CN105358648B - Adhesive composition, transparency conducting layer adhesive phase, laminated body and image display device - Google Patents

Adhesive composition, transparency conducting layer adhesive phase, laminated body and image display device Download PDF

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CN105358648B
CN105358648B CN201480036263.6A CN201480036263A CN105358648B CN 105358648 B CN105358648 B CN 105358648B CN 201480036263 A CN201480036263 A CN 201480036263A CN 105358648 B CN105358648 B CN 105358648B
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methyl
adhesive phase
weight
transparency conducting
conducting layer
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CN105358648A (en
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秋月伸介
外山雄祐
保井淳
高桥俊贵
永田瑞穗
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Nitto Denko Corp
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Nitto Denko Corp
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Priority claimed from JP2014130740A external-priority patent/JP6363410B2/en
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Priority claimed from PCT/JP2014/067062 external-priority patent/WO2014208696A1/en
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  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Nonlinear Science (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Laminated Bodies (AREA)
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Abstract

The purpose of the present invention is to provide a kind of adhesive compositions, described adhesive composition can form adhesive phase, described adhesive layer it is excellent in adhesion, and even if in the case where being laminated over transparent conductive layer, the corrosion of above-mentioned transparency conducting layer is also suppressed, and can inhibit the rising of the sheet resistance value of above-mentioned transparency conducting layer.The present invention is a kind of adhesive composition, which is characterized in that described adhesive composition is used to form the adhesive phase contacted with the transparency conducting layer of the transparent conductive base with transparency conducting layer, and described adhesive composition contains：Carboxylic (methyl) acrylate copolymer that weight average molecular weight is 1,200,000~3,000,000, isocyanates system crosslinking agent and the following general formula (1) compound represented (in formula, R1And R2It is each independently hydrogen atom or may include the hydrocarbon residue of the carbon atom number 1~18 of oxygen atom), the content of general formula (1) compound represented is 0.005~3 parts by weight relative to carboxylic 100 parts by weight of (methyl) acrylate copolymer.

Description

Adhesive composition, transparency conducting layer adhesive phase, laminated body and image are shown Device
Technical field
The present invention relates to be used to form to connect with the above-mentioned transparency conducting layer of the transparent conductive base with transparency conducting layer The adhesive composition of tactile adhesive phase and the transparency conducting layer adhesive phase formed by above-mentioned adhesive composition.This Outside, the present invention relates to successively include base material film, above-mentioned transparency conducting layer adhesive phase and transparency conducting layer laminated body, will be upper State the image display device that laminated body is used as touch panel.
Background technology
In recent years, by for the liquid crystal display device of mobile phone, portable music player etc., image display device with The input unit that touch panel is applied in combination gradually is popularized.In touch panel, use comprising glass plate or transparent resin The base material (such as transparent and electrically conductive film) of transparency conducting layer is formed on the transparent base of film, for example, in electrostatic capacity In touch panel, the layer at transparent layer for being formed in the base material with the transparency conducting layer is laminated with the stacking of double-sided adhesive sheet Body is fixed on other base materials via the adhesive phase of the laminated body.
Above-mentioned transparency conducting layer is, for example, to be deposited metal of the tin indium oxide (ITO) etc. with high transparency and electric conductivity and shape At.There is good etching characteristic, and amorphous in etching work procedure of the above-mentioned tin indium oxide (ITO) in the patterning of wiring Property (amorphous) tin indium oxide (ITO) it is more advantageous, be often used the tin indium oxide (ITO) of amorphism (amorphous).
In general adhesive, in order to improve the cohesiveness of adhesive composition, carboxyl group-containing monomer etc. is used to be used as adhesive Ingredient.However, in the case that such adhesive phase comprising sour component is in direct contact with transparency conducting layer, made due to acid Bright conductive layer corrodes, and therefore, it is difficult to be used for the purposes.
For the purpose of metal erosion as solving the problems, such as, it is proposed that the various adhesives with preventing metal corrosion Composition.Specifically, it is proposed that：The adhesive combination for adding the nitrogen atom ingredient of specific quantity sour component content is made to reduce Object (for example, see patent document 1)；Make adhesive combination as main component containing the acrylic resin either with or without acidic-group Object (for example, see patent document 2)；Including not having the adhesive (example of (methyl) acrylate copolymer of acidic-group substantially Such as referring to patent document 3).
In addition, as the adhesive containing phosphate compound, it is known that for example containing side chain have hydroxyl and alkylene oxide The acrylic acid series copolymer of chain, ionic compound, curing agent and phosphate compound antistatic acrylic system adhesive (such as Referring to patent document 4).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-144002 bulletins
Patent document 2：Japanese Unexamined Patent Application Publication 2011-225835 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2013-018227 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2007-2111 bulletins
Invention content
Problems to be solved by the invention
The adhesive composition of above patent document 1~3 due to reduce the sour component containing carboxy resin etc. content or Sour component is not used in person, therefore plays certain effect in terms of the effect for inhibiting metal erosion.However, in above patent document 1 In~3 adhesive composition, the content of above-mentioned sour component is few, therefore the cohesiveness of resin is insufficient, the bases such as bonding force, retentivity Plinth physical property is insufficient, the abundant performance especially hard to say having as transparency conducting layer adhesive.
In addition, the antistatic acrylic system adhesive of patent document 4 is used as the adhesive of surface protection bonding film, use It is insufficient in bonding force, bonding reliability etc. when transparency conducting layer.
Therefore, the purpose of the present invention is to provide a kind of adhesive composition, described adhesive composition can form viscous Mixture layer, described adhesive layer it is excellent in adhesion, and even if stacking over transparent conductive layer in the case of, it is above-mentioned transparent The corrosion of conductive layer is also suppressed, and can inhibit the rising of the sheet resistance value of above-mentioned transparency conducting layer.In addition, of the invention Purpose also reside in provide the transparency conducting layer adhesive phase formed by above-mentioned adhesive composition, include successively base material film, The laminated body of above-mentioned transparency conducting layer adhesive phase and transparency conducting layer, the image that above-mentioned laminated body is used as to touch panel are shown Showing device.
The means used to solve the problem
The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that, by the way that following adhesives are made Above-mentioned purpose may be implemented, so as to complete the present invention in composition.
That is, the present invention relates to a kind of adhesive compositions, which is characterized in that it is to be used to form and have transparency conducting layer Transparent conductive base above-mentioned transparency conducting layer contact adhesive phase adhesive composition,
It contains carboxylic (methyl) acrylate copolymer, the isocyanates that weight average molecular weight is 1,200,000~3,000,000 It is crosslinking agent and the following general formula (1) compound represented,
(in formula, R1And R2It is each independently hydrogen atom or may include the hydrocarbon residue of the carbon atom number 1~18 of oxygen atom),
The content of above-mentioned general formula (1) compound represented is relative to above-mentioned carboxylic (methyl) acrylate copolymer 100 parts by weight are 0.005~3 parts by weight.
Above-mentioned carboxylic (methyl) acrylate copolymer will contain (methyl) acrylate and carboxyl group-containing monomer Obtained from polymerizing monomer components,
Above-mentioned carboxyl group-containing monomer relative to formed whole monomers of above-mentioned carboxylic (methyl) acrylate copolymer at It is preferably 0.05~10 parts by weight to divide 100 parts by weight.
Above-mentioned adhesive composition preferably comprises phosphoric acid, and contains the R selected from general formula (1)1And R2In any one is former for hydrogen The R of the phosphate monoester and general formula (1) of the hydrocarbon residue, another one is the carbon atom number 1~18 that may include oxygen atom1And R2For can Include the phosphate of one or more of di-phosphate ester of hydrocarbon residue of carbon atom number 1~18 of oxygen atom.
Above-mentioned adhesive composition preferably comprises phosphoric acid and phosphate monoester.In addition, the total amount phase of phosphoric acid and phosphate monoester Total amount (100 weight %) for above-mentioned general formula (1) compound represented is preferably 80 weight % or more.
The hydrocarbon residue of above-mentioned carbon atom number 1~18 is preferably the alkyl of the linear chain or branched chain of carbon atom number 1~10.
Above-mentioned isocyanates system crosslinking agent is excellent relative to 100 parts by weight of above-mentioned carboxylic (methyl) acrylate copolymer It is selected as 0.01~10 parts by weight.
Furthermore it is preferred that containing peroxide system crosslinking agent.
It is preferred that above-mentioned transparency conducting layer is formed by tin indium oxide.
It is preferred that above-mentioned tin indium oxide is noncrystalline tin indium oxide.
Moreover, it relates to a kind of transparency conducting layer adhesive phase, which is characterized in that it is combined by above-mentioned adhesive Object is formed.
Moreover, it relates to a kind of laminated body, which is characterized in that it includes base material film, above-mentioned transparency conducting layer successively With adhesive phase and with the transparent conductive base of transparency conducting layer, above-mentioned transparency conducting layer adhesive phase with it is above-mentioned transparent The transparency conducting layer of conductive substrate contacts.
Above-mentioned base material film preferably has in at least one side containing iodine and/or the iodine system polarizing film of iodide ion transparency protected The iodine system polarizing coating of film.Herein, " the iodine system polarizing film containing iodine and/or iodide ion " refers to the iodine system polarizing film containing iodine, contains Iodine system polarizing film, the iodine system polarizing film containing both iodine and iodide ion for having iodide ion can be used compatibly in the present invention and be appointed It is a kind of.
In addition, the present invention relates to a kind of image display devices, which is characterized in that above-mentioned laminated body is used as touch panel.
Invention effect
The adhesive composition of the present invention is due to comprising carboxylic (methyl) acrylate copolymer, having Gao Ning Poly- power has high bonding force by the adhesive phase that the adhesive composition is formed.In addition, the adhesive composition of the present invention is most Pipe includes carboxylic (methyl) acrylate copolymer as sour component, in the bonding that will be formed by the adhesive composition In the case of oxidant layer stacking over transparent conductive layer, the corrosion of transparency conducting layer can also be inhibited, transparency conducting layer can be inhibited Sheet resistance rise.It is thought that due to：General formula (1) compound represented for containing is in the adhesive composition of the present invention In the case of phosphoric acid, which forms passivation overlay film, Huo Zhe in the metal ion of layer at transparent layer and transparency conducting layer In the case that general formula (1) compound represented is phosphate, which is selectively adsorbed in layer at transparent layer and shape At the H in overlay film, with adhesive phase+Repel each other to repel H+, therefore the corrosion of transparency conducting layer is interfered, and surface can be inhibited The rising of resistance value.In addition, the isocyanates system crosslinking agent contained in the adhesive composition of the present invention is sometimes due to derived from acid The catalyst effect of ingredient and gelation occurs, but the present invention adhesive composition in, include the specific acid of specific quantity Phosphate, therefore the gelation can be controlled, there is good working life.
Description of the drawings
Fig. 1 is the sectional view for an embodiment for schematically showing the image display device of the present invention.
Fig. 2 is the sectional view for an embodiment for schematically showing the image display device of the present invention.
Fig. 3 is the sectional view for an embodiment for schematically showing the image display device of the present invention.
Specific implementation mode
1. adhesive composition
The adhesive composition of the present invention is characterized in that, is to be used to form and the electrically conducting transparent with transparency conducting layer Property base material above-mentioned transparency conducting layer contact adhesive phase adhesive composition,
It contains carboxylic (methyl) acrylate copolymer, the isocyanates that weight average molecular weight is 1,200,000~3,000,000 It is crosslinking agent and the following general formula (1) compound represented,
(in formula, R1And R2It is each independently hydrogen atom or may include the hydrocarbon residue of the carbon atom number 1~18 of oxygen atom),
The content of above-mentioned general formula (1) compound represented is relative to above-mentioned carboxylic (methyl) acrylate copolymer 100 parts by weight are 0.005~3 parts by weight.
