than 0.5 μm.For by the metal level 30 of this thin film or the gold of fine rule Belonging to the metal level 30 that wiring is constituted, the optical laminate of the present invention also shows that good resistance to metal protection.Particularly at gold Belong to and connect up such as thickness and be below 3 μm and time live width is below 10 μm, or thickness is below 3 μm and live width be 10 μm with Under, when utilizing sputtering method to be formed, it is also possible to suppress it to corrode, particularly can corrode with inhibition point.

Metal level 30 can be such as the hardware cloth of the touch input element that touch input formula liquid crystal indicator is had Line layer (i.e. electrode layer).In the case of Gai, metal level 30 be generally by the character pattern with regulation.It is metal line by metal level 30 One example of the situation of layer is shown in Fig. 8.Optical laminate shown in Fig. 8 can also omit resin bed 50.By pattern On the metal level 30 changed in the case of stacking adhesive phase 20, binding agent 20 can also have the portion not contacted with metal level 30 Point.Metal level 30 can also be the continuous film containing above-mentioned metal or alloy.

It addition, metal level 30 both can be single layer structure, it is also possible to be 2 layers or the multiple structure of more than 3 layers.As multilamellar The metal level of structure, such as, can enumerate the layer (wire netting etc.) containing metal of the 3-tier architecture represented with molybdenum/aluminum/molybdenum.

As shown in Fig. 4 and Fig. 5 etc., the metal level 30 of for example, metal wiring layer can also be formed on substrate 40, should In the case of, the optical laminate of the present invention can comprise this substrate 40.The formation of metal level 30 on the substrate 40 is the most permissible Utilization sputtering is carried out.Substrate 40 can be the transparency carrier constituting liquid crystal cells contained in touch input element.Substrate 40 is excellent Elect glass substrate as.As the material of glass substrate, such as, can enumerate soda-lime glass, glass with lower alkali content, alkali-free glass etc..Metal Layer 30 both can be formed at the comprehensive of substrate 40, it is also possible to is formed at one part.Form the gold being patterned on the substrate 40 Belong to when layer 30, when the part on the surface of substrate 40 forms metal level 30, the part meeting of adhesive phase 20 and example Substrate 40 as being made up of glass directly contacts, yet with adhesive phase 20 and glass close of the optical laminate of the present invention Conjunction property is the most excellent, therefore optical laminate and possess the liquid crystal indicator of this optical laminate in this case resistance to Property is the most excellent for a long time.

By the blooming 1 with adhesive phase being pressed from both sides across its adhesive phase on metal level 30 (or above-mentioned resin bed) 20 laminatings, it is possible to obtain optical laminate 5,6.Make the blooming 1 with adhesive phase is fitted with metal level 30 After going out optical laminate, in the case of having any the best situation, it is necessary to by the blooming 1 with adhesive phase from metal level Peel off in 30, again other the blooming 1 with adhesive phase is fitted on metal level 30, i.e. needs so-called reprocessing Operation.The blooming 1 with adhesive phase of the present invention is difficult to the surface of the metal level 30 after peeling off from metal level 30 and produces Raw fuzzy, culls etc., re-workability is excellent.According to the blooming 1 with adhesive phase of the present invention, even if at laminating binding agent The surface of layer 20 is not metal level 30 but when glass substrate or ITO layer, it is also possible to demonstrate good re-workability.

＜ liquid crystal indicator ＞

The liquid crystal indicator of the present invention comprises the blooming 1 with adhesive phase of the invention described above, more typically In the case of comprise above-mentioned optical laminate.The liquid crystal indicator of the present invention can suppress the corrosion of metal level 30, it addition, display Go out good durability.

The liquid crystal indicator of the present invention preferably has the touch input formula liquid crystal indicator of touch panel function.Touch Touch input type liquid crystal indicator and possess the touch input element and backlight comprising liquid crystal cells.The composition of touch panel can To be known any modes such as Out-cell type, On-cell type, In-cell type, the additionally manner of execution of touch panel Can be to be known any mode such as resistive film mode, capacitive way (surface type capacitive way, porjection type capacitive way). The blooming 1 with adhesive phase of the present invention both can be configured at the visible side of touch input element (liquid crystal cells), it is possible to To be configured at backlight side, it is also possible to be configured at two side sides.The type of drive of liquid crystal cells can be to be TN mode, VA mode, IPS Known any modes such as mode, multidomain mode, OCB mode.In the liquid crystal indicator of the present invention, optical laminate 5, The substrate 40 that 6 are had can be the substrate (typically glass substrate) included in above-mentioned liquid crystal cells.

