WO2014208696A1

WO2014208696A1 - Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer for transparent conductive layer, laminate, and image display device

Info

Publication number: WO2014208696A1
Application number: PCT/JP2014/067062
Authority: WO
Inventors: 伸介秋月; 雄祐外山; 淳保井; 高橋　俊貴; みずほ永田
Original assignee: 日東電工株式会社
Priority date: 2013-06-28
Filing date: 2014-06-26
Publication date: 2014-12-31
Also published as: TWI695048B; TW201510145A

Abstract

The purpose of the present invention is to provide a pressure-sensitive adhesive composition with excellent adhesiveness, which, even when laminated on a transparent conductive layer, suppresses corrosion of the transparent conductive layer, and which enables the formation of a pressure-sensitive adhesive layer capable of inhibiting increases in the surface resistance value of the transparent conductive layer. This pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer which is in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer is characterized by containing a carboxyl group-containing (meth)acrylic acid ester copolymer having a weight-average molecular weight of 1,200,000-3,000,000, an isocyanate cross-linking agent, and a compound represented by general formula (1) (in the formula, R1 and R2 are independently a hydrogen atom or a 1-18 carbon atom hydrocarbon residue optionally containing an oxygen atom), and the content of the compound represented by general formula (1) is 0.005-3 parts by weight per 100 parts by weight of the carboxyl group-containing (meth)acrylic acid ester copolymer.

Description

Adhesive composition, adhesive layer for transparent conductive layer, laminate, and image display device

The present invention relates to a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer, and a pressure-sensitive adhesive for a transparent conductive layer formed from the pressure-sensitive adhesive composition. The agent layer. Furthermore, this invention relates to the image display apparatus which uses a base film, the said adhesive layer for transparent conductive layers, and the laminated body which contains a transparent conductive layer in this order, and the said laminated body as a touch panel.

Recently, an input device using a touch panel in combination with a liquid crystal display device or an image display device used for a mobile phone, a portable music player or the like has become widespread. In the touch panel, a base material (for example, a transparent conductive film) in which a transparent conductive layer is formed on a transparent base material made of a glass plate or a transparent resin film is used. For example, in a capacitive touch panel, A laminate in which a double-sided PSA sheet is laminated on the surface of the transparent conductive layer of the substrate having the transparent conductive layer is formed, and is fixed to another substrate via the PSA layer of the laminate.

The transparent conductive layer is formed by evaporating a metal having high transparency and conductivity, such as indium tin oxide (ITO). The indium tin oxide (ITO) has good etching characteristics in the etching process at the time of patterning of the wiring, and moreover, amorphous (amorphous) indium tin oxide (ITO) is more advantageous, Often used.

In general pressure-sensitive adhesives, a carboxyl group-containing monomer or the like is used as a pressure-sensitive adhesive component in order to increase the cohesive strength of the pressure-sensitive adhesive component. However, when such a pressure-sensitive adhesive layer containing an acid component is in direct contact with the transparent conductive layer, the transparent conductive layer is corroded by acid, so that it has been difficult to use in this application.

For the purpose of solving such a problem of metal corrosion, various pressure-sensitive adhesive compositions having metal corrosion prevention properties have been proposed. Specifically, a pressure-sensitive adhesive composition in which a specific amount of a nitrogen atom-containing component is added to reduce the acid component content (for example, see Patent Document 1), and an acrylic resin having no acidic group as a main component. Proposed pressure-sensitive adhesive compositions (for example, see Patent Document 2), pressure-sensitive adhesives containing a (meth) acrylic polymer substantially free of acidic groups (for example, see Patent Document 3), and the like have been proposed.

Moreover, as an adhesive containing a phosphate ester compound, for example, an acrylic copolymer having a hydroxyl group and an alkylene oxide chain in the side chain, an ionic compound, a curing agent, and an antistatic acrylic adhesive containing a phosphate ester compound (For example, see Patent Document 4).

JP 2010-144002 A Special table 2011-225835 gazette JP 2013-018227 A Japanese Patent Laid-Open No. 2007-2111

The pressure-sensitive adhesive compositions of Patent Documents 1 to 3 have a certain effect on the metal corrosion inhibition effect because the content of the acid component such as a carboxyl group-containing resin is reduced or no acid component is used. Is. However, in the pressure-sensitive adhesive compositions of Patent Documents 1 to 3, since the content of the acid component is small, the cohesive strength of the resin is insufficient, and basic physical properties such as adhesive strength and holding power are insufficient. In particular, it cannot be said that it has sufficient performance as an adhesive for a transparent conductive layer.

Furthermore, the antistatic acrylic pressure-sensitive adhesive disclosed in Patent Document 4 is used as a pressure-sensitive adhesive for a surface protective pressure-sensitive adhesive film, and is not sufficient in terms of adhesive strength, adhesion reliability, etc. for a transparent conductive layer. There wasn't.

Therefore, the present invention is excellent in adhesiveness, and even when laminated on the transparent conductive layer, corrosion of the transparent conductive layer is suppressed, and an increase in the surface resistance value of the transparent conductive layer can be suppressed. It aims at providing the adhesive composition which can form an adhesive layer. Furthermore, the present invention provides a laminate comprising, in this order, a pressure-sensitive adhesive layer for a transparent conductive layer, a base film, the pressure-sensitive adhesive layer for a transparent conductive layer, and a transparent conductive layer formed from the pressure-sensitive adhesive composition, Another object of the present invention is to provide an image display apparatus using the touch panel as a touch panel.

As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by using the following pressure-sensitive adhesive composition, and have completed the present invention.

That is, the present invention is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer,
A carboxyl group-containing (meth) acrylic acid ester copolymer having a weight average molecular weight of 1,200,000 to 3,000,000, an isocyanate-based crosslinking agent, and the following general formula (1):

(Wherein R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom)
Containing a compound represented by
The pressure-sensitive adhesive characterized in that the content of the compound represented by the general formula (1) is 0.005 to 3 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer. The agent composition.

The carboxyl group-containing (meth) acrylic acid ester copolymer is obtained by polymerizing a monomer component containing a (meth) acrylic acid ester and a carboxyl group-containing monomer,
The carboxyl group-containing monomer is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of all monomer components forming the carboxyl group-containing (meth) acrylic acid ester copolymer.

The pressure-sensitive adhesive composition contains phosphoric acid, and one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. Phosphoric acid monoester which is a hydrocarbon residue of ˜18, and R ¹ and R ² of the general formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom It is preferable to contain one or more phosphate esters selected from the group consisting of phosphate diesters.