In the present invention, R in above-mentioned general formula (1) can compatibly be used1And R2It is the phosphoric acid (H of hydrogen atom3PO4), separately Outside, the salt (metal salt, ammonium salt of sodium, potassium and magnesium etc. etc.) of the phosphoric acid can also compatibly be used.
Furthermore it is possible to compatibly use at least R in above-mentioned general formula (1)1And R2One of be that may include the carbon atom number of oxygen atom The phosphate of 1~18 hydrocarbon residue.As the hydrocarbon residue for the carbon atom number 1~18 that may include oxygen atom, carbon atom number 1 can be enumerated ~18 alkyl, the alkenyl of carbon atom number 1~18, the aryl of carbon atom number 6~18 ,-(CH2CH2O)nR3(R3For carbon atom number 1 The aryl of~18 alkyl, the alkenyl of carbon atom number 1~18 or carbon atom number 6~18, the integer that n is 0~15) etc..In addition, alkane Base, alkenyl can be that straight-chain may be branched.Among these, as the hydrocarbon residue of above-mentioned carbon atom number 1~18, preferably The alkyl of the linear chain or branched chain of carbon atom number 1~10, the aryl of carbon atom number 6~18, the straight chain of more preferable carbon atom number 2~6 Or the alkyl of branch.
In addition, in the present invention, as general formula (1) compound represented, such as shown in general formula (2) preferably below Phosphate ester acid,
(in formula, R1Ibid, R3For the alkyl or alkenyl of carbon atom number 1~18, the integer that n is 0~15).
The R of general formula (2)1With the R of general formula (1)1Equally, it is hydrogen atom or to may include the carbon atom number 1~18 of oxygen atom Hydrocarbon residue.As the hydrocarbon residue for the carbon atom number 1~18 that may include oxygen atom, it can enumerate and above similarly may include oxygen The hydrocarbon residue of the carbon atom number 1~18 of atom.R as general formula (2)1, preferably hydrogen atom, carbon atom number 1~18 straight chain Or the alkyl of branch or the aryl of carbon atom number 6~18, the more preferably linear chain or branched chain of hydrogen atom or carbon atom number 1~10 Alkyl, the further preferably alkyl of the linear chain or branched chain of hydrogen atom or carbon atom number 2~6.As R3, carbon original can be enumerated The aryl of the alkyl of subnumber 1~18, the alkenyl of carbon atom number 1~18 or carbon atom number 6~18, preferably carbon atom number 1~18 Alkyl, carbon atom number 6~18 aryl, the more preferably alkyl of carbon atom number 1~10, further preferably carbon atom number 2 ~6 alkyl.In addition, the integer that n is 0~15, preferably 0~10 integer.In addition, in the present invention, from preventing deterioration Viewpoint is set out, and polyethylene oxide structure (CH is not preferably included2CH2O) (i.e. n=0 in formula (2)).
As phosphate ester acid shown in general formula (2), from the viewpoint of the adsorption effect to transparency conducting layer, preferably R1 For hydrogen atom and R3For the phosphate monoester of the alkyl of the linear chain or branched chain of carbon atom number 1~18, more preferable R1For hydrogen atom and R3For The phosphate monoester of the alkyl of the linear chain or branched chain of carbon atom number 1~10, further preferred R1For hydrogen atom and R3For carbon atom number 2 The phosphate monoester of the alkyl of~6 linear chain or branched chain.
In addition, in the present invention it is possible to general formula (2) compound represented being mixed with two or more, furthermore it is possible to make With general formula (2) compound represented and the phosphoric acid (R of general formula (1)1=R2=hydrogen atom) mixture.In general, general formula (2) Shown in phosphate ester acid in most cases with monoesters (R1=hydrogen atom) and diester (R1=it may include the carbon atom number 1 of oxygen atom ~18 hydrocarbon residue) the form of mixture obtain, can also be in the mixture of above-mentioned monoesters and diester further in addition It is used after stating phosphoric acid.
In the present invention, the salt (metal of sodium, potassium and magnesium etc. of general formula (2) compound represented can also compatibly be used Salt, ammonium salt etc.).
As the commercially available product of phosphate ester acid shown in above-mentioned general formula (2), can enumerate：Toho Chemical Industry Co., Ltd. (JP) Tokyo-To, Japan " Phosphanol SM-172 " (R of general formula (2) of system1=R3=C8H17, n=0, mono-/bis mixture, acid value：219mgKOH/ G), " Phosphanol the GF-185 " (R of general formula (2)1=R3=C13H27, n=0, mono-/bis mixture, acid value：158mgKOH/ G), " Phosphanol the BH-650 " (R of general formula (2)1=R3=C4H9, n=1, mono-/bis mixture, acid value：388mgKOH/ G), " Phosphanol the RS-410 " (R of general formula (2)1=R3=C13H27, n=4, mono-/bis mixture, acid value：105mgKOH/ G), " Phosphanol the RS-610 " (R of general formula (2)1=C13H27、R3=C13H27, n=6, mono-/bis mixture, acid value： 82mgKOH/g), " Phosphanol the ML-220 " (R of general formula (2)1=R3=C12H25, n=2, mono-/bis mixture), " Phosphanol ML-200 " (R of general formula (2)1=R3=C12H25, n=0, mono-/bis mixture), " Phosphanol ED- The 200 " (R of general formula (2)1=R3=C8H17, n=1, mono-/bis mixture), " Phosphanol RL-210 " (R of general formula (2)1 =R3=C18H37, n=2, mono-/bis mixture), " Phosphanol GF-339 (R of general formula (2)1=R3=C6H13~C10H21 Mixing, n=0, mono-/bis mixture), " Phosphanol the GF-199 " (R of general formula (2)1=R3=C12H25, n=0, list/ Two mixtures), " Phosphanol RL-310 " (R of general formula (2)1=R3=C18H37, n=3, mono-/bis mixture), it is solar Learn " NIKKOL DDP-2 " (R of general formula (2) of Co. Ltd. system1=R3=C12H25~C15H31Mixture, n=2), " Phosphanol LP-700 " (R of general formula (2)1=R3=C6H5, n=6, mono-/bis mixture), big eight chemical industry strain formula " AP-1 " (R of general formula (2) of commercial firm1=R3=CH3, n=0, mono-/bis mixture, acid value：650mgKOH/g or more), " AP-4 " (R of general formula (2)1=R3=C4H9, n=0, mono-/bis mixture, acid value：452mgKOH/g), " DP-4 " (general formula (2) R1=R3=C4H9, n=0, mono-/bis mixture, acid value：292mgKOH/g), " the MP-4 " (R of general formula (2)1=H, R3= C4H9, n=0, mono-/bis mixture, acid value：670mgKOH/g), " the AP-8 " (R of general formula (2)1=R3=C8H17, n=0, list/ Two mixtures, acid value：306mgKOH/g), " the AP-10 " (R of general formula (2)1=R3=C10H21, n=0, mono-/bis mixture, acid Value：263mgKOH/g), " the MP-10 " (R of general formula (2)1=H, R3=C10H21, n=0, mono-/bis mixture, acid value： 400mgKOH/g), " JP-508 " (R of general formula (2) of north of the city Chemical Co., Ltd.1=R3=C8H17, n=0, mono-/bis mixing Object, acid value：288mgKOH/g), " the JP-513 " (R of general formula (2)1=R3=C13H27, n=0, mono-/bis mixture), " JP- The 524R " (R of general formula (2)1=R3=C24H49, n=0, mono-/bis mixture), " DBP " (R of general formula (2)1=R3=C4H9, n= 0, mono-/bis mixture, acid value：266mgKOH/g), " the LB-58 " (R of general formula (2)1=R3=C8H17, n=0, diester, acid Value：173mgKOH/g), the mono phosphoric acid ester N-butyl (O=P (OH) of SIGMA-ALDRICH2(OC4H9), the R of general formula (2)1=H, R3=C4H9, n=0, product type：CDS001281, monoester) etc. and their salt.It should be noted that above-mentioned " mono-/bis Mixture " indicates the monoesters (R of general formula (2)1=H) and the diester (R of general formula (2)1=it may include the carbon atom number 1~18 of oxygen atom Hydrocarbon residue) mixture, such as in the case of Phosphanol SM-172, indicate the monoesters (R of general formula (2)1=H, R3= C8H17, n=0) with the diester (R of general formula (2)1=R3=C8H17, n=0) mixture.The monoesters of above-mentioned " mono-/bis mixture " with The mixed proportion of diester can basis31The measurement result of P-NMR calculates.Assay method is as described in embodiment.
(1) compound represented of general formula used in the present invention or general formula (2) compound represented can use independent 1 Kind can also be mixed with two or more, and from the viewpoint of the adsorption effect to transparency conducting layer, be preferably selected from phosphoric acid, phosphorus Mixture of more than two kinds in acid monoester and di-phosphate ester more preferably includes phosphoric acid and includes selected from phosphate monoester and phosphoric acid The mixture of one or more of diester phosphate especially preferably includes the mixture of phosphate monoester and phosphoric acid.In the present invention In, when can also use independent a kind in phosphoric acid, phosphate monoester and di-phosphate ester, but phosphoric acid is used alone, bond sometimes The working life of agent composition becomes inadequate.In addition, phosphoric acid is the very high compound of polarity, with (methyl) acrylic ester copolymer The compatibility of object is simultaneously insufficient, therefore phosphoric acid oozes out into adhesive layer surface sometimes, and result is generated in terms of durability and asked Topic.In addition, if phosphate (phosphate monoester and/or di-phosphate ester) is used only without using phosphoric acid, in very harsh condition Under durability (such as thermal cycling test etc.) in terms of lead to the problem of sometimes.In the present invention, from the corruption for inhibiting transparency conducting layer Erosion and it is very harsh under conditions of durability balance from the perspective of, most preferably with include the phosphorus of phosphoric acid and phosphate monoester Sour based compound.In addition, the total amount of phosphoric acid and phosphate monoester is not particularly limited, change relative to shown in above-mentioned general formula (1) The total amount (100 weight %) for closing object is preferably 80 weight % or more.Herein, phosphate monoester refers to the R of general formula (1)1And R2Middle one For hydrocarbon residue that hydrogen atom, another one are the carbon atom number 1~18 that may include oxygen atom compound (in the case of general formula (2), It is R1For the compound of hydrogen atom), di-phosphate ester refers to the R of general formula (1)1And R2To may include the carbon atom number 1~18 of oxygen atom The compound of hydrocarbon residue (be R in the case of general formula (2)1For may include oxygen atom carbon atom number 1~18 hydrocarbon residue Compound).
About the adsorption effect to above-mentioned transparency conducting layer, it is believed that transparency conducting layer and above-mentioned phosphoric acid based compound with by It is that HSAB rules define, i.e. " Lewis acid-base theoryby " it is related, by the way that hard base is combined with hard acid, combines soft base with soft acid, by This adsorption effect is high, and high anti-degradation effects can be obtained in result.I.e. for example, the In of ITO belong to defined by HSAB rules it is hard Acid, for phosphoric acid based compound, phosphoric acid, phosphate monoester, di-phosphate ester are followed successively by hard base to soft base, therefore according to said sequence It is effectively adsorbed in ITO, as a result, high anti-degradation effects can be obtained.
In addition, using in the case of the mixture of monoester and diester, preferably include the mixture of a large amount of monoesters. The mixed proportion (weight ratio) of the mixture of above-mentioned monoester and diester is preferably monoester：Diester=6：4~9：1, more Preferably 7：3~9：1.For the above reasons, due to comprising a large amount of monoesters, thus to the adsorption effect of transparency conducting layer height, It is therefore preferred.