[embodiment]

Hereinafter, provide embodiment and comparative example and the present invention is carried out more specific description, but the present invention is not by this A little examples limit.Hereinafter, represent that usage amount, part of content and % are as long as no particularly pointing out, it is simply that weight basis.

＜ manufactures example 1: the adhesive phase manufacture ＞ of (methyl) acrylic resin (A-1)

In the reaction vessel possessing condensing tube, nitrogen ingress pipe, thermometer and blender, add shown in table 1 (numerical value of table 1 is weight portion to composition.) monomer and 81.8 parts of solution being obtained by mixing of ethyl acetate.By the sky in reaction vessel After gas is replaced with nitrogen, making interior temperature is 60 DEG C.Thereafter, it is added in ethyl acetate 10 parts and is dissolved with azodiisobutyronitrile 0.12 part Solution.After mutually synthermal holding 1 hour, while interior temperature is remained 54～56 DEG C, to add 17.3 parts/Hr of speed Ethyl acetate is added continuously in reaction vessel so that the concentration of polymer substantially 35%.Adding from ethyl acetate Add beginning until after interior temperature is remained 54～56 DEG C by 12 hours, adding ethyl acetate and the concentration of polymer be adjusted to 20%, obtain the ethyl acetate solution of (methyl) acrylic resin (A-1).The weight of (methyl) acrylic resin (A-1) Average molecular weight Mw is 1,390,000, and the ratio Mw/Mn of weight average molecular weight Mw and number-average molecular weight Mn is 5.32.At gel permeation chromatography (GPC) in elution curve, the composition of Mw139 ten thousand demonstrates single peak, does not see in the scope of Mw1000～2,500,000 Other peak.

＜ manufactures example 2: the adhesive phase manufacture ＞ of (methyl) acrylic resin (A-2)

In addition to being set to by the composition of monomer as shown in table 1, obtain (methyl) acrylic acid series tree identically with manufacture example 1 The ethyl acetate solution (resin concentration: 20%) of fat (A-2).Weight average molecular weight Mw of (methyl) acrylic resin (A-2) Being 1,410,000, Mw/Mn is 4.71.In the elution curve of GPC, the composition of Mw141 ten thousand demonstrates single peak, at Mw1000～ The scope of 2500000 is not seen other peak.

In superincumbent manufacture example, weight average molecular weight Mw and number-average molecular weight Mn measure as follows, as color in GPC device " the Shodex GPC that spectrum 4 Tosoh (strain) of post arranged in series " the TSKgel XL " that make and 1 Showa electrician (strain) are made KF-802 " add up to 5, use oxolane as eluent, in sample solution concentration 5mg/mL, sample import volume 100 μ L, temperature 40 DEG C, flow velocity is under conditions of 1mL/ minute, utilizes polystyrene standard conversion to be measured.Obtain GPC elution curve time Condition is also set to same.

Glass transition temperature Tg is to use the differential scanning calorimeter of SII Nano Technology Co., Ltd. (DSC) " EXSTAR DSC6000 ", in a nitrogen atmosphere, is measuring temperature range-80～50 DEG C, programming rate 10 DEG C/min Under conditions of be measured.

By the composition of the monomer in each manufacture example, (numerical value of table 1 is weight portion.) and the elution curve of GPC on Peak number (being expressed as " GPC peak number " in table 1) in the scope of Mw1000～2,500,000 is concentrated and is shown in table 1.

[table 1]

The abbreviation being positioned in " monomer composition " hurdle of table 1 refers to following monomer.

BA: butyl acrylate (glass transition temperature of homopolymer :-54 DEG C),

MA: acrylic acid methyl ester. (glass transition temperature of homopolymer: 10 DEG C),

HEA: acrylic acid 2-hydroxy methacrylate.