It is preferable that the pressure-sensitive adhesive composition contains phosphoric acid and phosphoric acid monoester. Moreover, it is preferable that the total amount of phosphoric acid and phosphoric acid monoester is 80 weight% or more with respect to the whole quantity (100 weight%) of the compound represented by the said General formula (1).

The hydrocarbon residue having 1 to 18 carbon atoms is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.

The isocyanate-based crosslinking agent is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer.

Furthermore, it is preferable to contain a peroxide-based crosslinking agent.

The transparent conductive layer is preferably formed from indium tin oxide.

The indium tin oxide is preferably amorphous indium tin oxide.

The present invention also relates to a pressure-sensitive adhesive layer for a transparent conductive layer, which is formed from the pressure-sensitive adhesive composition.

Moreover, this invention contains the transparent conductive base material which has a base film, the said adhesive layer for transparent conductive layers, and the transparent conductive layer in this order, and the said adhesive layer for transparent conductive layers is the said transparent conductive substrate. It is related with the laminated body characterized by contacting with the transparent conductive layer of this.

The base film is preferably an iodine polarizing film having a transparent protective film on at least one side of an iodine polarizer containing iodine and / or iodine ions. Here, “iodine-based polarizer containing iodine and / or iodine ions” means iodine-based polarizer containing iodine, iodine-based polarizer containing iodine ions, iodine containing both iodine and iodine ions It is a system polarizer, and any of them can be suitably used in the present invention.

Furthermore, this invention relates to the image display apparatus characterized by using the said laminated body as a touchscreen.

Since the pressure-sensitive adhesive composition of the present invention includes a carboxyl group-containing (meth) acrylic acid ester copolymer, the pressure-sensitive adhesive composition has a high cohesive force, and the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition has a high adhesive force. . Moreover, although the adhesive composition of this invention contains the carboxyl group-containing (meth) acrylic acid ester copolymer which is an acid component, the adhesive layer formed from the said adhesive composition is used as a transparent conductive layer. Also when laminated | stacked on top, corrosion of a transparent conductive layer can be suppressed and the surface resistance raise of a transparent conductive layer can be suppressed. This is because when the compound represented by the general formula (1) contained in the pressure-sensitive adhesive composition of the present invention is phosphoric acid, the phosphoric acid is passivated with the metal ions of the transparent conductive layer on the surface of the transparent conductive layer. When the film is formed or the compound represented by the general formula (1) is a phosphate ester, the phosphate ester is selectively adsorbed on the surface of the transparent conductive layer to form a film. Since H ⁺ is repelled and kept away, it is considered that corrosion of the transparent conductive layer is hindered and an increase in the surface resistance value can be suppressed. The isocyanate-based crosslinking agent contained in the pressure-sensitive adhesive composition of the present invention may gel due to the catalytic effect of the acid component, but in the pressure-sensitive adhesive composition of the present invention, a specific acidic phosphate ester is specified. Since the amount is included, the gelation can be controlled and the pot life is good.

It is sectional drawing which shows typically one Embodiment of the image display apparatus of this invention. It is sectional drawing which shows typically one Embodiment of the image display apparatus of this invention. It is sectional drawing which shows typically one Embodiment of the image display apparatus of this invention.

1. Pressure-sensitive adhesive composition The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer,
A carboxyl group-containing (meth) acrylic acid ester copolymer having a weight average molecular weight of 1,200,000 to 3,000,000, an isocyanate-based crosslinking agent, and the following general formula (1):

(Wherein R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom) And
The content of the compound represented by the general formula (1) is 0.005 to 3 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer.

In the present invention, phosphoric acid (H ₃ PO ₄ ) in which both R ¹ and R ^{2 in} the general formula (1) are hydrogen atoms can also be suitably used, and a salt of the phosphoric acid (Metal salts such as sodium, potassium, and magnesium, ammonium salts, and the like) can also be suitably used.

In addition, in the general formula (1), a phosphate ester in which at least ^one of R ¹ and R ² is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom is also preferably used. it can. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms,- (CH ₂ CH ₂ O) _n R ³ (R ³ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n is 0 to And an integer of 15.). The alkyl group and alkenyl group may be linear or branched. Among these, the hydrocarbon residue having 1 to 18 carbon atoms is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, and has 2 to 6 carbon atoms. A linear or branched alkyl group is more preferred.

In the present invention, examples of the compound represented by the general formula (1) include the following general formula (2):

(Wherein R ¹ is the same as defined above, R ³ is an alkyl group having 1 to 18 carbon atoms or an alkenyl group, and n is an integer of 0 to 15). Acid esters are preferred.

R ¹ in the general formula (2) is the same as R ¹ in the general formula (1), a hydrogen atom, or may contain an oxygen atom, a hydrocarbon residue having 1 to 18 carbon atoms. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include the same ones as described above. R ^{1 in the} general formula (2) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. A linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a linear or branched alkyl group having 2 to 6 carbon atoms is more preferable. Examples of R ³ include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms. An alkyl group having 1 to 18 carbon atoms and a carbon number An aryl group having 6 to 18 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 2 to 6 carbon atoms is more preferable. N is an integer of 0 to 15, and preferably an integer of 0 to 10. In the present invention, does not contain polyethylene oxide structure _{_(CH} 2 CH 2 O) _(i.e., in formula (2), n = 0) it is from the viewpoint of preventing deterioration.

As the acidic phosphate represented by the general formula (2), R ¹ is a hydrogen atom, and R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms from the viewpoint of the adsorption effect on the transparent conductive layer. The phosphoric acid monoester is preferably a phosphoric acid monoester in which R ¹ is a hydrogen atom and R ³ is a linear or branched alkyl group having 1 to 10 carbon atoms, and R ¹ is a hydrogen atom, More preferred are phosphoric acid monoesters in which R ³ is a linear or branched alkyl group having 2 to 6 carbon atoms.

In the present invention, two or more compounds represented by the general formula (2) may be used in combination, and the compound represented by the general formula (2) and phosphoric acid (general formula (1) And R ¹ = R ² = hydrogen atom) may be used. In general, the acidic phosphate represented by the general formula (2) is a monoester (R ¹ = hydrogen atom) and diester (R ¹ = hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom) ), And the phosphoric acid may be further added to the mixture of the monoester and the diester.

In the present invention, salts of the compound represented by the general formula (2) (metal salts such as sodium, potassium and magnesium, ammonium salts, etc.) can also be suitably used.