In addition, as described above, in the present invention, it is preferred in phosphate based compound (especially phosphate monoester) further Phosphoric acid is added, the additive amount of phosphoric acid is preferably 10~400 parts by weight, more relative to 100 parts by weight of phosphate based compound at this time Preferably 10~100 parts by weight, from the viewpoint of the adsorption effect to adherend, preferably 10~50 parts by weight.In addition, from From the perspective of durability under conditions of very harsh, the additive amount of phosphoric acid is relative to 100 parts by weight of phosphate based compound Preferably 10~100 parts by weight, more preferably 10~80 parts by weight.
In addition, the acid value of phosphate cpd used in the present invention be preferably 900mgKOH/g or less, more preferably 50~ 800mgKOH/g, preferably 50~700mgKOH/g.In addition, from the viewpoint of the operability in production, above-mentioned acid phosphate The acid value of ester be preferably 80~400mgKOH/g, more preferably 80~350mgKOH/g, further preferably 100~ 300mgKOH/g, particularly preferably 100~280mgKOH/g.By making the acid value of phosphate ester acid be in above range, thus There is the rising for the sheet resistance value that can inhibit transparency conducting layer, and the trend of the durability to heating-humidification can be improved, To which the acid value of preferably phosphate ester acid is in above range.In addition, phosphate ester acid is sometimes as adhesive group of the invention The catalysts for closing the cross-linking reaction of isocyanates system crosslinking agent contained in object play a role, sometimes adhesive composition Working life shortens.However, being above range by making the acid value of phosphate ester acid, thus having can inhibit as catalysts Effect trend, therefore from the viewpoint of the working life of adhesive composition, it is upper preferably to make the acid value of phosphate ester acid State range.In addition, from the viewpoint of effective effect for playing inhibition gelation, preferably added according to additive amount described below The phosphate ester acid of acid value with above range.
In addition, in the present invention, acid phosphorus shown in above-mentioned general formula (1) compound represented, general formula (2) can also be used The polymers such as dimer, the trimer of acid esters etc..
The additive amount of above-mentioned general formula (1) compound represented is relative to carboxylic (methyl) acrylate described below 00 parts by weight of copolymer 1 be 0.005~3 parts by weight, preferably 0.005~2.5 parts by weight, more preferably 0.01~1 parts by weight, Further preferably 0.01~2 parts by weight, particularly preferably 0.02~0.4 parts by weight.By making general formula (1) compound represented Additive amount be above range in, the rising of the sheet resistance value of transparency conducting layer can be inhibited, and can make to heating-plus Wet durability improves, and is therefore preferred.In addition, in the present invention it is possible to change using shown in general formula of more than two kinds (1) Object is closed, but in this case, can be added in such a way that total amount is above range.
In the present invention, even if in the bonding formed by the adhesive composition comprising above-mentioned general formula (1) compound represented Transparency conducting layer is laminated in oxidant layer, the sheet resistance of transparency conducting layer can also be inhibited to rise.It is thought that due to：In the present invention Adhesive composition in the case that general formula (1) compound represented for containing is phosphoric acid, the phosphoric acid is in transparency conducting layer table The metal ion of face and transparency conducting layer forms passivation overlay film, alternatively, the case where general formula (1) compound represented is phosphate Under, which is selectively adsorbed in layer at transparent layer and forms overlay film, with the H in adhesive phase+Repel each other to arrange Denounce H+, therefore the corrosion of transparency conducting layer is interfered, and the rising of sheet resistance value can be inhibited.
For corrosion signified herein, in the case of metal oxide, with the machine different from common metal erosion The raw corrosion of haircut.
In the case of the metal oxide of ITO etc, corrosion reaction makes gold under conditions of there are general acidic materials The problems such as belonging to oxide dissolving, as a result generating the resistance value rising of the layer (metal oxide layer) comprising the metal oxide.Separately Outside, in the case of the substance other than above-mentioned acidic materials, which penetrates into metal oxide layer, makes the current-carrying of metal oxide Transport factor declines, therefore generates the rising of resistance value.
Due to the difference of the mechanism of action of above-mentioned metal erosion and the corrosion of metal oxide, for metal as ITO Oxide does not observe the effect for inhibiting corrosion even with general antirust agent sometimes yet.
General formula used in the present invention (1) compound represented is acidic materials, but corrode caused by the acidic materials Influence it is small, by forming overlay film etc. on the surface of metal or metal oxide, it is suppressed that is contained within the adhesive layer is sour, other Resistance value caused by the substance of deterioration is caused to rise.
The effect of inhibition corrosion derived from general formula (1) compound represented, especially in the metal oxygen for transparency conducting layer Effect is big in the case of compound, in addition, playing better effect in the case of ITO.
(methyl) acrylate copolymer carboxylic used in the present invention is not particularly limited, such as is preferably：It will Carboxylic (methyl) acrylate obtained from polymerizing monomer components containing (methyl) acrylate and carboxyl group-containing monomer is total Polymers, more preferably：(methyl) alkyl acrylate of the alkyl with carbon atom number 4~18 will be contained as main component and Carboxylic (methyl) acrylate obtained from polymerizing monomer components containing carboxylic (methyl) alkyl acrylate is total Polymers.It should be noted that (methyl) alkyl acrylate refers to alkyl acrylate and/or alkyl methacrylate, this (methyl) in invention is same meaning.
As the alkyl of carbon atom number 4~18, the various alkyl of straight-chain or branched can be used.Have as above-mentioned The concrete example of (methyl) alkyl acrylate of the alkyl of carbon atom number 4~18, may be exemplified out for example：(methyl) acrylic acid is just Butyl ester, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid are just Pentyl ester, (methyl) isoamyl acrylate, (methyl) isoamyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid heptan Ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid Different nonyl ester, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, positive ten diester of (methyl) acrylic acid, (methyl) propylene The different myristin of acid, positive 13 ester of (methyl) acrylic acid, (methyl) tetradecyl acrylate, (methyl) stearyl acrylate, (first Base) octadecyl ester or (methyl) dodecyl acrylate etc..They may be used singly or in combin.These it In, more preferably there is (methyl) acrylate of the alkyl of carbon atom number 4~10, the positive fourth of further preferred (methyl) acrylic acid Ester, (methyl) acrylic acid-2-ethyl caproite, particularly preferred (methyl) n-butyl acrylate.
(methyl) alkyl acrylate of the above-mentioned alkyl with carbon atom number 4~18 is relative to the carboxylic (first of formation Base) 100 parts by weight of monomer component of acrylate copolymer are preferably 50 parts by weight or more, preferably more than 60 parts by weight, more More than preferably 70 parts by weight, more than further preferably 80 parts by weight, more than particularly preferably 90 parts by weight.
As carboxyl group-containing monomer, can using without particular limitation, there is (methyl) acryloyl group or vinyl etc. to contain The polymerizable functional group of unsaturated double-bond and the monomer with carboxyl.As carboxyl group-containing monomer, it can be cited for example that：Acrylic acid, Methacrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid Deng these can be used alone or are applied in combination.
Carboxyl group-containing monomer is excellent relative to 100 parts by weight of monomer component for forming carboxylic (methyl) acrylate copolymer It is selected as 0.05~10 parts by weight, more preferably 0.3~10 parts by weight.By making carboxyl group-containing monomer be Ke Yiti in above range The cohesiveness of high carboxylic (methyl) acrylate copolymer, can obtain sufficient bonding force, retentivity, therefore preferably make Carboxyl group-containing monomer is in above range.
In addition, being formed in the monomer component of carboxylic (methyl) acrylate copolymer, there is carbon atom in addition to above-mentioned Other than (methyl) alkyl acrylate of the alkyl of number 4~18, carboxylic (methyl) alkyl acrylate, it can also add and contain Carboxylic monomer, monomer containing aryl, other comonomers.
As hydroxyl monomer, can using without particular limitation, there is (methyl) acryloyl group or vinyl etc. to contain The polymerizable functional group of unsaturated double-bond and the monomer with hydroxyl.As hydroxyl monomer, such as it may be exemplified out (methyl) Acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid The own ester of 6- hydroxyls, (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) acrylic acid 10- hydroxyls last of the ten Heavenly stems ester, (methyl) acrylic acid 12- Hydroxylauric ester, (methyl) acrylic acid (4- hydroxymethylcyclohexyls) methyl esters etc., they, which can use independent a kind or mix, makes Use two or more.Among them, preferably (methyl) 2-Hydroxy ethyl acrylate, acrylic acid 4- hydroxybutyls, from can be efficiently Ensure to set out in terms of with the crosslinking position of the isocyanate group of isocyanates system crosslinking agent, therefore acrylic acid 4- hydroxybutyls are excellent Choosing.
Hydroxyl single phase is preferred for 100 parts by weight of monomer component for forming carboxylic (methyl) acrylic copolymer For below 10 parts by weight, more preferably 0.1~10 parts by weight, further preferably 0.1~3 parts by weight.
As monomer containing aryl, can using without particular limitation, there is (methyl) acryloyl group or vinyl etc. to have The polymerizable functional group of unsaturated double-bond and the monomer with aryl.As monomer containing aryl, it can be mentioned, for example (methyl) propylene (methyl) benzyl acrylates such as acid phenenyl ester, (methyl) benzyl acrylate.
Single phase containing aryl is excellent for 100 parts by weight of monomer component for forming carboxylic (methyl) acrylate copolymer It is selected as 30 parts by weight or less, more preferably 1~20 parts by weight, further preferably 5~15 parts by weight.
As other comonomers, as long as being related to the polymerization of unsaturated double-bond with (methyl) acryloyl group or vinyl etc. Property functional group be just not particularly limited, it can be cited for example that (methyl) propyl acrylate etc. have carbon atom number 3 or less 19 or more Alkyl (methyl) alkyl acrylate；(methyl) cyclohexyl acrylate, (methyl) acrylic acid norbornene ester, (methyl) acrylic acid Isobornyl thiocyanoacetate etc. (methyl) acrylate ring type hydrocarbyl carbonate；Such as the vinyl esters such as vinyl acetate, vinyl propionate；Such as The styrenic monomers such as styrene；Such as (methyl) glycidyl acrylate, (methyl) acrylic acid methylglycidyl esters etc. Containing epoxy based monomers；Such as (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate etc. contain Alkoxy monomeric； Such as the cyano-containings monomer such as acrylonitrile, methacrylonitrile；Such as the functionalities list such as 2- methacryloxyethyl isocyanates Body；Such as the olefinic monomers such as ethylene, propylene, isoprene, butadiene, isobutene；Such as the vinyl ethers list such as vinyl ethers Body；Such as the halogen atoms monomer class such as vinyl chloride；Such as n-vinyl pyrrolidone, N- vinyl-Epsilon-caprolactams, first The ring-type nitrogen containing monomer such as base vinyl pyrrolidone；Etc..
In addition, as co-polymerized monomer, can enumerate：Such as N- N-cyclohexylmaleimides, N- isopropyls Malaysia acyl The maleimides amine system monomers such as imines, N- lauryls maleimide, N-phenylmaleimide；Such as N- methyl clothing health Acid imide, N- ethyl clothing health acid imide, N- butyl clothing health acid imide, N- octyl clothing health acid imide, N-2- ethylhexyl clothing The clothing health imide series monomers such as health acid imide, N- cyclohexyl clothing health acid imide, N- lauryl clothing health acid imides；Such as N- (first Base) acryloyl-oxy methylene succinimide, N- (methyl) acryloyl -6- oxygroup hexa-methylenes succinimide, N- The succinimides system monomers such as eight methylene succinimide of (methyl) acryloyl -8- oxygroups；Such as styrene sulfonic acid, allyl Base sulfonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) acrylic acid sulphur propyl ester, The monomers containing sulfonic group such as (methyl) propane sulfonic acid.