＜ embodiment 1～8, comparative example 1～9 ＞

(1) preparation of adhesive composition

The ethyl acetate solution (resin concentration: 20%) of (methyl) acrylic resin obtained in above-mentioned manufacture example In, relative to the solid constituent 100 parts of this solution, the silane shown in the table 2 of the amount (weight portion) shown in mixture table 2 respectively Compound (B), ionic compound (C) and isocyanates system cross-linking agent (D), then so that solid component concentration is 14% Mode is added ethyl acetate and is obtained adhesive composition.For the use level of each gradation composition shown in table 2, used Commodity when containing solvent etc., be the parts by weight as effective ingredient contained therein.

[table 2]

Noting at foot of each gradation composition represented with abbreviation in table 2.

(silane compound)

B-1: the silane compound represented with following formula:

[changing 14]

B-2: the silane compound represented with following formula:

[changing 15]

B-3:3-glycidoxypropyltrime,hoxysilane, the trade name obtained from SHIN-ETSU HANTOTAI's chemical industry (strain) “KBM403”。

(ionic compound)

C-1: the ionic compound represented with following formula:

[changing 16]

C-2: the ionic compound represented with following formula:

[changing 17]

C-3: double (trifyl) imide li,

C-4: double (fluorosulfonyl) acid imide potassium,

Double (fluorosulfonyl) imide salts of C-5:N-decyl pyridine,

C-6:N-picoline four (pentafluorophenyl group) borate,

C-7:N-decyl pyridine four (pentafluorophenyl group) borate,

C-8:N-octyl group-4-picoline hexafluorophosphate.

(isocyanates system cross-linking agent)

Ethyl acetate solution (the solid component concentration of the trimethylolpropane adduct of D-1: XDI 75%), the trade name " TAKENATE D-110N " obtained from Mitsui Chemicals (strain).

(2) making of adhesive phase

Each adhesive composition of preparation in above-mentioned (1) is used adhesive applicator so that side that dried thickness is 20 μm Formula, is coated on the barrier film being made up of the polyethylene terephthalate film implementing demoulding process and (obtains from LINTEC (strain) Trade name " PLR-382051 ") the demoulding process face, 100 DEG C be dried 1 minute and produce adhesive phase (binding agent Sheet).

(3) with the making of blooming (P-1) of adhesive phase

By average degree of polymerization about 2400,99.9 moles of % of saponification degree, polyvinyl alcohol film ((strain) Kuraray of thickness 60 μm The trade name " Kuraray Vinylon VF-PE#6000 " of system) impregnated in the pure water of 37 DEG C after, 30 DEG C impregnated in containing In the aqueous solution (iodine/potassium iodide/water (weight ratio)=0.04/1.5/100) of iodine and potassium iodide.Thereafter, impregnated at 56.5 DEG C Containing in potassium iodide and boron aqueous acid (potassium iodide/boric acid/water (weight ratio)=12/3.6/100).By pure with 10 DEG C of film After water cleans, it is dried at 85 DEG C, obtains having adsorbed iodine the polaroid of thickness about 23 μm being orientated on polyvinyl alcohol.Stretching is main Will carry out in the operation that iodine staining and boric acid process, total stretching ratio is 5.3 times.

In the one side of the polaroid of gained, press from both sides across the adhesive laminating thickness being made up of the aqueous solution of polyvinyl alcohol resin Transparent protective film (the trade name that Konica Minolta Opt (strain) makes being made up of tri acetyl cellulose membrane of 25 μm “KC2UA”〕.Then in the face with tri acetyl cellulose membrane opposite side of above-mentioned polaroid, folder is across by polyethenol series tree Zero phase difference film (the Japan Zeon being made up of cyclic polyolefin hydrocarbon system resin of adhesive thick 23 μm of laminating that the aqueous solution of fat is constituted The trade name " ZEONOR " that (strain) makes), produce polarization plates.Then, contrary with the face contacting polaroid to zero phase difference film The face of side, after implementing the Corona discharge Treatment for improving adaptation, utilizes the bonding made in laminating machine laminating above-mentioned (2) Behind the face (binding agent aspect) with barrier film opposite side of oxidant layer, ripening 7 under conditions of temperature 23 DEG C, relative humidity 65% My god, obtain the blooming (P-1) with adhesive phase.