As a commercial product of the acidic phosphate ester represented by the general formula (2), “Phosphanol SM-172” (R ¹ = R ³ = C _{8 in the} general formula (2) manufactured by Toho Chemical Industry Co., Ltd.) H ₁₇ , n = 0, mono-di mixture, acid value: 219 mg KOH / g), “phosphanol GF-185” (R ¹ = R ³ = C ₁₃ H ₂₇ in general formula (2), n = 0, Mono-di mixture, acid value: 158 mg KOH / g), “Phosphanol BH-650” (R ¹ = R ³ = C ₄ H ₉ in general formula (2), n = 1, mono-di mixture, acid value : 388 mg KOH / g), “Phosphanol RS-410” (R ¹ = R ³ = C ₁₃ H ₂₇ in general formula (2), n = 4, mono-di mixture, acid value: 105 mg KOH / g), “ Phosphanol RS-610 "(R ^{1 in} general formula (2) = C ₁₃ H ₂₇ , R ³ = C ₁₃ H ₂₇ , n = 6, mono-di mixture, acid value: 82 mg KOH / g), “phosphanol ML-220” (R ¹ = R ^{3 in the} general formula (2) = C ₁₂ H ₂₅ , n = 2, mono-di mixture), “Phosphanol ML-200” (R ¹ = R ³ of general formula (2) = C ₁₂ H ₂₅ , n = 0, mono-di mixture ), “Phosphanol ED-200” (R ¹ = R ³ = C ₈ H ₁₇ , n = 1, mono-di mixture of general formula (2)), “Phosphanol RL-210” (general formula (2) 2) R ¹ = R ³ = C ₁₈ H ₃₇ , n = 2, mono-di mixture), “phosphanol GF-339 (R ¹ = R ³ = C ₆ H ₁₃ -C in formula (2) mixing ₁₀ H _21, n = 0, mono di mixture), "Phosphanol GF-199 ^{^{_{_{(R 1 = R 3 = C}}}} 12 H 25, n = 0 in formula (2), mono di ^{^{mixture), R 1 = R 3 =}} C of "Phosphanol RL-310" (the general formula (2) ₁₈ H ₃₇ , n = 3, mono-di mixture), “Nikkor DDP-2” manufactured by Nikko Chemicals Co., Ltd. (R ¹ = R ³ = C ₁₂ H ₂₅ to C ₁₅ H _{31 in} the general formula (2)) Mixture, n = 2), “Phosphanol LP-700” (R ¹ = R ³ = C ₆ H ₅ , n = 6, mono-di mixture of general formula (2)), Daihachi Chemical Industry Co., Ltd. "AP-1" in the manufacturing ^{^{_{(R 1 = R 3 = CH}}} 3, n = 0 in formula (2), mono di mixture acid value: 650mgKOH / g or higher), "AP-4" (formula ( ^{^{_{_{R 1 = R 3 = C 4}}}} H 9, n = 0, mono di mixture of 2), acid value: 452mgKOH / g), "DP-4" ( ^{^{_{_{R 1 = R 3 = C 4}}}} H 9, n = 0 in general formula (2), mono di mixture acid value: 292mgKOH / g), "MP-4" (Formula (2) ^R 1 = H , R ³ = C ₄ H ₉ , n = 0, mono-di mixture, acid value: 670 mg KOH / g), “AP-8” (R ¹ = R ³ = C ₈ H ₁₇ in general formula (2), n = 0, mono-di mixture, acid value: 306 mg KOH / g), “AP-10” (R ¹ = R ³ = C ₁₀ H ₂₁ in general formula (2), n = 0, mono-di mixture, acid value : 263 mgKOH / g), “MP-10” (R ¹ = H, R ³ = C ₁₀ H ₂₁ in formula (2), n = 0, mono-di mixture, acid value: 400 mgKOH / g), Johoku Chemical “JP-508” (R ¹ = R ³ = C ₈ H _{17 in} the general formula (2), n = 0, mono-di mixture, acid value: 28 8 mg KOH / g), “JP-513” (R ¹ = R ³ = C ₁₃ H ₂₇ in general formula (2), n = 0, mono-di mixture), “JP-524R” (in general formula (2) R ¹ = R ³ = C ₂₄ H ₄₉ , n = 0, mono-di mixture), “DBP” (R ¹ = R ³ = C ₄ H ₉ in general formula (2), n = 0, mono-di mixture , Acid value: 266 mg KOH / g), “LB-58” (R ¹ = R ³ = C ₈ H ₁₇ in general formula (2), n = 0, diester, acid value: 173 mg KOH / g), SIGMA-ALDRICH Mono-N-butyl phosphate (O = P (OH) ₂ (OC ₄ H ₉ ), R ¹ = H, R ³ = C ₄ H ₉ in general formula (2), n = 0, Product Number: CDS001281 , Monoesters) and their salts Kill. Incidentally, the "mono-di mixture" may include R ^{1 =} an oxygen atom (R ^{1 =} H in the general formula (2)) and diesters monoester (Formula (2), 1 carbon atoms For example, in the case of phosphanol SM-172, monoesters (R ¹ = H, R ³ = C ₈ H in the general formula (2)) are shown. ₁₇ , n = 0) and a diester (R ¹ = R ³ = C ₈ H _{17 in} the general formula (2), n = 0). The mixing ratio of the monoester and the diester of the “mono / di mixture” can be calculated from the measurement result of ³¹ P-NMR. The measuring method is as described in the examples.

The compound represented by the general formula (1) or the compound represented by the general formula (2) used in the present invention may be used alone or in combination of two or more. From the viewpoint of the adsorption effect on the transparent conductive layer, it is preferably a mixture of two or more selected from the group consisting of phosphoric acid, phosphoric acid monoester, and phosphoric acid diester, containing phosphoric acid, and phosphorous A mixture containing one or more phosphate esters selected from the group consisting of an acid monoester and a phosphate diester is more preferable, and a mixture containing a phosphate monoester and phosphoric acid is particularly preferable. In the present invention, one kind selected from the group consisting of phosphoric acid, phosphoric acid monoester, and phosphoric acid diester can be used alone, but when phosphoric acid is used alone, the pot life of the pressure-sensitive adhesive composition May be insufficient. Phosphoric acid is a very polar compound, and its compatibility with (meth) acrylic acid ester copolymer is not sufficient, so phosphoric acid bleeds out to the surface of the adhesive layer, resulting in durability. There may be a problem with this point. Moreover, when phosphoric acid is not used and only phosphoric acid ester (phosphoric acid monoester and / or phosphoric acid diester) is used, there is a problem in durability under extremely severe conditions (for example, heat cycle test). There is a case. In the present invention, it is most preferable to use a phosphoric acid-based compound containing phosphoric acid and phosphoric acid monoester from the viewpoint of the balance between the suppression of the corrosion of the transparent conductive layer and the durability under extremely severe conditions. The total amount of phosphoric acid and phosphoric acid monoester is not particularly limited, but is preferably 80% by weight or more based on the total amount (100% by weight) of the compound represented by the general formula (1). Here, the phosphoric acid monoester is a carbon atom having 1 to 18 carbon atoms in which ^one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom and the other may contain an oxygen atom. It is a compound that is a hydrogen residue (in the case of the general formula (2), a compound in which R ¹ is a hydrogen atom), and a phosphoric acid diester is a compound in which R ¹ and R ^{2 in} the general formula (1) are oxygen atoms A compound which is a hydrocarbon residue having 1 to 18 carbon atoms which may be contained (in the case of the general formula (2), R ¹ may contain an oxygen atom and a hydrocarbon residue having 1 to 18 carbon atoms may be contained. Compound which is a group).