In addition, as co-polymerized monomer, it can be cited for example that：(methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid The glycol system propylene such as polypropylene glycol ester, (methyl) acrylic methoxy glycol ester, (methyl) methoxyethyl polypropylene glycol Acid ester monomer；And such as (methyl) tetrahydrofurfuryl acrylate, fluorine (methyl) acrylate etc. containing heterocycle, halogen atom third Olefin(e) acid ester system monomer etc..
In addition, as co-polymerized monomer, multi-functional monomer can be used.As multi-functional monomer, tool can be enumerated There is the compound etc. of the unsaturated double-bonds such as 2 or more (methyl) acryloyl groups, vinyl.It can be cited for example that：Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, trimethylolpropane Three (methyl) acrylate, tetraethylene glycol two (methyl) acrylate etc. (single or poly-) ethylene glycol two (methyl) acrylate, third Two (the first of (single or poly-) aklylene glycol such as glycol two (methyl) acrylate etc. (single or poly-) propylene glycol two (methyl) acrylate Base) acrylate, it can additionally enumerate：Neopentyl glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylic acid Ester, pentaerythrite two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) propylene The carboxylate of (methyl) acrylic acid and polyalcohol such as acid esters, dipentaerythritol six (methyl) acrylate；Divinylbenzene etc. is more Functional ethylene's based compound；(methyl) allyl acrylate, (methyl) vinyl acrylate etc. have reactive unsaturated double-bond Compound etc..In addition, as multi-functional monomer, the skeleton in polyester, epoxy resin, carbamate etc. can also be used Upper addition have 2 or more as unsaturated double-bonds such as (methyl) acryloyl group of functional group same as monomer component, vinyl Polyester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate etc..
The ratio of other comonomers relative to formed the monomer of above-mentioned carboxylic (methyl) acrylate copolymer at Divide 100 parts by weight to be preferably 30 parts by weight or less, be more preferably 25 parts by weight or less, being more preferably 20 parts by weight or less, Below particularly preferably 15 parts by weight.If the ratio of above-mentioned comonomer is excessive, it is likely that occur by the adhesive of the present invention The adhesive phase that composition is formed is to adhesion characteristics such as the adaptation declines of the various adherends such as glass, film, transparency conducting layer Decline.
The weight average molecular weight of (methyl) acrylate copolymer carboxylic used in the present invention is 1,200,000~3,000,000, Preferably 1,200,000~2,700,000, more preferably 1,400,000~2,500,000.If weight average molecular weight is less than 1,200,000, in terms of heat resistance It is undesirable.In addition, if weight average molecular weight is less than 1,200,000, low molecular weight compositions increase in adhesive composition, this is low sometimes Molecular weight constituent oozes out from adhesive phase and damages the transparency.In addition, carboxylic less than 1,200,000 using weight average molecular weight The adhesive phase that (methyl) acrylate copolymer obtains is sometimes in solvent resistance, mechanical characteristic etc. difference.In addition, if weight is equal Molecular weight is more than 3,000,000, then a large amount of retarder thinner is needed in order to adjust to the viscosity for coating, from the viewpoint of cost It is undesirable.In addition, from the viewpoint of corrosion resistance, durability it is also preferred that weight average molecular weight within the above range.On It states weight average molecular weight and refers to and be measured by GPC (gel permeation chromatography), convert calculated value according to polystyrene.
The manufacture of such carboxylic (methyl) acrylate copolymer can suitably select polymerisation in solution, ontology poly- Manufacturing method well known to conjunction, emulsion polymerization, various free radical polymerizations etc., is not particularly limited.In addition, gained is carboxylic (methyl) acrylate copolymer can be any one in random copolymer, block copolymer, graft copolymer etc..
In polymerisation in solution, it can be used and be used as polymer solvent such as ethyl acetate, toluene.As specific polymerisation in solution Example, reaction condition are：Under the inactive gas air-flow such as nitrogen, add polymerization initiator, usually at 50~70 DEG C or so carry out 5~ Reaction in 30 hours or so.
The polymerization initiator, chain-transferring agent, emulsifier etc. that can be used for free radical polymerization are not particularly limited, and can suitably select Select use.It should be noted that the weight average molecular weight of carboxylic (methyl) acrylate copolymer can be caused by polymerizeing Agent, the usage amount of chain-transferring agent, reaction condition are controlled, its usage amount is suitably adjusted according to their type.
As polymerization initiator, can enumerate for example：Bis- (the 2- amidino groups third of 2,2 '-azodiisobutyronitriles, 2,2 '-azos Alkane) dihydrochloride, the double &#91 of 2,2 '-azos;2- (5- methyl -2- imidazoline -2- bases) Bing Wan ]Dihydrochloride, 2,2 '-are occasionally Bis- (the 2- methyl-props amidine) dithionates of nitrogen, 2,2 '-azos bis- (N, N '-dimethyleneisobutylamidines), 2,2 '-azos are double [N- (2- carboxy ethyls) -2- methyl-prop Mis ]Hydrate (trade name：VA-057, Wako Pure Chemical Industries, Ltd.'s system) Etc. azo initiators；The persulfates such as potassium peroxydisulfate, ammonium persulfate；Two (2- ethylhexyls) peroxy dicarbonates, two (4- tert-butylcyclohexyls) peroxy dicarbonate, peroxide-butyl carbonate, new peroxide tert-butyl caprate, peroxide Change the tertiary own ester of neopentanoic acid, tert-Butyl peroxypivalate, dilauroyl peroxide, two positive decoyl of peroxidating, peroxidating 2- ethyls Caproic acid 1,1,3,3- tetramethyls butyl ester, two (4- methyl benzoyls) peroxide, dibenzoyl peroxide, peroxidating isobutyl The peroxide systems such as tert-butyl acrylate, 1,1- bis- (tertiary hexyl peroxy) hexamethylene, tert-butyl hydroperoxide, hydrogen peroxide cause Agent；The combination of persulfate and sodium hydrogensulfite, combination of peroxide and sodium ascorbate etc. are by peroxide and reducing agent Redox series initiators being composed etc., but not limited to this.
Above-mentioned polymerization initiator can be used alone, and in addition can also be mixed with two or more, and content on the whole is opposite It is preferably 0.005~1 parts by weight in forming 100 parts by weight of monomer component of above-mentioned carboxylic (methyl) acrylate copolymer Left and right.
As chain-transferring agent, it can be cited for example that：Lauryl mercaptan, glycidyl mercaptan, thioacetic acid, 2- sulfydryls Ethyl alcohol, thioacetic acid, thioglycolic acid 2- ethylhexyls, 2,3- dimercapto -1- propyl alcohol etc..Chain-transferring agent can individually make With in addition can also being mixed with two or more, content on the whole is 0.1 weight relative to 100 parts by weight of total amount of monomer component It is following to measure part or so.
In order to improve the adaptation under the conditions of high temperature and humidity, various silane can be added in adhesive composition of the invention Coupling agent.As silane coupling agent, the arbitrarily silane coupling agent with appropriate functional group can be used.It, can as functional group To enumerate for example：Vinyl, epoxy group, amino, sulfydryl, (methyl) acryloxy, acetoacetyl, isocyanate group, benzene Vinyl, polythiaether base etc..Specifically, it can be cited for example that：Vinyltriethoxysilane, vinyl tripropoxy silicon Alkane, vinyl silane triisopropoxide, vinyltributoxysilane etc. contain vinyl silicane coupling agent；γ-glycidoxy Propyl trimethoxy silicane, γ-glycidoxypropyl group triethoxysilane, 3- glycidoxypropyl diethoxies Silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane etc. contain epoxy silane coupling；Gamma-amino propyl front three Oxysilane, N- β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, N- (2- amino-ethyls) 3- ammonia Base hydroxypropyl methyl dimethoxysilane, γ-triethoxysilyl-N- (1,3- dimethylbutylenes) propylamine, N- benzene Base-gamma-amino propyl trimethoxy silicane etc. contains amino silicane coupling agent；γ-mercapto propyl methyl dimethoxy silane etc. Containing mercaptosilane coupling agents；To silane coupling agents containing styryl such as styryltrimethoxysilanes；γ-acryloxy Propyl trimethoxy silicane, γ-methacryloxypropyl etc. are coupled containing (methyl) acryl silane Agent；The coupling agents containing isocyanato silanes such as 3- isocyanate group propyl-triethoxysilicanes；Bis- (triethoxysilyls third Base) coupling agent of base silane containing polythiaether such as four thioethers；Etc..
Above-mentioned silane coupling agent can be used alone, and in addition can also be mixed with two or more, and content on the whole is opposite In 100 parts by weight of monomer component for constituting above-mentioned carboxylic (methyl) acrylate copolymer be preferably 1 parts by weight or less, more Preferably 0.01~1 parts by weight, further preferably 0.02~0.8 parts by weight, particularly preferably 0.05~0.7 parts by weight.If The combined amount of silane coupling agent is more than 1 parts by weight, then generates unreacted coupling agent ingredient, undesirable in terms of durability.
It should be noted that the feelings of free radical polymerization and the copolymerization of above-mentioned monomer component can be passed through in above-mentioned silane coupling agent Under condition, the silane coupling agent can be used as above-mentioned monomer component.Its ratio is relative to composition above-mentioned carboxylic (methyl) 100 parts by weight of monomer component of acrylate copolymer are preferably 0.005~0.7 parts by weight.
By that comprising isocyanates system crosslinking agent, can assign durable with adhesive in the adhesive composition of the present invention The relevant cohesiveness of property.
Isocyanates system crosslinking agent refers to having 2 or more isocyanate group (including by sealer or more in 1 molecule Dimerization etc. is by the isocyanates regenerative functional group of isocyanate group temporary protection) compound.
As isocyanates system crosslinking agent, the aromatic series such as toluene di-isocyanate(TDI), xylene diisocyanate can be enumerated The aliphatic isocyanic acid such as the alicyclic isocyanates such as isocyanates, isophorone diisocyanate, hexamethylene diisocyanate Ester etc..
More specifically, it can be mentioned, for example：The lower aliphatics such as tetramethylene diisocyanate, hexamethylene diisocyanate Polyisocyanates；Cyclopentylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate etc. are alicyclic different Cyanate；2,4 toluene diisocyanate, 4,4 '-methyl diphenylene diisocyanates, benzene dimethylene diisocyanate, The aromatic diisocyanates class such as polymethylene polyphenyl isocyanate；Trimethylolpropane/toluene di-isocyanate(TDI) trimer Addition product (trade name：Coronate L, Nippon Polyurethane Industry Co., Ltd.'s system), trimethylolpropane/hexa-methylene two it is different Cyanate trimer addition product (trade name：Coronate HL, Nippon Polyurethane Industry Co., Ltd.'s system), hexa-methylene two it is different Isocyanuric acid ester body (the trade name of cyanate：Coronate HX, Nippon Polyurethane Industry Co., Ltd.'s system) etc. isocyanates add At object, the trimethylolpropane addition product (trade name of benzene dimethylene diisocyanate：D110N, Mitsui Chemicals, Inc System), the trimethylolpropane addition product (trade name of hexamethylene diisocyanate：D160N, Mitsui Chemicals, Inc's system)； The addition product of polyethers polyisocyanates, polyester polyisocyanates and they and various polyalcohols；With isocyanurate-bond, contracting Polyisocyanates etc. after the progress such as two urea bonds, allophanic acid ester bond is multiple functionalized.Among these, since reaction speed is fast, because And it is preferable to use aliphatic isocyanates.