(4) with the making of blooming (P-2) of adhesive phase

By average degree of polymerization about 2400,99.9 moles of % of saponification degree, polyvinyl alcohol film ((strain) Kuraray of thickness 30 μm The trade name " Kuraray Vinylon VF-PE#3000 " of system) impregnated in the pure water of 37 DEG C after, 30 DEG C impregnated in containing In the aqueous solution (iodine/potassium iodide/water (weight ratio)=0.04/1.5/100) of iodine and potassium iodide.Thereafter, impregnated at 56.5 DEG C Containing in potassium iodide and boron aqueous acid (potassium iodide/boric acid/water (weight ratio)=12/3.6/100).By pure with 10 DEG C of film After water cleans, it is dried at 85 DEG C, obtains having adsorbed iodine the polaroid of thickness about 12 μm being orientated on polyvinyl alcohol.Stretching Mainly carrying out in the operation that iodine staining and boric acid process, total stretching ratio is 5.3 times.

In the one side of the polaroid of gained, press from both sides across the adhesive laminating thickness being made up of the aqueous solution of polyvinyl alcohol resin Transparent protective film (the trade name that Konica Minolta Opt (strain) makes being made up of tri acetyl cellulose membrane of 25 μm " KC2UA "), produce polarization plates.Then in the face with the face opposite side being fitted with protecting film of polaroid, laminating machine is utilized Fit behind the face (binding agent aspect) with barrier film opposite side of the adhesive phase made in above-mentioned (2), in temperature 23 DEG C, relatively Ripening 7 days under conditions of humidity 65%, obtain the blooming (P-2) with adhesive phase.

(5) with the resistance to metal protection evaluation of blooming of adhesive phase

The blooming with adhesive phase (P-1) made in above-mentioned (3) is cut the examination of the size into 20mm × 50mm Testing sheet, folder is fitted in the metal level side of the glass substrate with metal level across adhesive phase.As the glass with metal level Substrate, employs the glass substrate of the metallic aluminum utilizing sputtering stacking thickness about 500nm on alkali-free glass surface (Geomatec company system).By the optical laminate of gained temperature 60 C, relative humidity 90% baking oven in keeping 500 hours After, fit with adhesive phase from polarization plates surface through magnifier (Lupe) observation from the back side illuminaton light of glass substrate The state of the metal level of the part of blooming, for spot corrosion (a diameter of more than 0.1mm and can be through the generation in hole of light), Following benchmark is utilized to be evaluated.The results are shown in Table 3.

5: layer on surface of metal can't see completely spot corrosion and nebulousurine,

4: the number of spot corrosion produced at layer on surface of metal is less than 2,

3: the number of spot corrosion produced at layer on surface of metal is 3～5,

2: the number of spot corrosion produced at layer on surface of metal is more than 6,

1: in the multiple spot corrosion of generation comprehensively of layer on surface of metal, and also create nebulousurine.

(6) with the durability evaluation of blooming of adhesive phase

By the blooming with adhesive phase (P-1) made in above-mentioned (3) so that the tensile axis direction of polarization plates is length The mode on limit cuts as peeling off barrier film after the size of 200mm × 150mm, and the binding agent aspect exposed is fitted in glass substrate On.By the test film (being pasted with the blooming with adhesive phase of glass substrate) being pasted with glass substrate of gained at high pressure In still, with temperature 50 C, pressure 5kg/cm²(490.3kPa) pressurize 20 minutes.As glass substrate, employ Corning public The alkali-free glass of department's system, trade name " Eagle XG ".Optical laminate to gained, implements following 3 kind durability examination Test.

(endurancing)

Under the drying condition of temperature 85 DEG C keep 750 hours heat resistant test,

In the environment of temperature 60 C, relative humidity 90% keep 750 hours hot resistance test,

Keep under the drying condition of temperature 85 DEG C 30 minutes, under the drying condition of temperature-40 DEG C, then keep 30 Minute, this operation is set to 1 circulation, this operation is repeated heat shock resistance (HS) test of 400 circulations.