The adsorption effect on the transparent conductive layer is considered that the transparent conductive layer and the phosphoric acid-based compound are defined by the HSAB rule, that is, it is related to the “law of hard and soft acid base”. Combining a soft acid with a soft base has a high adsorption effect, and as a result, it is considered that a high deterioration preventing effect can be obtained. That is, for example, In of ITO corresponds to a hard acid defined by the HSAB rule, and the phosphoric acid compound is changed from a hard base to a soft base in the order of phosphoric acid, phosphoric monoester, and phosphoric diester. It can be adsorbed to ITO effectively in order, and as a result, it is considered that a high deterioration preventing effect can be obtained.

Further, when a mixture of a monoester and a diester is used, a mixture containing a large amount of a monoester is preferable. The mixing ratio (weight ratio) of the mixture of the monoester and diester is preferably monoester: diester = 6: 4 to 9: 1, more preferably 7: 3 to 9: 1. preferable. For the above reason, it is preferable to include a large amount of monoester, since the adsorption effect on the transparent conductive layer is high.

Further, as described above, in the present invention, it is preferable to further add phosphoric acid to the phosphoric ester compound (particularly phosphoric monoester). In this case, the amount of phosphoric acid added is phosphoric ester compound 100. The amount is preferably 10 to 400 parts by weight, more preferably 10 to 100 parts by weight, and more preferably 10 to 50 parts by weight from the viewpoint of the adsorbing effect on the adherend. Further, from the viewpoint of durability under very severe conditions, the amount of phosphoric acid added is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the phosphoric ester compound. More preferably, it is a part.

The acid value of the phosphoric acid compound used in the present invention is preferably 900 mgKOH / g or less, more preferably 50 to 800 mgKOH / g, and preferably 50 to 700 mgKOH / g. Further, from the viewpoint of handling in production, the acid value of the acidic phosphate is preferably 80 to 400 mgKOH / g, more preferably 80 to 350 mgKOH / g, and 100 to 300 mgKOH / g. More preferred is 100 to 280 mgKOH / g. It is preferable that the acid value of the acidic phosphoric acid ester is within the above range, so that the increase in the surface resistance value of the transparent conductive layer can be suppressed and the durability against heating and humidification can be improved. . In addition, the acidic phosphate ester may act as a reaction catalyst for the crosslinking reaction of the isocyanate-based crosslinking agent contained in the pressure-sensitive adhesive composition of the present invention, which may shorten the pot life of the pressure-sensitive adhesive composition. It was. However, it is preferable from the viewpoint of the pot life of the pressure-sensitive adhesive composition, because the acid value of the acidic phosphate ester tends to be able to suppress the action as a reaction catalyst by setting the acid value in the above range. Moreover, it is preferable from the viewpoint that an acidic phosphate ester having an acid value in the above range is added in an addition amount to be described later so that the gelation suppressing effect can be efficiently exhibited.

In the present invention, a compound represented by the general formula (1), a dimer such as an acidic phosphate ester represented by the general formula (2), and a multimer such as a trimer can also be used. .

The amount of the compound represented by the general formula (1) is 0.005 to 3 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer described later, Is preferably 2.5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.01 to 2 parts by weight, and 0.02 to 0.4 parts by weight. It is particularly preferred. When the amount of the compound represented by the general formula (1) is within the above range, an increase in the surface resistance value of the transparent conductive layer can be suppressed, and durability against heating and humidification can be improved. Is preferable. In the present invention, two or more compounds represented by the general formula (1) can be used. In that case, the total amount can be added within the above range.

In this invention, even if a transparent conductive layer is laminated | stacked on the adhesive layer formed from the adhesive composition containing the compound represented by the said General formula (1), the surface resistance raise of a transparent conductive layer can be suppressed. Is. This is because when the compound represented by the general formula (1) contained in the pressure-sensitive adhesive composition of the present invention is phosphoric acid, the phosphoric acid is passivated with the metal ions of the transparent conductive layer on the surface of the transparent conductive layer. When the film is formed or the compound represented by the general formula (1) is a phosphate ester, the phosphate ester is selectively adsorbed on the surface of the transparent conductive layer to form a film. Since H ⁺ is repelled and kept away, it is considered that corrosion of the transparent conductive layer is hindered and an increase in the surface resistance value can be suppressed.

Regarding corrosion here, metal oxides are corroded by a mechanism different from general metal corrosion.

In the case of a metal oxide such as ITO, the corrosion reaction dissolves the metal oxide in the presence of a general acidic substance, and as a result, the resistance of the layer containing the metal oxide (metal oxide layer). This causes problems such as an increase in value. Further, in the case of a substance other than the acidic substance, the substance soaks into the metal oxide layer and decreases the carrier mobility of the metal oxide, so that the resistance value increases.

Due to the difference in the action mechanism between the metal corrosion and the metal oxide corrosion described above, there is a case where the corrosion inhibitory effect is not seen even when a general rust inhibitor is used for the metal oxide such as ITO.

Although the compound represented by the general formula (1) used in the present invention is an acidic substance, the influence of corrosion by the acidic substance is small, and a pressure-sensitive adhesive layer is formed by forming a film or the like on the surface of a metal or metal oxide. The rise in resistance due to acids and other substances that cause deterioration is suppressed.

The effect of inhibiting corrosion by the compound represented by the general formula (1) is particularly great when it is a metal oxide used for a transparent conductive layer, and even better when it is ITO.

The carboxyl group-containing (meth) acrylic acid ester copolymer used in the present invention is not particularly limited. For example, it is obtained by polymerizing a monomer component containing a (meth) acrylic acid ester and a carboxyl group-containing monomer. Preferably obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms as a main component and also containing a carboxyl group-containing alkyl (meth) acrylate. More preferably. Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.