The mixed proportion of isocyanates system crosslinking agent in the adhesive composition of the present invention is not particularly limited, such as phase It is preferably 0.01~10 parts by weight for above-mentioned carboxylic 100 parts by weight of (methyl) acrylate copolymer, is more preferably 0.01~5 parts by weight.
In addition, in the adhesive composition of the present invention, preferably peroxidating is used together with above-mentioned isocyanates system crosslinking agent Object system crosslinking agent.
As above-mentioned peroxide system crosslinking agent, various peroxide can be used.As peroxide, two can be enumerated (2- ethylhexyls) peroxy dicarbonate, two (4- tert-butylcyclohexyls) peroxy dicarbonates, dicetyl peroxydicarbonate two The tertiary own ester of secondary butyl ester, new peroxide tert-butyl caprate, peroxidating neopentanoic acid, tert-Butyl peroxypivalate, two bay of peroxidating Acyl, two positive decoyl of peroxidating, peroxidating isobutyric acid 1,1,3,3- tetramethyls butyl ester, peroxidating 2 ethyl hexanoic acid 1,1,3,3- Tetramethyl butyl ester, two (4- methyl benzoyls) peroxide, dibenzoyl peroxide, peroxidating tert-butyl isobutyrate etc..This It is excellent for cross-linking reaction efficiency among a little, particularly preferably use two (4- tert-butylcyclohexyls) peroxy dicarbonates, mistake Aoxidize two lauroyl, dibenzoyl peroxide.
The mixed proportion of peroxide system crosslinking agent in the adhesive composition of the present invention is not particularly limited, such as phase It is preferably 10 parts by weight or less, more preferably 0.01 for above-mentioned carboxylic 100 parts by weight of (methyl) acrylate copolymer ~10 parts by weight, further preferably 0.01~5 parts by weight.
In addition, as crosslinking agent, can also use in addition to above-mentioned isocyanates system crosslinking agent, peroxide system crosslinking agent Crosslinking agent.
As crosslinking agent, organic system crosslinking agent other than the above, multi-functional metallo-chelate can be enumerated.As above-mentioned Organic system crosslinking agent in addition can enumerate epoxy crosslinking agent, carbodiimide system crosslinking agent, imines system crosslinking agent, oxazolines It is crosslinking agent, aziridine system crosslinking agent etc..Multi-functional metallo-chelate is polyvalent metal atom and organic compound covalent bond Close or coordination bonding at substance.As polyvalent metal atom, can enumerate Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc..As in the organic compound for carrying out covalent bonding or coordination bonding Atom can enumerate oxygen atom etc., and can enumerate Arrcostab, alcoholic compound, carboxylic acid compound, etherificate as organic compound closes Object, ketone compound etc..These crosslinking agents can use independent a kind or two or more is applied in combination.
In addition, in the adhesive composition of the present invention, can be fitted in the range of not departing from the object of the invention as needed When use viscosity modifier, stripping conditioning agent, tackifier, plasticizer, softening agent；Including glass fibre, glass microballoon, metal The filler of powder, other inorganic powders etc.；Pigment, colorant (pigment, dyestuff etc.), pH adjusting agent (acid or alkali), antioxidant, The additives such as ultra-violet absorber.
The adhesive composition of the present invention includes carboxylic (methyl) acrylate copolymer, the crosslinking of isocyanates system Agent can form adhesive phase by making the binder composition cross-links.What is contained in the adhesive composition of the present invention is logical Formula (1) compound represented is due to the crosslinking rush to crosslinking agents such as isocyanates system crosslinking agent, peroxide system crosslinking agents The gel fraction of adhesive phase can be improved from manufacturing the starting stage into the adhesive composition of effect, therefore the present invention.Its As a result, the adhesive phase of excellent in workability can be obtained.
In the adhesive composition of the present invention, in order to improve processability, productivity, make adhesive composition heat cross-linking The gel fraction of the adhesive phase after 2 hours after (155 DEG C, 2 minutes) is preferably set to 45~95 weight %, is more preferably set as 55 ~95 weight %, 60~85 weight % are further preferably set as.In the case that gel fraction is less than 45 weight %, due to adhesive Layer is excessively soft, if therefore be processed in this state, have in processing and generate the problems such as adhering to adhesive paste on blade Trend.In addition, lead to the problem of impression in the coiling process of adhesive phase after cross-linking and generate in appearance, therefore productivity It is deteriorated.It should be noted that the measurement of the gel fraction of adhesive phase can be carried out in the method described in embodiment.
2. transparency conducting layer adhesive phase
The transparency conducting layer adhesive phase of the present invention is characterized in that, is formed by above-mentioned adhesive composition.As Adhesive composition can use invention discussed above adhesive composition.In addition, the forming method of adhesive phase exists Described in hereafter.
3. laminated body
The laminated body of the present invention is characterized in that, includes base material film, above-mentioned transparency conducting layer adhesive phase and tool successively There are the transparent conductive base of transparency conducting layer, above-mentioned transparency conducting layer adhesive phase saturating with above-mentioned transparent conductive base Bright conductive layer contact.
As transparency conducting layer adhesive phase, the adhesive composition of the present invention by mentioned earlier can be used to be formed Adhesive phase.
The forming method of above-mentioned adhesive phase is not particularly limited, but can be that above-mentioned adhesive is coated on various base materials Composition is dried using driers such as oven heats, and the volatilizations such as solvent is made to form adhesive phase, which is transferred to Method on above-mentioned base material film；Above-mentioned adhesive composition can also be directly coated on above-mentioned base material film to form adhesive Layer.
As above-mentioned base material, it is not particularly limited, such as can enumerate：The various base materials such as mold release film, transparent resin film base material.
As the coating method to above-mentioned base material film, base material, various methods can be used.Specifically, it can be cited for example that Sprayer, roller coating, roller lick coating, intaglio plate coating, reverse roll coating, roller brush cloth, spraying, dip roll coating, rod coating, cutter painting, Airblade coating, lip coating, utilizes the methods of the extrusion coating methods of die coating machine etc. at curtain coating.
Drying condition (temperature, time) is not particularly limited, can be appropriate according to composition, concentration of adhesive composition etc. Setting, for example, 80~170 DEG C or so (preferably 90~200 DEG C) and 1~60 minute (preferably 2~30 minutes).
The thickness (after dry) of adhesive phase is for example preferably 5~100 μm, is more preferably 10~60 μm, further preferably It is 12~40 μm.In the case that the thickness of adhesive phase is less than 5 μm, there are the adaptation variation to adherend, high temperature, high temperature and humidity Under the insufficient trend of durability.On the other hand, in the case that the thickness of adhesive phase is more than 100 μm, adhesive phase is formed When adhesive composition cannot fully be dried when being coated and dried, there is the face of gas bubbles left or adhesive phase to generate thickness Unevenness, to which apparent problem is easy to become significant trend.
As the constituent material of above-mentioned mold release film, it can be mentioned, for example：Polyethylene, polypropylene, polyethylene terephthalate, The porous materials such as the resin films such as polyester film, paper, cloth, non-woven fabrics, net, foamed sheet, metal foil and their laminated body etc. are suitable Sheet etc., but for the excellent aspect of surface smoothness, it is preferable to use resin film.
As the resin film, it can be cited for example that：Polyethylene film, polybutene film, polybutadiene film, gathers polypropylene screen Methylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate Film, polyurethane film, vinyl-vinyl acetate copolymer film etc..
The thickness of above-mentioned mold release film is usually 5~200 μm, preferably 5~100 μm or so.It can be as needed to above-mentioned Mold release film carries out：The demoulding of releasing agent, silicon dioxide powder using silicone-based, fluorine system, chain alkyl system or fatty acyl amine system etc. And antifouling process；The antistatic treatment of application type, interior plus type, vapor deposition type etc..Especially, suitable by the surface to above-mentioned mold release film When carrying out the lift-off processings such as silicone-treated, chain alkyl processing, fluorine processing, the stripping from above-mentioned adhesive phase can be further increased From property.
It as above-mentioned transparent resin film base material, is not particularly limited, the various resin films with the transparency can be used.It should Resin film is formed by 1 tunic.For example, as the material, polyethylene terephthalate, polyethylene naphthalate can be enumerated Equal polyester based resins, acetic acid esters system resin, polyether sulfone system resin, polycarbonate-based resin, polyamide series resin, polyimides system Resin, polyolefin-based resins, (methyl) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyphenyl second Alkene system resin, polyvinyl alcohol resin, polyarylate system resin, polyphenylene sulfide system resin etc..It is particularly preferably poly- among these Ester system resin, polyimides system resins and polyether sulfone system resin.The thickness of above-mentioned transparent resin film base material is preferably 15~200 μ m。
In addition, can have anchor layer between base material film and adhesive phase.The material for forming anchor layer does not limit especially It is fixed, it can be cited for example that：Various polymerization species, the colloidal sol of metal oxide, silicon dioxide gels etc..In addition, above-mentioned being formed Antistatic agent can be contained in the Anchor Agent of anchor layer.In addition, the thickness of anchor layer is not particularly limited, preferably 5~300nm Left and right.
In addition, in above-mentioned Anchor Agent, for the bad of the adhesive phase or base material film for inhibiting to generate when with anchor coating layer touch The purpose of change etc., can mix various additives, in addition for the purpose for assigning function to anchor coating, can mix various additions Agent.For example, antioxidant, anti-deterioration agent, ultra-violet absorber, fluorescent whitening agent etc. can be added.
Base material film used in laminated body as the present invention can use resin film, be used to form liquid crystal display device The various films such as the optical film of equal image display devices, the kind thereof is not particularly limited.As above-mentioned resin film, can enumerate in this theory Resin film described in bright book.As above-mentioned optical film, polarizing coating can be enumerated.Polarizing coating is generally used in the single side of polarizing film Or the two-sided upper polarizing coating with transparent protective film.
Polarizing film is not particularly limited, and can use various polarizing films.As polarizing film, it can be cited for example that：Make iodine, two These dichroic substances of color dyestuff are adsorbed in polyvinyl alcohol mesentery, part formalizing polyvinyl alcohol mesentery, ethylene-acetate second Polarizing film obtained from being uniaxially stretched after the hydrophilic macromolecule films such as the partly-hydrolysed film of enoate copolymer system；Polyvinyl alcohol The polyenoid such as dehydration treatment or the dehydrochlorinated products of polyvinyl chloride system alignment films etc..Among them, polyvinyl alcohol is preferably comprised The polarizing film of the dichroic substances such as mesentery and iodine, further preferably the iodine system polarizing film of iodine and/or iodide ion.In addition, these are partially The thickness of piece of shaking is not particularly limited, it is however generally that is 5~80 μm or so.
Polarizing film made of being uniaxially stretched after being dyed to polyvinyl alcohol mesentery with iodine can for example manufacture as follows： It is dyed by the way that polyvinyl alcohol to be impregnated in the aqueous solution of iodine, is stretched to 3~7 times of former length, is thus made.According to It needs to be impregnated in the aqueous solution of potassium iodide that may include boric acid, zinc sulfate, zinc chloride etc. etc..In addition, as needed Polyvinyl alcohol mesentery water can be impregnated in before dyeing to wash.By being washed to polyvinyl alcohol mesentery, thus may be used To wash contamination and the anti-blocking agent of polyvinyl alcohol mesentery surface, additionally having is prevented by making polyethenol series membrane swelling Dye unequal non-uniform effect.Stretching can be carried out after with iodine staining, can also Edge Coloring side stretch, in addition can also Iodine staining is used after the stretch.It can also be stretched in the aqueous solution of boric acid, potassium iodide etc. or water-bath.