Visualization respectively test after optical laminate, utilize visualization with or without adhesive phase tilting, come off, send out The cosmetic variation such as bubble, have rated durability according to following metewand.The results are shown in Table 3.

4: can't see completely tilting, come off, the cosmetic variation such as foaming,

3: be hardly visible tilting, come off, the cosmetic variation such as foaming,

2: tilt, come off, the cosmetic variation such as foaming slightly substantially,

1: be clearly seen that tilting, come off, the cosmetic variation such as foaming.

(7) with the re-workability evaluation of blooming of adhesive phase

The blooming with adhesive phase (P-1) made in above-mentioned (3) is cut the size into 25mm × 150mm Test film.From test film, peel off barrier film, its binding agent face is pasted on the glass substrate.Gained is pasted with glass substrate Test film (being pasted with the blooming with adhesive phase of glass substrate) in autoclave, with temperature 50 C, pressure 5kg/ cm²(490.3kPa) pressurize 20 minutes.Then, keeping 48 hours in the baking oven of 50 DEG C, then at temperature 23 DEG C, relative humidity In the atmosphere of 50%, from test film, blooming speed with 300mm/ minute together with adhesive phase is shelled along 180 ° of directions From.Observe the state of the glass baseplate surface after peeling off, utilize following benchmark to be evaluated.The results are shown in Table 3.

4: can't see completely on the surface of glass substrate fuzzy wait,

3: be hardly visible on the surface of glass substrate fuzzy wait,

2: on the surface of glass substrate it can be seen that fuzzy wait,

1: on the surface of glass substrate it can be seen that the residual of adhesive phase.

(8) with the decolourising property evaluation of blooming of adhesive phase

The blooming with adhesive phase (P-2) made in above-mentioned (4) is cut as shelling after the size of 30mm × 30mm From barrier film, the binding agent aspect exposed is fitted on glass substrate.As glass substrate, employ Corning company Alkali-free glass, trade name " Eagle XG ".Optical laminate to gained, uses the spectrophotometer (day with integrating sphere The goods name " V7100 " that this light splitting (strain) is made) determine the MD absorbance in the scope of wavelength 380～780nm and TD absorbance, Calculate the monomer absorbance under each wavelength, degree of polarization, recycle the JIS Z 8701:1999 " method for expressing-XYZ table color of color System and X₁₀Y₁₀Z₁₀Color specification system " 2 degree of visuals field (illuminant-C) carry out visibility correction, obtain the visibility correction list before long duration test Body absorbance (Ty) and visibility correction degree of polarization (Py).And, by optical laminate so that the triacetyl cellulose of polarization plates Film side is detector side, mode from glass substrate side incident light is placed in the spectrophotometer with integrating sphere.

Monomer absorbance and degree of polarization are defined by the formula respectively:

Monomer absorbance (λ)=0.5 × (Tp (λ)+Tc (λ))

Degree of polarization (λ)=100 × (Tp (λ)-Tc (λ))/(Tp (λ)+Tc (λ))

Tp (λ) is the light of the rectilinearly polarized light utilizing incident wavelength X (nm) and the relation mensuration of parallel-nicol prism Learning the absorbance (%) of duplexer, Tc (λ) is the rectilinearly polarized light utilizing incident wavelength X (nm) and Nicol crossed The absorbance (%) of the optical laminate that relation measures.

Then, by this optical laminate temperature 80 DEG C, relative humidity 90% hygrothermal environment under place 24 hours, then Place after 24 hours in the environment of temperature 23 DEG C, relative humidity 60%, utilize with long duration test before identical method obtain durable Ty and Py after test.Thereafter, Py and Ty before being individually subtracted test from Py and Ty after test and before calculating long duration test After variable quantity, obtain degree of polarization variable quantity (Δ Py) and monomer absorbance variable quantity (Δ Ty).Δ Py is shown in table 3.