As the alkyl group having 4 to 18 carbon atoms, various linear or branched ones can be used. Specific examples of the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms include, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl ( (Meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) Acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, n-to Decyl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, or dodecyl (meth) acrylate and the like. These can be used alone or in combination. Among these, (meth) acrylates having an alkyl group having 4 to 10 carbon atoms are more preferable, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable, and n-butyl (meth) acrylate is particularly preferable. preferable.

The alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is 50 parts by weight or more with respect to 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer. Preferably, it is 60 parts by weight or more, more preferably 70 parts by weight or more, still more preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more.

As the carboxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These may be used alone or in combination. Can be used.

The carboxyl group-containing monomer is preferably 0.05 to 10 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer. It is more preferable that Setting the carboxyl group-containing monomer within the above range is preferable because the cohesive force of the carboxyl group-containing (meth) acrylic acid ester copolymer can be improved and sufficient adhesive force and holding power can be obtained.

The monomer component for forming the carboxyl group-containing (meth) acrylic acid ester copolymer includes, in addition to the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms and the carboxyl group-containing alkyl (meth) acrylate. , Hydroxyl group-containing monomers, aryl group-containing monomers, and other copolymerization monomers can be added.

As the hydroxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( And (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and the like. Two or more kinds can be mixed and used. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is more preferable because a crosslinking point with an isocyanate group of the isocyanate-based crosslinking agent can be efficiently secured. preferable.

The hydroxyl group-containing monomer is preferably 10 parts by weight or less, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer. Is more preferable, and 0.1 to 3 parts by weight is even more preferable.

As the aryl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an aryl group can be used without particular limitation. Examples of the aryl group-containing monomer include (meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate.

The aryl group-containing monomer is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight based on 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer. Part is more preferable. *

The other copolymerization monomer is not particularly limited as long as it has a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. For example, propyl (meth) acrylate or the like Alkyl (meth) acrylates having an alkyl group having 3 or less carbon atoms or 19 or more carbon atoms; (meth) acrylic acid alicyclic hydrocarbons such as cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate Esters; for example, vinyl esters such as vinyl acetate and vinyl propionate; for example, styrenic monomers such as styrene; for example, epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; (Meth) acrylic acid methoxyethyl, (meth) acrylic acid et Alkoxy group-containing monomers such as silyl; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; functional monomers such as 2-methacryloyloxyethyl isocyanate; olefins such as ethylene, propylene, isoprene, butadiene and isobutylene For example, vinyl ether monomers such as vinyl ether; halogen atom-containing monomers such as vinyl chloride; and cyclic nitrogen-containing monomers such as N-vinyl pyrrolidone, N-vinyl-ε-caprolactam, methyl vinyl pyrrolidone, etc. Can be mentioned.

Examples of copolymerizable monomers include maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; for example, N-methylitaconimide, N-ethylitaconimide, N Itaconimide monomers such as butyl itaconimide, N-octyl itaconimide, N-2-ethylhexylitaconimide, N-cyclohexyl itaconimide, N-lauryl itaconimide; N- (meth) acryloyloxymethylene succinimide, N- Succinimide monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide; for example, styrene sulfonic acid Examples include sulfonic acid group-containing monomers such as allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalene sulfonic acid. It is done.

In addition, as the copolymerizable monomer, for example, glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate Other examples include, for example, tetrahydrofurfuryl (meth) acrylate, a heterocyclic ring such as fluorine (meth) acrylate, and an acrylate monomer containing a halogen atom.

Furthermore, a polyfunctional monomer can be used as the copolymerizable monomer. Examples of the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, etc. (mono or poly) In addition to (mono or poly) alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pen Esterified product of (meth) acrylic acid and polyhydric alcohol such as erythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; polyfunctional vinyl compound such as divinylbenzene; allyl (meth) acrylate, (meth) Examples thereof include compounds having a reactive unsaturated double bond such as vinyl acrylate. In addition, as a polyfunctional monomer, polyester (meta) having two or more unsaturated double bonds such as (meth) acryloyl group and vinyl group as functional groups similar to the monomer component is added to a skeleton such as polyester, epoxy, and urethane. ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like can also be used.

The proportion of the other copolymerization monomer is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, with respect to 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic ester copolymer. Part by weight or less is more preferable, and 15 parts by weight or less is particularly preferable. If the proportion of the copolymerization monomer is too large, adhesive properties such as reduced adhesion to various adherends such as glass and films of the adhesive layer formed from the adhesive composition of the present invention, and transparent conductive layers, etc. May decrease.

The weight average molecular weight of the carboxyl group-containing (meth) acrylic acid ester copolymer used in the present invention is 1,200,000 to 3,000,000, preferably 1,200,000 to 2,700,000, and more preferably 1,400,000 to 2,500,000. If the weight average molecular weight is less than 1,200,000, it is not preferable from the viewpoint of heat resistance. Moreover, when the weight average molecular weight is less than 1,200,000, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer, which may impair transparency. Moreover, the pressure-sensitive adhesive layer obtained using a (meth) carboxyl group-containing (meth) acrylic acid ester copolymer having a weight average molecular weight of less than 1,200,000 may have poor solvent resistance and mechanical properties. On the other hand, if the weight average molecular weight is larger than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable from the viewpoint of cost. Moreover, it is preferable from a viewpoint of corrosion resistance and durability because a weight average molecular weight exists in the said range. The weight average molecular weight is a value calculated by polystyrene conversion measured by GPC (gel permeation chromatography).

The production of such a carboxyl group-containing (meth) acrylic acid ester copolymer can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations, and is not particularly limited. Moreover, any of a random copolymer, a block copolymer, a graft copolymer, etc. may be sufficient as the carboxyl group-containing (meth) acrylic acid ester copolymer obtained.

In solution polymerization, for example, ethyl acetate or toluene is used as a polymerization solvent. As a specific example of solution polymerization, the reaction is carried out under an inert gas stream such as nitrogen and a polymerization initiator is added, usually at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.

The polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used. The weight average molecular weight of the carboxyl group-containing (meth) acrylic acid ester copolymer can be controlled by the amount of the polymerization initiator, the amount of chain transfer agent used, and the reaction conditions. Is adjusted.

Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2 -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, -Sec-butylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1 , 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t -Hexylperoxy) peroxide initiators such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides such as combinations of persulfate and sodium bisulfite, peroxides and sodium ascorbate And redox initiators combined with reducing agents. That, without being limited thereto.

The polymerization initiator may be used alone, or may be used in combination of two or more, but the total content is the carboxyl group-containing (meth) acrylic acid ester copolymer. The amount is preferably about 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer component to be formed.

Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to

In the pressure-sensitive adhesive composition of the present invention, various silane coupling agents can be added in order to improve adhesion under high-temperature and high-humidity conditions. As the silane coupling agent, one having any appropriate functional group can be used. Examples of the functional group include vinyl group, epoxy group, amino group, mercapto group, (meth) acryloxy group, acetoacetyl group, isocyanate group, styryl group, polysulfide group and the like. Specifically, for example, vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycol Epoxy group-containing silane coupling agents such as sidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N- (1,3-dimethylbutylidene) Propylamine, N-phenyl-γ Amino group-containing silane coupling agents such as aminopropyltrimethoxysilane; γ-mercaptopropylmethyldimethoxysilane and other mercapto group-containing silane coupling agents; p-styryltrimethoxysilane and other styryl group-containing silane coupling agents; (Meth) acrylic group-containing silane coupling agents such as acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane; bis (triethoxysilyl) And polysulfide group-containing silane coupling agents such as propyl) tetrasulfide.

The silane coupling agent may be used alone or in combination of two or more, but the total content is the same as the carboxyl group-containing (meth) acrylic acid ester copolymer. The amount is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.8 part by weight based on 100 parts by weight of the monomer component to be formed. 0.05 to 0.7 parts by weight is particularly preferable. When the amount of the silane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is generated, which is not preferable from the viewpoint of durability.

In addition, when the silane coupling agent can be copolymerized with the monomer component by radical polymerization, the silane coupling agent can be used as the monomer component. The ratio is preferably 0.005 to 0.7 parts by weight with respect to 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer.

The pressure-sensitive adhesive composition of the present invention can impart cohesive force related to the durability of the pressure-sensitive adhesive by including an isocyanate-based crosslinking agent.

The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by blocking agents or quantification) in one molecule.

Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexa Isocyanurate bodies of tylene diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals, Inc.), Trimethylolpropane adduct of hexamethylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals); polyether polyisocyanate, polyester polyisocyanate, and adducts of these with various polyols, isocyanurate bond, burette bond And polyisocyanate polyfunctionalized with an allophanate bond. Among these, it is preferable to use an aliphatic isocyanate because the reaction rate is high.

The blending ratio of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition of the present invention is not particularly limited. For example, 0.01 to 10 weights with respect to 100 weight parts of the carboxyl group-containing (meth) acrylic acid ester copolymer. Part is preferable, and 0.01 to 5 parts by weight is more preferable.

In the pressure-sensitive adhesive composition of the present invention, it is preferable to use a peroxide-based crosslinking agent together with the isocyanate-based crosslinking agent.

Various peroxides are used as the peroxide-based crosslinking agent. Examples of peroxides include di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, and t-butylperoxyneodecanoate. , T-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, and the like. Among these, di (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide, which are particularly excellent in crosslinking reaction efficiency, are preferably used.

Although the compounding ratio of the peroxide type crosslinking agent in the pressure-sensitive adhesive composition of the present invention is not particularly limited, for example, 10 parts by weight or less with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer. The amount is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight.

Further, as the cross-linking agent, other cross-linking agents such as the isocyanate cross-linking agents and peroxide cross-linking agents can be used.

Examples of the crosslinking agent include organic crosslinking agents and polyfunctional metal chelates other than those described above. Examples of organic crosslinking agents other than the above include epoxy crosslinking agents, carbodiimide crosslinking agents, imine crosslinking agents, oxazoline crosslinking agents, and aziridine crosslinking agents. A polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned. Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents can be used alone or in combination of two or more.

Furthermore, the pressure-sensitive adhesive composition of the present invention includes a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and other inorganic powders as necessary. Additives such as fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers and the like are used as appropriate without departing from the scope of the present invention. You can also

The pressure-sensitive adhesive composition of the present invention contains a carboxyl group-containing (meth) acrylic acid ester copolymer and an isocyanate-based crosslinking agent, and can form a pressure-sensitive adhesive layer by crosslinking the pressure-sensitive adhesive composition. it can. Since the compound represented by the general formula (1) contained in the pressure-sensitive adhesive composition of the present invention has a cross-linking promoting effect of a crosslinking agent such as an isocyanate-based crosslinking agent or a peroxide-based crosslinking agent, the pressure-sensitive adhesive of the present invention. The composition can increase the gel fraction of the pressure-sensitive adhesive layer from the initial production stage. As a result, a pressure-sensitive adhesive layer excellent in processability can be obtained.

In the pressure-sensitive adhesive composition of the present invention, in order to improve processability and productivity, the gel fraction of the pressure-sensitive adhesive layer after 2 hours after heat-crosslinking (155 ° C., 2 minutes) of the pressure-sensitive adhesive composition is 45 to It is preferably 95% by weight, more preferably 55 to 95% by weight, and still more preferably 60 to 85% by weight. When the gel fraction is less than 45% by weight, since the pressure-sensitive adhesive layer is too soft, processing in this state tends to cause problems such as sticking of the blade during processing. In addition, dents are generated in the step of winding the pressure-sensitive adhesive layer after crosslinking, resulting in problems in appearance, resulting in poor productivity. In addition, the measurement of the gel fraction of an adhesive layer can be performed by the method as described in an Example.

2. Pressure-sensitive adhesive layer for transparent conductive layer The pressure-sensitive adhesive layer for transparent conductive layer of the present invention is formed from the pressure-sensitive adhesive composition. As the pressure-sensitive adhesive composition, the above-mentioned pressure-sensitive adhesive composition of the present invention can be used. Moreover, the formation method of an adhesive layer is mentioned later.

3. Laminated body The laminated body of this invention contains the transparent conductive base material which has a base film, the said adhesive layer for transparent conductive layers, and a transparent conductive layer in this order, and the said adhesive layer for transparent conductive layers is the said transparent conductive layer. It contacts the transparent conductive layer of a conductive substrate.

As the pressure-sensitive adhesive layer for the transparent conductive layer, a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition of the present invention can be used.

The method for forming the pressure-sensitive adhesive layer is not particularly limited, but the pressure-sensitive adhesive composition is applied on various substrates, dried by a dryer such as a heat oven, and the pressure-sensitive adhesive layer is formed by evaporating the solvent and the like. A method of transferring the pressure-sensitive adhesive layer onto the base film may be used, or the pressure-sensitive adhesive composition may be directly applied onto the base film to form a pressure-sensitive adhesive layer.

The substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate.

Various methods are used as the coating method on the base film or base material. Specifically, for example, fountain coater, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, Daiko Examples of the method include an extrusion coating method using a catalyst.