In addition, in the present invention, it is 10 μm of slim polarizing films below that can also use thickness.Go out from the viewpoint of slimming For hair, which is preferably 1~7 μm.The uneven thickness of such slim polarizing film is few, visual excellence, and size It is with low uncertainty, therefore excellent in te pins of durability, the thickness of polarizing coating is made in addition can also realize slimming, such slim in this regard Polarizing film be preferred.
As slim polarizing film, can typically enumerate：In Japanese Unexamined Patent Application 51-069644 bulletins, Japanese Unexamined Patent Publication No. 2010/100917 2000-338329 bulletins, No. 2010/100917 pamphlet of International Publication No., International Publication No. brochure Slim polarizing coating described in son, No. 4751481 specifications of Japan Patent or Japanese Unexamined Patent Publication 2012-073563 bulletins.These Slim polarizing coating can be obtained by following preparation method：Including by polyvinyl alcohol resin (hereinafter also referred to PVA systems resin) layer and The preparation method of process and the process dyed that stretching is stretched with resin base material with the state of laminated body.If it is the system Method is supported due to being stretched with resin base material even if then PVA resins are thin, thus also can be not caused by stretching It is stretched under conditions of a problem that fracture.
As above-mentioned slim polarizing coating, including the process stretched with the state of laminated body and the process dyed Preparation method among, from can high magnification stretch so as to improve polarization property from the aspect of, preferably：Using in International Publication No. 2010/100917 pamphlet, No. 4751481 specifications of No. 2010/100917 pamphlet of International Publication No. or Japan Patent, The preparation method of that process stretched included in boric acid aqueous solution described in Japanese Unexamined Patent Publication 2012-073563 bulletins Obtained slim polarizing coating, especially preferably：By in No. 4751481 specifications of Japan Patent, Japanese Unexamined Patent Publication 2012- Being included in described in No. 073563 bulletin carries out the preparation method institute of the complementary process stretched in the air before being stretched in boric acid aqueous solution Obtained slim polarizing coating.
The material of transparent protective film as the one side or two-sided setting that are formed in above-mentioned polarizing film, preferably clear, machine The excellent materials such as tool intensity, thermal stability, moisture shielding, isotropism.For example, can enumerate：Poly terephthalic acid second The polyester based polymers such as diester, polyethylene naphthalate；The cellulose-based polymerization such as diacetyl cellulose, triacetyl cellulose Object；The acrylic acid series polymeric compounds such as polymethyl methacrylate；The benzene such as polystyrene, acrylonitritrile-styrene resin (AS resins) Ethylene-based polymer；Makrolon based polymer etc..In addition, example as the polymer for forming above-mentioned transparent protective film, also It can enumerate：Polyethylene, polypropylene, ring system polyolefin or polyolefin, ethylene-propylene copolymer etc. with norbornene structure Polyolefin polymer；Vinyl chloride-based polymer；The amides based polymer such as nylon, aromatic polyamide；Imide series polymer, Sulfone based polymer, polyether sulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol system polymer, partially Dichloroethylene based polymer, polyvinyl butyral based polymer, aromatic ester based polymer, polyoxymethylene based polymer, epoxy The blend etc. of polymer or above-mentioned polymer.Transparent protective film can also be with acrylic acid series, carbamate system, acrylic acid The thermohardening types such as carbamate system, epoxy, silicone-based, ultraviolet curing resin the form of cured layer formed.
The thickness of protective film can be suitably determined, but in general, from the side such as the workability such as intensity, operability, film Face is set out, and is 1~500 μm or so.
Above-mentioned polarizing film is usually closely sealed via water system adhesive etc. with protective film.As water system adhesive, may be exemplified Go out isocyanates system adhesive, polyethenol series adhesive, gelatin system adhesive, ethylene base system latex system, aqueous polyurethane, water It is polyester etc..Except these, as the adhesive between polarizing film and transparent protective film, ultraviolet hardening gluing can be enumerated Agent, electronic beam solidified adhesive etc..Electronic beam solidified polarizing coating is shown with adhesive to above-mentioned various transparent protective films Suitable cementability.In addition, metallic compound filler can be contained in adhesive used in the present invention.
Not being bonded on the face of polarizing film for above-mentioned transparent protective film can implement hard conating, antireflection process, with anti-sticking Even, the processing for the purpose of diffusing or is anti-dazzle.
In the present invention, as base material film, can use the above-mentioned iodine system polarizing film containing iodine and/or iodide ion extremely Few one side has the iodine system polarizing coating of transparent protective film.By the transparency conducting layers such as the iodine system polarizing coating and ITO across adhesive In the case of layer stackup, oozes out into above-mentioned adhesive phase there is also the micro iodine from iodine system polarizing coating and corrode ITO etc. thoroughly The problem of bright conductive layer.However, as described above, the general formula contained in the adhesive phase formed by the adhesive composition of the present invention (1) compound represented forms overlay film in layer at transparent layer, therefore is also possible to prevent to be moved to from the iodine that polarizing film oozes out Layer at transparent layer.
In addition, as the optical film other than polarizing coating, for example,：Reflecting plate, half transmitting plate, phase plate (packet Include the wave plates such as 1/2,1/4), compensation film for angular field of view, brightness enhancement film etc. be occasionally used for being formed liquid crystal display device etc. as optical layer Optical film.They can be used alone as optical film, in addition, can be laminated on above-mentioned polarizing coating in actual use 1 layer or 2 layers with On use.
Furthermore it is possible to implement activation process to above-mentioned optical film.Various methods may be used in activation process, such as can adopt With sided corona treatment, low pressure UV processing, corona treatment etc..
It as the transparent conductive base with transparency conducting layer, is not particularly limited, can use well known with saturating The transparent conductive base of bright conductive layer, but in general, use the base material over the transparent substrate with transparency conducting layer.
As transparent base, as long as with the transparency, it can be cited for example that：Resin film, the base material for including glass etc. (such as sheet, membranaceous, plate base material etc.) etc., particularly preferred resin film.The thickness of transparent base is not particularly limited, preferably It is 10~200 μm or so, more preferably 15~150 μm or so.
It as the material of above-mentioned resin film, is not particularly limited, the various plastic materials with the transparency can be enumerated.Example Such as, as the material, the polyester based resins such as polyethylene terephthalate, polyethylene naphthalate can be enumerated；Acetic acid esters Be resin, polyether sulfone system resin, polycarbonate-based resin, polyamide series resin, polyimides system resins, polyolefin-based resins, (methyl) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol It is resin, polyarylate system resin, polyphenylene sulfide system resin etc..Polyester based resin, polyimides are particularly preferably among these It is resin and polyether sulfone system resin.
In addition, for above-mentioned transparent base, can sputtering, corona discharge, flame, ultraviolet light photograph be implemented to its surface in advance Penetrate, electron beam irradiation, chemical conversion, the etching processes such as oxidation or primary coat processing, come improve be arranged over the transparent substrate it is transparent Adaptation of the conductive layer to above-mentioned transparent base.In addition, before transparency conducting layer is arranged, solvent can be utilized clear as needed It washes, ultrasonic cleaning etc. is dusted, cleans.
As the constituent material of above-mentioned transparency conducting layer, be not particularly limited, can be used selected from by indium, tin, zinc, gallium, antimony, The metal oxide of at least one kind of metal in the group that titanium, silicon, zirconium, magnesium, aluminium, gold, silver, copper, palladium, tungsten form.It is aoxidized in the metal Metallic atom shown in can also containing above-mentioned group as needed in object.For example, it is preferable to using tin indium oxide (ITO), contain The tin oxide etc. of antimony particularly preferably uses ITO.In addition, among ITO, since noncrystalline tin indium oxide significantly embodies The effect of the present invention, therefore preferably noncrystalline tin indium oxide.As ITO, preferably comprise 80~99 weight % of indium oxide and 1~20 weight % of tin oxide.
The thickness of above-mentioned transparency conducting layer is not particularly limited, be preferably set as 10nm or more, more preferably 15~40nm, into One step is preferably 20~30nm.
It as the forming method of above-mentioned transparency conducting layer, is not particularly limited, known method may be used.Specifically For, such as may be exemplified out vacuum vapour deposition, sputtering method, ion plating method.Alternatively, it is also possible to be used according to required film thickness Method appropriate.
As the thickness of the base material with above-mentioned transparency conducting layer, 15~200 μm can be enumerated.In addition, from the sight of filming Point consideration, preferably 15~150 μm, more preferably 15~50 μm.There is above-mentioned transparency conducting layer being used in a manner of resistive film Base material in the case of, such as 100~200 μm of thickness can be enumerated.In addition, the case where being used with electrostatic capacity Under, such as preferably 15~100 μm of thickness, in particular, with the requirement of further filming in recent years, more preferably 15~ 50 μm of thickness, further preferably 20~50 μm of thickness.
Furthermore it is possible to which priming coat, anti-oligomer layer etc. is arranged between transparent conductive film and transparent base as needed.
4. image display device
As described above, the case where adhesive phase of the present invention is even laminated with the adhesive phase over transparent conductive layer Under, it can also inhibit the corrosion of transparency conducting layer, the sheet resistance of transparency conducting layer can be inhibited to rise.Therefore, of the invention As long as the scheme that adhesive phase is contacted with the transparency conducting layer of the image display device with transparency conducting layer can fit Preferably use.
For example, the laminated body for having the adhesive phase of the present invention, which can be suitably employed in manufacture and constitute, has input unit ((plasma is aobvious by liquid crystal display device, organic EL (electroluminescent) display device, PDP for the image display device of (touch panel etc.) Show device tablet), Electronic Paper etc.), the base material (component) of the equipment such as input unit (touch panel etc.) or the base for these equipment Material (component), it is particularly possible to be suitably employed in the optical element of manufacture touch panel.In addition, no matter resistive film mode, electrostatic The mode of the touch panel of capacity mode etc etc. can use.
In addition, cutting, being printed obtained from the processing such as resist, etching, silver inks printing to the laminated body implementation of the present invention Transparent and electrically conductive film may be used as optical device base material (optical component).As optical device base material, as long as having light The base material for learning characteristic is just not particularly limited, it can be cited for example that：Constitute image display device (liquid crystal display device, organic EL (electroluminescent) display device, PDP (plasma display panels), Electronic Paper etc.), the equipment such as input unit (touch panel etc.) Base material (component) or base material (component) for these equipment.
The concrete example of image display device as the adhesive phase for using the present invention, it can be mentioned, for example：By electrically conducting transparent Layer is used for the image display device of antistatic layer purposes；Image by transparency conducting layer for the electrode applications of touch panel is shown Device.As the image display device that transparency conducting layer is used for antistatic layer purposes, specifically, for example,：Such as Shown in Fig. 1, composition includes 5/ driving electrodes of polarizing coating 1/ adhesive phase, 2/ antistatic layer, 3/ glass substrate, 4/ liquid crystal layer, 6/ glass 4/ adhesive phase of substrate, 2/ polarizing coating 1, and above-mentioned antistatic layer 3, driving electrodes 6 are shown by the image that transparency conducting layer is formed Device.The adhesive phase of the present invention can be used as to the adhesive phase 2 of the upside (viewing side) of the image display device.In addition, As the image display device by transparency conducting layer for the electrode applications of touch panel, for example,：It is configured to polarize 1/ adhesive phase of film, 2/ antistatic layer and 7/ glass substrate of sensor layer, 4/ liquid crystal layer, 5/ driving electrodes and 8/ glass of sensor layer 4/ adhesive phase of substrate, 2/ polarizing coating 1 (in-cell types touch panel, Fig. 2) or be configured to 1/ adhesive phase 2/ of polarizing coating resist it is quiet Electric layer and 6/ glass substrate of sensor layer 7/ sensor layer, 9/ glass substrate, 4/ liquid crystal layer, 5/ driving electrodes, 4/ adhesive phase 2/ are partially Vibrating diaphragm 1 (on-cell types touch panel, Fig. 3), and antistatic layer and sensor layer 7, sensor layer 9, driving electrodes 6 are by saturating The image display device that bright conductive layer is formed.The polarizing coating with adhesive phase of the present invention can be used to show as the image to fill The polarizing coating (1,2) with adhesive phase for the upside (viewing side) set.