[table 3]

＜ manufactures example 3: the adhesive phase manufacture ＞ of (methyl) acrylic resin (A-1)

In the reaction vessel possessing condensing tube, nitrogen ingress pipe, thermometer and blender, add shown in table 4 (numerical value of table 4 is weight portion to composition.) monomer and 81.8 parts of solution being obtained by mixing of ethyl acetate.By the sky in reaction vessel After gas is replaced with nitrogen, making interior temperature is 60 DEG C.Thereafter, it is added in ethyl acetate 10 parts and is dissolved with azodiisobutyronitrile 0.12 part Solution.After mutually synthermal holding 1 hour, while interior temperature is remained 54～56 DEG C, to add 17.3 parts/Hr of speed Ethyl acetate is added continuously in reaction vessel so that the concentration of polymer substantially 35%.Adding from ethyl acetate Add beginning until after interior temperature is remained 54～56 DEG C by 12 hours, adding ethyl acetate and the concentration of polymer be adjusted to 20%, obtain the ethyl acetate solution of (methyl) acrylic resin (A-1).The weight of (methyl) acrylic resin (A-1) Average molecular weight Mw is 1,390,000, and the ratio Mw/Mn of weight average molecular weight Mw and number-average molecular weight Mn is 5.32.At gel permeation chromatography (GPC) in elution curve, the composition of Mw139 ten thousand demonstrates single peak, does not see in the scope of Mw1000～2,500,000 Other peak.

By the composition of the monomer in each manufacture example, (numerical value of table 4 is weight portion.) and the elution curve of GPC on Peak number (being expressed as " GPC peak number " in table 4) in the scope of Mw1000～2,500,000 is concentrated and is shown in table 4.

[table 4]

The abbreviation being positioned in " monomer composition " hurdle of table 4 refers to following monomer.

BA: butyl acrylate (glass transition temperature of homopolymer :-54 DEG C),

HEA: acrylic acid 2-hydroxy methacrylate.

＜ embodiment 9, comparative example 10～11 ＞

(1) preparation of adhesive composition

The ethyl acetate solution (resin concentration: 20%) of (methyl) acrylic resin obtained in above-mentioned manufacture example In, relative to the solid constituent 100 parts of this solution, the silane shown in the table 5 of the amount (weight portion) shown in mixture table 5 respectively Compound (B), ionic compound (C) and isocyanates system cross-linking agent (D), then so that solid component concentration is 14% Mode is added ethyl acetate and is obtained adhesive composition.For the use level of each gradation composition shown in table 5, used Commodity when containing solvent etc., be the parts by weight as effective ingredient contained therein.

[table 5]

Noting at foot of each gradation composition represented with abbreviation in table 5.

(silane compound)

B-1: the silane compound shown in following formula:

[changing 18]

(ionic compound)

Double (fluorosulfonyl) imide salts of C-5:N-decyl pyridine,

C-8:N-octyl group-4-picoline hexafluorophosphate.

(isocyanates system cross-linking agent)

(2) making of adhesive phase

(3) with the making of blooming (P-1) of adhesive phase

(4) with the resistance to metal protection evaluation of blooming of adhesive phase

The blooming with adhesive phase (P-1) made in above-mentioned (3) is cut the examination of the size into 20mm × 50mm Testing sheet, folder is fitted in the metal level side of the glass substrate with metal level across adhesive phase.As the glass with metal level Substrate, employed utilize on alkali-free glass surface the sputtering stacking silver alloy of thickness about 500nm (using silver as main constituent and Containing palladium and the alloy of copper, APC) glass substrate (Geomatec company system) of layer.By the optical laminate of gained in temperature 60 DEG C, in the baking oven of relative humidity 90% after keeping 500 hours, pass through from polarization plates surface from the rear projection light of glass substrate The state of the metal level of the part of the blooming fitted with adhesive phase observed by magnifier, (a diameter of for spot corrosion More than 0.1mm and can be through the generation in hole of light), utilize following benchmark to be evaluated.The results are shown in Table 6.

3: the number of spot corrosion produced at layer on surface of metal is 3～5,

[table 6]

The explanation of symbol

1 with the blooming of adhesive phase, 2 polaroids, 3 first resin moldings, 4 second resin moldings, 5,6,7,8 light Learn duplexer, 10 bloomings, 10a, 10b polarization plates, 20 adhesive phases, 30 metal levels, 40 substrates, 50 resin beds.