The drying conditions (temperature, time) are not particularly limited and can be appropriately set depending on the composition, concentration, etc. of the pressure-sensitive adhesive composition, and are, for example, about 80 to 170 ° C., preferably 90 to 200 ° C. 1 to 60 minutes, preferably 2 to 30 minutes.

The thickness (after drying) of the pressure-sensitive adhesive layer is, for example, preferably 5 to 100 μm, more preferably 10 to 60 μm, and further preferably 12 to 40 μm. When the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the adhesion to the adherend becomes poor, and the durability under high temperature and high temperature and humidity tends to be insufficient. On the other hand, when the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, the pressure-sensitive adhesive composition is not sufficiently dried during the application and drying of the pressure-sensitive adhesive layer, and bubbles remain or the surface of the pressure-sensitive adhesive layer. There is a tendency that unevenness in thickness occurs and problems in appearance tend to become apparent.

Examples of the constituent material of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. An appropriate thin leaf body can be used, but a resin film is preferably used from the viewpoint of excellent surface smoothness.

Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene. -Vinyl acetate copolymer film.

The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. For the release film, if necessary, release agent and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.

The transparent resin film substrate is not particularly limited, and various resin films having transparency are used. The resin film is formed of a single layer film. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable. The thickness of the transparent resin film substrate is preferably 15 to 200 μm.

Further, an anchor layer may be provided between the base film and the pressure-sensitive adhesive layer. The material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, metal oxide sols, and silica sols. Further, the anchor agent forming the anchor layer can contain an antistatic agent. The thickness of the anchor layer is not particularly limited, but is preferably about 5 to 300 nm.

In addition, the anchor agent can be blended with various additives for the purpose of suppressing deterioration of the pressure-sensitive adhesive layer and the base film generated when coming into contact with the anchor coat layer, and imparting a function to the anchor coat layer. Various additives can be blended for the purpose. For example, antioxidants, deterioration inhibitors, ultraviolet absorbers, fluorescent brighteners, and the like can be added.

As the base film used in the laminate of the present invention, various films such as a resin film and an optical film used for forming an image display device such as a liquid crystal display device can be used, and the type is not particularly limited. Examples of the resin film include the resin films described in this specification. Examples of the optical film include a polarizing film. As the polarizing film, one having a transparent protective film on one side or both sides of a polarizer is generally used.

The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable, and an iodine polarizer containing iodine and / or iodine ions is more preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.

A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.

In the present invention, a thin polarizer having a thickness of 10 μm or less can also be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.

As the thin polarizer, typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, WO2010 / 100917, or a patent. The thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

As the thin polarizing film, International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing. In particular, those obtained by a production method including a step of stretching in a boric acid aqueous solution as described in International Publication No. 2010/100917 pamphlet, or Japanese Patent No. 47514881 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable. Those obtained by a production method including a step of stretching in the air before stretching in a boric acid aqueous solution described in the specification of 4751481 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.

As a material for forming the transparent protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include blends of the polymer. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.

The thickness of the protective film can be determined as appropriate, but is generally about 1 to 500 μm from the viewpoints of workability such as strength and handleability, and thin film properties.

The polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films. The adhesive used in the present invention can contain a metal compound filler.

The surface of the transparent protective film to which the polarizer is not bonded may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.

In the present invention, an iodine-based polarizing film having a transparent protective film on at least one surface of the iodine-based polarizer containing iodine and / or iodine ions can be used as the substrate film. When the iodine-based polarizing film and a transparent conductive layer such as ITO are laminated via an adhesive layer, a trace amount of iodine from the iodine-based polarizing film oozes into the adhesive layer, which is transparent such as ITO. There was also a problem of corroding the conductive layer. However, since the compound represented by the general formula (1) contained in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention forms a film on the surface of the transparent conductive layer as described above, it stains from the polarizer. It is also possible to prevent the released iodine from moving to the surface of the transparent conductive layer.

Examples of the optical film other than the polarizing film include liquid crystal display devices such as a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a viewing angle compensation film, and a brightness enhancement film. What becomes an optical layer which may be used for formation of etc. is mentioned. These can be used alone as an optical film, or can be laminated on the polarizing film in practical use to be used in one layer or in two or more layers.

Also, the optical film can be activated. Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.

The transparent conductive substrate having a transparent conductive layer is not particularly limited, and a known one can be used. Generally, a transparent conductive layer having a transparent conductive layer on a transparent substrate is used. ing.

The transparent substrate may be any material as long as it has transparency, and examples thereof include a resin film and a substrate made of glass (for example, a sheet-like, film-like, or plate-like substrate). A film is particularly preferred. The thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 μm, more preferably about 15 to 150 μm.

The material of the resin film is not particularly limited, and various plastic materials having transparency can be mentioned. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

In addition, the transparent base material is subjected to an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, or undercoating treatment on the surface in advance, and the transparent conductive layer provided thereon You may make it improve the adhesiveness with respect to a transparent base material. Moreover, before providing a transparent conductive layer, you may remove and clean by solvent washing | cleaning, ultrasonic washing | cleaning, etc. as needed.

The constituent material of the transparent conductive layer is not particularly limited and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten. A metal oxide of at least one metal is used. The metal oxide may further contain a metal atom shown in the above group, if necessary. For example, indium tin oxide (ITO), tin oxide containing antimony, and the like are preferably used, and ITO is particularly preferably used. Among ITO, amorphous indium tin oxide is preferable because the effect of the present invention is remarkably exhibited. ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

The thickness of the transparent conductive layer is not particularly limited, but is preferably 10 nm or more, more preferably 15 to 40 nm, and further preferably 20 to 30 nm.

The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness.

The thickness of the substrate having the transparent conductive layer can be 15 to 200 μm. Further, from the viewpoint of thinning, the thickness is preferably 15 to 150 μm, and more preferably 15 to 50 μm. When the substrate having the transparent conductive layer is used in a resistive film system, for example, a thickness of 100 to 200 μm can be mentioned. In addition, when used in the electrostatic capacity method, for example, a thickness of 15 to 100 μm is preferable, and in particular, a thickness of 15 to 50 μm is more preferable due to a recent demand for further thinning, and a thickness of 20 to 50 μm is more preferable. .

Moreover, an undercoat layer, an oligomer prevention layer, and the like can be provided between the transparent conductive layer and the transparent substrate as necessary.

4). As described above, the pressure-sensitive adhesive layer of the present invention can suppress corrosion of the transparent conductive layer even when the pressure-sensitive adhesive layer is laminated on the transparent conductive layer, and increase the surface resistance of the transparent conductive layer. It can be suppressed. Therefore, the pressure-sensitive adhesive layer of the present invention can be suitably used as long as it is an aspect in contact with the transparent conductive layer of the image display device having the transparent conductive layer.