Embodiment
Hereinafter, using embodiment, the present invention is described in detail, but the present invention without departing from its purport the case where constituting Under embodiment not limited to the following.In addition, in each example, part, % are weight basis.
Production Example 1 (making of base material film (1))
There is the polyvinyl alcohol (PVA) of 9 μm of thickness for forming a film on amorphism polyethylene terephthalate (PET) base material The laminated body of layer carries out the aerial assisting tension of 130 DEG C of draft temperature, thus generates stretching laminated body.Then, it is laminated to stretching Body is dyed, and coloring laminated body is thus generated.And then laminated body will be coloured in the boric acid aqueous solution of 65 DEG C of temperature according to total Stretching ratio is that 5.94 times of mode is stretched together with amorphism PET base material, generates the light of the PVA layers comprising 4 μ m-thicks Learn film laminated body.Two sections of stretchings in this way, the PVA molecules of the PVA layers to form a film out in amorphism PET base material take in high-order To, be orientated in high-order in one direction in the form of more iodide ion complex compounds by dyeing adsorbed iodine, high-performance can be used as Polarizing film.In addition, being bonded soap on one side in the surface pva coating system adhesive of the polarizing film of the optical film laminate on one side The acrylic resin film (transparent protective film (1)) for changing treated 40 μ m-thicks, then removes amorphism PET base material, makes Polarizing coating is protected using the single side of slim polarizing film.Hereinafter, calling it as base material film (1).
Production Example 2 (making of base material film (2))
The PVA film of 80 μm of thickness in 30 DEG C, the iodine solution of 0.3% concentration is dyed 1 in speed than side between different rollers Minute, while being stretched to 3 times.Later, while 60 DEG C the boric acid comprising 4% concentration, 10% concentration potassium iodide aqueous solution in 0.5 minute side of dipping stretch so that total stretching ratio is up to 6 times.Next, in 30 DEG C of the potassium iodide for including 1.5% concentration Aqueous solution in impregnate 10 seconds, after thus being cleaned, dry 4 minutes at 50 DEG C, obtained the polarizing film of 20 μm of thickness.This Outside, while in a surface of polarizing film coating PVA systems adhesive, side is bonded the acrylic acid series tree of 40 μ m-thicks after saponification process Adipose membrane (transparent protective film (1)) then utilizes PVA systems adhesive in the norborneol of 40 μm of another surface coating thickness of polarizing film Alkene mesentery (transparent protective film (2)), to make two-sided protection polarizing coating.Hereinafter, calling it as base material film (2).
Production Example 3 (making of the solution containing acrylate copolymer (A-1))
In the reaction vessel for having condenser pipe, nitrogen ingress pipe, thermometer and agitating device, it is added together with ethyl acetate 95 parts of butyl acrylate, 1 part of acrylic acid 4- hydroxybutyls, 4 parts of acrylic acid and be 1 part relative to 100 parts of monomer (solid constituent) 2 as initiator, 2 '-azodiisobutyronitriles (AIBN) are allowed to react 7 hours under stream of nitrogen gas in 60 DEG C.Later, exist Ethyl acetate is added in the reaction solution, has obtained the solution of the acrylate copolymer (A-1) containing weight average molecular weight 2,000,000 (30 weight % of solid content concentration).
Production Example 4~10 (making of the solution containing acrylate copolymer (A-2)~(A-8))
Other than being changed to the composition of monomer to form shown in table 1, is got similarly with Production Example 3 and contained propylene The solution of acid ester copolymer (A-2)~(A-8) (solid content concentration of each solution is 30 weight %).
Production Example 11 (making of the solution containing acrylate copolymer (A-9))
In the reaction vessel for having condenser pipe, nitrogen ingress pipe, thermometer and agitating device, it is added together with ethyl acetate 84.9 parts of butyl acrylate, 0.1 part of acrylic acid 4- hydroxybutyls, 5 parts of acrylic acid, 10 parts of benzyl acrylate and as initiator Relative to monomer (solid constituent), 100 parts are 1 part of AIBN, are reacted 7 hours in 60 DEG C under stream of nitrogen gas.Later, anti-at it It answers and ethyl acetate is added in liquid, obtained the solution (solid of the acrylate copolymer (A-9) containing weight average molecular weight 2,000,000 30 weight % of content concn).
【Table 1】
Abbreviation difference in table 1 is as described below.
BA：Butyl acrylate
BzA：Benzyl acrylate
AA：Acrylic acid
HEA：2-Hydroxy ethyl acrylate
HBA：Acrylic acid 4- hydroxybutyls
In addition, the weight average molecular weight of the acrylate copolymer obtained in Production Example 3~11 passes through measurement side below Method is measured.
The measurement > of the weight average molecular weight (Mw) of < acrylate copolymers
The weight average molecular weight of made acrylate copolymer is measured by GPC (gel permeation chromatography).
Device：Tosoh society system, HLC-8220GPC
Column：
Sample column：Tosoh society system, TSK guard column Super HZ-H (1)+TSK gel Super HZM- H (2)
Reference column：Tosoh society system, TSKgel Super H-RC (1)
Flow：0.6mL/min
Injection rate：10μL
Column temperature：40℃
Eluent：THF
Inject sample solution concentration：0.2 weight %
Detector：Differential refractometer
It should be noted that weight average molecular weight is calculated by polystyrene conversion.
Embodiment 1
(preparation of acrylic adhesive composition)
For solution (30 weight of solid content concentration containing acrylate copolymer (A-1) obtained in Production Example 3 Measure %) every 100 parts of solid constituent, cooperation as crosslinking agent hexamethylene diisocyanate with trimethylolpropane add Close object (trade name：TAKENATE D160N, Mitsui Chemicals, Inc's system) 0.1 part, 0.3 part of dibenzoyl peroxide, conduct Phosphanol SM-172 (trade name, the acid value of phosphate ester acid：219mgKOH/g, Toho Chemical Industry Co., Ltd.'s system) 0.07 part, as γ-glycidoxypropyltrime,hoxysilane (trade name of silane coupling agent：KBM-403, SHIN-ETSU HANTOTAI Learn Industrial Co., Ltd system) 0.075 part and as phenolic antioxidant pentaerythrite Si &#91;3- (3,5- di-t-butyls- 4- hydroxy phenyls) 0.3 part of propionic ester (IRGANAOX 1010, BASF Japan Co. Ltd. systems), it is viscous to have obtained acrylic acid series Mixture composite.
(making of the base material film with adhesive phase)
With sprayer (Off ァ ウ Application テ ン コ ー タ ー) by above-mentioned acrylic adhesive composition even application in The surface of the processed polyethylene terephthalate film of silicone series stripping agent (base material), in 155 DEG C of air circulating type constant temperature It is 2 minutes dry in baking oven, form the adhesive phase of 20 μm of thickness on the surface of base material.Next, making to be formed with adhesive phase Diaphragm transposing in base material film (1) not protective film face, made the base material film with adhesive phase.
Embodiment 2~4
The number that the additive amount of phosphate ester acid is changed to from 0.07 part described in table 3, in addition to this, with embodiment 1 The base material film with adhesive phase is similarly made.
Embodiment 5
Phosphanol SM-172 (trade name, Toho Chemical Industry Co., Ltd.'s system) are changed to for 0.07 part Phosphanol RS-410 (trade name, acid value：105mgKOH/g, Toho Chemical Industry Co., Ltd.'s system) 0.07 part, remove this In addition, the base material film with adhesive phase has been made similarly to Example 1.
Embodiment 6
Phosphanol SM-172 (trade name, Toho Chemical Industry Co., Ltd.'s system) are changed to phosphoric acid for 0.07 part (reagent is superfine) 0.05 part of (Wako Pure Chemical Industries, Ltd.'s system) has made band bonding similarly to Example 1 in addition to this The base material film of oxidant layer.
Embodiment 7~11
The solution comprising acrylate copolymer (A-1) obtained in Production Example 3 is changed to respectively in Production Example 4 What is obtained in~7 includes the solution of acrylate copolymer (A-2)~(A-5), and does not add peroxidating in embodiment 8 Dibenzoyl has made the base material film with adhesive phase similarly to Example 1 in addition to this.
Embodiment 12~14
In (making of the base material film with adhesive phase) of embodiment 1, base material film (1) is changed in Production Example 2 Obtained base material film (2), base material film (3) (polyethylene terephthalate (PET) film that 38 μm of thickness, Mitsubishi Chemical's polyester film Co. Ltd. system), base material film (4) (polyethylene terephthalate (PET) film that 100 μm of thickness, Mitsubishi Chemical's polyester film strain formula Commercial firm's system), in addition to this, the base material film with adhesive phase has been made similarly to Example 1.
Embodiment 15
Phosphanol SM-172 (trade name, Toho Chemical Industry Co., Ltd.'s system) are changed to MP-4 for 0.3 part (acid value：670mgKOH/g, Daihachi Chemical Industry Co., Ltd.'s system) 0.08 part, in addition to this, make similarly to Example 1 Base material film with adhesive phase.
Embodiment 16,17
The solution containing acrylate copolymer (A-1) obtained in Production Example 3 is changed to obtain in Production Example 11 The solution containing acrylate copolymer (A-9) arrived, and by MP-4 (acid values：670mgKOH/g, big eight chemical industry strain Formula commercial firm system) additive amount be changed to from 0.08 part in the additive amount described in table 3, in addition to this, similarly to Example 15 The base material film with adhesive phase is made.
Embodiment 18
In (making of the base material film with adhesive phase) of embodiment 17, base material film (1) is changed in Production Example 2 Obtained base material film (2) has made the base material film with adhesive phase similarly to Example 17 in addition to this.
Embodiment 19
By MP-4 (acid values：670mgKOH/g, Daihachi Chemical Industry Co., Ltd.'s system) 0.05 part be changed to phosphoric acid (reagent It is superfine) 0.08 part of (Wako Pure Chemical Industries, Ltd.'s system) and MP-4 (acid values：671mgKOH/g, big eight chemical industry strain formula meeting Society's system) 0.02 part of (phosphoric acid：MP-4=4：1 (weight ratio)), in addition to this, band adhesive has been made similarly to Example 16 The base material film of layer.
Embodiment 20~22
The type of the type of solution containing acrylate copolymer, phosphoric acid and/or phosphate and additive amount are changed to In the type and additive amount described in table 3, in addition to this, the base material film with adhesive phase has been made similarly to Example 1.
Comparative example 1
The additive amount of phosphate ester acid is changed to 5 parts from 0.07 part, in addition to this, is made similarly to Example 1 Base material film with adhesive phase.
Comparative example 2
The additive amount of phosphate ester acid is changed to 0.002 part from 0.07 part, in addition to this, is made similarly to Example 1 The base material film with adhesive phase is made.
Comparative example 3~5
The solution containing acrylate copolymer (A-1) obtained in Production Example 3 is changed to respectively in Production Example 8 The solution containing acrylate copolymer (A-6)~(A-8) obtained in~10, and do not add acid in comparative example 3,5 Formula phosphate has made the base material film with adhesive phase similarly to Example 1 in addition to this.
For the phosphate used in embodiment and comparative example, analyzed as described below.The results are shown in table 2.