Claims

1., with a blooming for adhesive phase, it comprises blooming and is laminated in the binding agent on its at least one face Layer,

Described adhesive phase is by containing (methyl) acrylic resin (A), silane compound (B) and ionic compound (C) Adhesive composition constitute,

In formula, A represents the alkane diyl of carbon number 1～20 or the ester ring type alkyl of the divalent of carbon number 3～20, constitutes this alkane Diyl and the-CH of this ester ring type alkyl₂-can also be by-O-or-C (=O)-displacement, R¹Represent carbon number 1～5 Alkyl, R²、R³、R⁴、R⁵And R⁶Represent alkyl or the alkoxyl of carbon number 1～5 of carbon number 1～5 independently of one another；

The anion of described ionic compound (C) is the anion in following group:

Blooming with adhesive phase the most according to claim 1, wherein,

The silane compound (B) represented with described formula (I) is the silane compound represented with following formula (II):

In formula, R¹、R³、R⁴、R⁵And R⁶Represent implication same as described above, R respectively⁷Representing the alkyl of carbon number 1～5, m represents The integer of 1～20.

Blooming with adhesive phase the most according to claim 2, wherein,

The integer that m is 4～20 in described formula (II).

Blooming with adhesive phase the most according to claim 2, wherein,

The integer that m is 6～8 in described formula (II).

Blooming with adhesive phase the most according to claim 2, wherein,

M in described formula (II) is 6.

Blooming with adhesive phase the most according to claim 1, wherein,

Described silane compound (B) is 1, double (trimethoxysilyl) hexane of 6-.

Blooming with adhesive phase the most according to claim 1, wherein,

The cation of described ionic compound (C) be the sun with the heterocycle structure containing nitrogen-atoms comprising unsaturated bond from Son.

Blooming with adhesive phase the most according to claim 1, wherein,

The cation of described ionic compound (C) is the pyridylium represented with following formula (III):

In formula, R⁸～R¹³Represent hydrogen atom independently of one another, can have the alkyl of substituent group, can have the alkene of substituent group Base, can have the alkynyl of substituent group, can have the aryl of substituent group, can have the heterocyclic radical of substituent group, hydroxyl, ether Base, carboxyl, carbonyl or halogen atom, it is also possible between adjacent substituent group, form ring.

Blooming with adhesive phase the most according to claim 1, wherein,

The content of the described silane compound (B) in described adhesive composition is relative to described (methyl) acrylic resin (A) 100 weight portions are 0.01～10 weight portions.

Blooming with adhesive phase the most according to claim 1, wherein,

Described (methyl) acrylic resin (A) is containing the Component units coming from the monomer with hydroxyl.

11. bloomings with adhesive phase according to claim 1, wherein,

Described (methyl) acrylic resin (A) is containing coming from the Component units of alkyl acrylate (a1) and coming from The Component units of alkyl acrylate (a2),

The glass transition temperature of the homopolymer of described alkyl acrylate (a1) is less than 0 DEG C, described alkyl acrylate (a2) The glass transition temperature of homopolymer be more than 0 DEG C.

12. bloomings with adhesive phase according to claim 1, wherein,

The weight average molecular weight of described (methyl) acrylic resin (A) is 500,000～2,500,000.

13. bloomings with adhesive phase according to claim 1, wherein,

Described adhesive composition is possibly together with isocyanates system cross-linking agent (D).

14. bloomings with adhesive phase according to claim 1, wherein,

Described adhesive composition contains substantially no three azole compounds.

15. 1 kinds of liquid crystal indicators, it comprises the optics with adhesive phase according to any one of claim 1～14 Film.

16. 1 kinds of adhesive compositions, it contains (methyl) acrylic resin (A), silane compound (B) and ionic Compound (C),

The anion of described ionic compound (C) is the anion in following group:

17. 1 kinds of bloomings with adhesive phase, it comprises blooming and is laminated at least one face of this blooming Adhesive phase, and fit in metal level for folder across described adhesive phase,

Described adhesive phase is formed by following adhesive composition:

Containing (methyl) acrylic resin (A), silane compound (B) and ionic compound (C),

The anion of described ionic compound (C) is the anion in following group:

18. 1 kinds of optical laminates, it comprises:

The blooming with adhesive phase according to any one of claim 1～14, and

It is layered in this metal level with the adhesive phase side of the blooming of adhesive phase.