(analysis method)
It is based on31The measurement result of P-NMR (Acetone-d6, room temperature), what calculating used in embodiment and comparative example The composition of phosphate.After the integrated value calculating mol% by measuring obtained peak, according to the alkyl chain of the alcohol component of ester Calculate content ratio (weight %).
(31P-NMR determination conditions)
Measurement device：Bruker Biospin,AVANCEIII-400
Observing frequency：160MHz(31P)
Flip angle (angles Off リ ッ プ)：30°
Measure solvent：Acetone-d6 (deuterated acetone)
Measuring temperature：Room temperature
Chemical shift reference：P=(OCH in Acetone-d63)3(31P；140ppm external standards)
【Table 2】
In table 2, phosphate monoester refers to the R of general formula (1)1And R2Any one of be hydrogen atom, another one be may include oxygen (general formula is R in the case of (2) to the compound of the hydrocarbon residue of the carbon atom number 1~18 of atom1For the compound of hydrogen atom), phosphoric acid Diester refers to the R of general formula (1)1And R2For may include oxygen atom carbon atom number 1~18 hydrocarbon residue compound (general formula (2) In the case of, it is R1For may include oxygen atom carbon atom number 1~18 hydrocarbon residue compound).For example, Phosphanol In the case of SM-172, " monoesters " indicates the R of general formula (2)1=H, R3=C8H17, n=0 compound, " diester " indicate general formula (2) R1=R3=C8H17, n=0 compound.
< gel fractions >
The acrylic adhesive composition obtained in embodiment and comparative example is set to carry out crosslinking in 2 minutes at 155 DEG C anti- It answers and obtains adhesive phase, after cross-linking reaction after 2 hours, adhesive phase 0.2g is taken, in the fluorine for having measured weight in advance Resin film (TEMISHNTF-1122, Nitto Denko Corp's system) (weight：Wa it is encased in), binding is so that acrylic acid series is viscous Mixture composite does not leak.As determination sample.Measure the weight (weight of determination sample：Wb), it is put into sample bottle. Ethyl acetate 40cc is added in sample bottle, places 7 days.Later, determination sample (fluororesin film+acrylic adhesive group is taken out Close object), the determination sample is 2 hours dry in 130 DEG C on aluminium cup.The weight (Wc) for measuring determination sample, is asked by following formula Go out gel fraction.
【Number 1】
< corrosion resistance tests >
Conductive film (the trade name of amorphism ITO layer will be formed on surface：ELECRYSTA (P400L), day east electrician Co. Ltd. system, below sometimes referred to as " transparent conductive base (E-1) ") cut into 15mm × 15mm, will in embodiment and After the base material film with adhesive phase obtained in comparative example cuts into 8mm × 8mm and the central portion that is fitted on the conductive film, Autoclave is added under conditions of 50 DEG C, 5 atmospheric pressure after 15 minutes, obtains the test sample of corrosion resistance.Using aftermentioned Measurement device measure the resistance value of obtained test sample, as " initial resistivity value ".
Later, by test sample put into temperature 60 C, humidity 90% environment in after 500 hours, measure resistance value make For " resistance value after damp and hot ".It should be noted that above-mentioned resistance value is to use Accent Optical Technologies What the HL5500PC of society was measured.According to " initial resistivity value " measured as described above and " resistance value after damp and hot ", Resistance change rate (%) is calculated with following formula, is evaluated according to evaluation criteria below.
【Number 2】
(evaluation criteria)
◎：Resistance change rate is less than 150% (ascensional range of resistance value caused by damp and hot is small (corrosion resistance is good))
○：Resistance change rate is 150% less than 300%
△：Resistance change rate is 300% less than 400%
×：Resistance change rate is that 400% or more (ascensional range of resistance value caused by damp and hot is big, and (corrosion resistance is not It is good))
In addition, in the base material film with adhesive phase of embodiment 1, in addition to above-mentioned transparent conductive base (E-1) with Outside, corrosion resistance test has been carried out using transparent conductive base below.
Transparent conductive base (E-2)：It is formed with the film (trade name of crystallinity ITO layer：V150-G5Y, day east electrician Co. Ltd. system)
Transparent conductive base (E-3)：It is formed with the glass of amorphism ITO layer
Transparent conductive base (E-4)：It is formed with the glass of crystallinity ITO layer
It should be noted that the manufacturing method of transparent conductive base (E-3) and transparent conductive base (E-4) is as follows It is described.
(making of transparent conductive base (E-3) and transparent conductive base (E-4))
Ito film is formed in a face of alkali-free glass by sputtering method, has made and has been led with crystallization the transparent of ito thin film Conductive substrate (E-4) and transparent conductive base (E-3) with amorphization ito film.For each base material, in reality 140 DEG C, heat treatment in 30 minutes have been carried out before applying the base material film fitting with adhesive phase obtained in example and comparative example.Crystallization Property ito thin film Sn ratios be 10 weight %.The Sn ratios of amorphism ito thin film are 3 weight %.It should be noted that ITO The calculation method of the Sn ratios of film is as described above.
Durability test (stripping and foaming) > of < adhesives
The diaphragm of the base material film with adhesive phase obtained in embodiment, comparative example is removed, fits in and is formed with knot The ito surface of the glass (transparent conductive base (E-4)) of crystalline substance ITO, 50 DEG C of progress, 5 atmospheric pressure, 15 minutes autoclaves After processing, in the heated oven of 80 DEG C and 100 DEG C of input and the constant temperature and humidity machine of 60 DEG C/90%RH and 85 DEG C/85%RH.Visually The stripping and foaming of base material film after observing 500 hours, are evaluated with following evaluation criteria.In addition, being recycled 1 hour with 1 Mode 85 DEG C and -40 DEG C of environment are implemented into (thermal cycling test (HS experiments)) after 300 cycles, visual observation polarizing coating Stripping and foaming, are evaluated with evaluation criteria below.
◎：Stripping or foaming are not confirmed completely.
○：Confirm the stripping or foaming of the degree for being unable to visual confirmation.
△：Confirm the small stripping or foaming for capableing of visual confirmation.
×：Confirm apparent stripping or foaming.
【Table 3】
【Table 4】
Abbreviation difference in table 3 is as described below.
(phosphate ester acid)
B-1：Phosphanol SM-172, acid value：219mgKOH/g, mono-/bis mixture, eastern nation chemical industry strain formula Commercial firm's system
B-2：Phosphanol RS-410, acid value：105mgKOH/g, mono-/bis mixture, eastern nation chemical industry strain formula Commercial firm's system
B-3：Phosphoric acid (reagent is superfine), Wako Pure Chemical Industries, Ltd.'s system
B-4：MP-4, acid value：670mgKOH/g, mono-/bis mixture, Daihachi Chemical Industry Co., Ltd.'s system
B-5：Mono phosphoric acid ester N-butyl (O=P (OH)2(OC4H9), product type：CDS001281),SIGMA-ALDRICH System
(crosslinking agent)
Peroxide system：Dibenzoyl peroxide
Isocyanates system：Trimethylolpropane benzene dimethylene diisocyanate (trade name：TAKENATE D110N) (three Well Chemical Co., Ltd. system)
(transparent conductive base)
E-1：Transparent conductive base (E-1)
E-2：Transparent conductive base (E-2)
E-3：Transparent conductive base (E-3)
E-4：Transparent conductive base (E-4)
Symbol description
1 polarizing coating
2 adhesive phases
3 antistatic layers
4 glass substrates
5 liquid crystal layers
6 driving electrodes
7 antistatic layers and sensor layer
8 driving electrodes and sensor layer
9 sensor layers

Claims (12)

1. a kind of polarizing coating with adhesive phase, which is characterized in that have base material film and transparency conducting layer adhesive phase
The transparency conducting layer adhesive phase is the electrically conducting transparent with the transparent conductive base with transparency conducting layer The adhesive phase of layer contact,
The transparency conducting layer adhesive phase is by containing：Carboxylic (methyl) third that weight average molecular weight is 1,200,000~3,000,000 The adhesive composition of olefin(e) acid ester copolymer, isocyanates system crosslinking agent and the following general formula (1) compound represented is formed,
In formula, R1And R2It is each independently hydrogen atom or may include the hydrocarbon residue of the carbon atom number 1~18 of oxygen atom,
The content of general formula (1) compound represented is relative to carboxylic 100 weight of (methyl) acrylate copolymer Amount part is 0.005~3 parts by weight.
2. the polarizing coating with adhesive phase as described in claim 1, which is characterized in that
Carboxylic (methyl) acrylate copolymer is the monomer that will contain (methyl) acrylate and carboxyl group-containing monomer Obtained from ingredient polymerization,
The carboxyl group-containing monomer is relative to the whole monomer components 100 for forming carboxylic (methyl) acrylate copolymer Parts by weight are 0.05~10 parts by weight.
3. the polarizing coating with adhesive phase as described in claim 1, which is characterized in that
Described adhesive composition contains phosphoric acid, and contains and be selected from
The R of general formula (1)1And R2In any one be hydrogen atom, another one is that may include that the hydrocarbon of the carbon atom number 1~18 of oxygen atom is residual The phosphate monoester of base and
The R of general formula (1)1And R2For may include oxygen atom carbon atom number 1~18 hydrocarbon residue di-phosphate ester
One or more of phosphate.
4. the polarizing coating with adhesive phase as claimed in claim 3, which is characterized in that
Described adhesive composition contains phosphoric acid and phosphate monoester.
5. the polarizing coating with adhesive phase as described in claim 1, which is characterized in that
The hydrocarbon residue of the carbon atom number 1~18 is the alkyl for the linear chain or branched chain that carbon atom number is 1~10.
6. the polarizing coating with adhesive phase as described in claim 1, which is characterized in that
Isocyanates system crosslinking agent is 0.01 relative to carboxylic 100 parts by weight of (methyl) acrylate copolymer ~10 parts by weight.
7. the polarizing coating with adhesive phase as described in claim 1, which is characterized in that
Also contain peroxide system crosslinking agent.
8. the polarizing coating with adhesive phase as described in claim 1, which is characterized in that
The transparency conducting layer is formed by tin indium oxide.
9. the polarizing coating with adhesive phase as claimed in claim 8, which is characterized in that
The tin indium oxide is noncrystalline tin indium oxide.
10. a kind of laminated body, which is characterized in that
Include successively：Polarizing coating as described in any one of claim 1 to 9 with adhesive phase and with the saturating of transparency conducting layer Bright conductive substrate,
The transparency conducting layer adhesive phase of the polarizing coating with adhesive phase is led with the transparent of the transparent conductive base Electric layer contacts.
11. laminated body as claimed in claim 10, which is characterized in that
The base material film is the iodine system for having transparent protective film in at least one side containing iodine and/or the iodine system polarizing film of iodide ion Polarizing coating.
12. a kind of image display device, which is characterized in that
Using the laminated body described in claim 10 or 11 as touch panel.
CN201480036263.6A 2013-06-28 2014-06-26 Adhesive composition, transparency conducting layer adhesive phase, laminated body and image display device Active CN105358648B (en)

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JP2014-000479 2014-01-06
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JP2014107237A JP6472172B2 (en) 2013-06-28 2014-05-23 Optical film pressure-sensitive adhesive composition, optical film pressure-sensitive adhesive layer, optical film with pressure-sensitive adhesive layer, liquid crystal display device, and laminate
JP2014-107237 2014-05-23
JP2014-130740 2014-06-25
JP2014130740A JP6363410B2 (en) 2013-06-28 2014-06-25 Adhesive composition, adhesive layer for transparent conductive layer, laminate, and image display device
PCT/JP2014/067062 WO2014208696A1 (en) 2013-06-28 2014-06-26 Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer for transparent conductive layer, laminate, and image display device

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