For example, the laminate having the pressure-sensitive adhesive layer of the present invention includes an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, and the like provided with an input device (touch panel or the like). ), A base material (member) constituting a device such as an input device (touch panel, etc.) or a base material (member) used in these devices, but it is particularly suitable for an optical base material for a touch panel. It can use suitably in manufacture of this. Moreover, it can be used irrespective of systems, such as a touch panel, such as a resistive film system and a capacitive system.

Moreover, the laminated body of the present invention is subjected to treatments such as cutting, resist printing, etching, silver ink printing, and the like, and the resulting transparent conductive film can be used as a substrate for optical devices (optical member). . The substrate for an optical device is not particularly limited as long as it is a substrate having optical characteristics. For example, an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), Examples include base materials (members) constituting devices such as electronic paper) and input devices (touch panels, etc.) or base materials (members) used in these devices.

Specific examples of the image display device using the pressure-sensitive adhesive layer of the present invention include, for example, an image display device that uses a transparent conductive layer as an antistatic layer, and an image display device that uses a transparent conductive layer as an electrode for a touch panel. Can be mentioned. Specifically, as an image display device using the transparent conductive layer as an antistatic layer, for example, as shown in FIG. 1, a polarizing film 1 / adhesive layer 2 / antistatic layer 3 / glass substrate 4 / liquid crystal Examples thereof include an image display device comprising a layer 5 / driving electrode 6 / glass substrate 4 / adhesive layer 2 / polarizing film 1 wherein the antistatic layer 3 and the driving electrode 6 are formed of a transparent conductive layer. The pressure-sensitive adhesive layer of the present invention can be used as the pressure-sensitive adhesive layer 2 on the upper side (viewing side) of the image display device. Further, as an image display device using the transparent conductive layer as an electrode for a touch panel, for example, polarizing film 1 / adhesive layer 2 / antistatic layer / sensor layer 7 / glass substrate 4 / liquid crystal layer 5 / driving electrode / sensor Layer 8 / glass substrate 4 / adhesive layer 2 / polarizing film 1 configuration (in-cell type touch panel, FIG. 2), polarizing film 1 / adhesive layer 2 / antistatic layer / sensor layer 7 / sensor layer 9 / glass substrate 4 / liquid crystal layer 5 / drive electrode 6 / glass substrate 4 / adhesive layer 2 / polarizing film 1 (on-cell type touch panel, FIG. 3), antistatic layer / sensor layer 7, sensor layer 9, drive electrode An image display device 6 is formed of a transparent conductive layer. The polarizing film with an adhesive layer of the present invention can be used as the polarizing film with an adhesive layer (1, 2) on the upper side (viewing side) of the image display device.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In each example, both parts and% are based on weight.

Production Example 1 (Preparation of base film (1))
A stretched laminate was produced by air-assisted stretching at a stretching temperature of 130 ° C. from a laminate in which a 9 μm-thick polyvinyl alcohol (PVA) layer was formed on an amorphous polyethylene terephthalate (PET) substrate. Next, a colored laminate was produced by dyeing the stretched laminate. Furthermore, the colored laminate is stretched integrally with an amorphous PET base material in boric acid water at a temperature of 65 ° C. so that the total stretch ratio is 5.94 times, and an optical film laminate including a PVA layer having a thickness of 4 μm. Generated body. By such two-stage stretching, the PVA molecules in the PVA layer formed on the amorphous PET base material are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the higher order in one direction as a polyiodine ion complex. And a high-functional polarizer. Further, after applying a saponified 40 μm thick acrylic resin film (transparent protective film (1)) while applying a polyvinyl alcohol-based adhesive on the surface of the polarizer of the optical film laminate, amorphous PET The base material was peeled off to produce a one-side protective polarizing film using a thin polarizer. Hereinafter, this is called a base film (1).

Production Example 2 (Preparation of base film (2))
A PVA film having a thickness of 80 μm was stretched up to 3 times while being dyed in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the film was stretched so that the total draw ratio was 6 times while immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 20 μm. Furthermore, after applying a saponified 40 μm thick acrylic resin film (transparent protective film (1)) while applying a PVA adhesive on one surface of the polarizer, on the other surface of the polarizer, A norbornene-based film (transparent protective film (2)) having a thickness of 40 μm was bonded with a PVA adhesive to prepare a double-sided protective polarizing film. Hereinafter, this is called a base film (2).

Production Example 3 (Preparation of a solution containing an acrylate copolymer (A-1))
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 95 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 4 parts of acrylic acid, and 2,2′-azobis as an initiator 1 part of isobutyronitrile (AIBN) was added to 100 parts of monomer (solid content) together with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylate copolymer (A-1) having a weight average molecular weight of 2 million (solid content concentration: 30% by weight).

Production Examples 4 to 10 (Preparation of solutions containing acrylic acid ester copolymers (A-2) to (A-8))
A solution containing the acrylic ester copolymers (A-2) to (A-8) was obtained in the same manner as in Production Example 3 except that the monomer composition was changed to the composition shown in Table 1 (respectively). (Solution concentration: 30% by weight)

Production Example 11 (Preparation of a solution containing an acrylate copolymer (A-9))
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 84.9 parts of butyl acrylate, 0.1 part of 4-hydroxybutyl acrylate, 5 parts of acrylic acid, 10 parts of benzyl acrylate, and an initiator Then, 1 part of AIBN was added to 100 parts of monomer (solid content) together with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylate copolymer (A-9) having a weight average molecular weight of 2 million (solid content concentration 30% by weight).

Abbreviations in Table 1 are as follows.
BA: butyl acrylate BzA: benzyl acrylate AA: acrylic acid HEA: 2-hydroxyethyl acrylate HBA: 4-hydroxybutyl acrylate

Further, the weight average molecular weight of the acrylate copolymer obtained in Production Examples 3 to 11 was measured by the following measuring method.
<Measurement of weight average molecular weight (Mw) of acrylic ester copolymer>
The weight average molecular weight of the prepared acrylate copolymer was measured by GPC (gel permeation chromatography).
Equipment: Tosoh Corporation, HLC-8220GPC
column:
Sample column: manufactured by Tosoh Corporation, TSK guard column Super HZ-H (1) + TSK gel Super HZM-H (2)
Reference column: TSKgel Super H-RC (1), manufactured by Tosoh Corporation
Flow rate: 0.6mL / min
Injection volume: 10 μL
Column temperature: 40 ° C
Eluent: THF
Injection sample concentration: 0.2% by weight
Detector: differential refractometer The weight average molecular weight was calculated in terms of polystyrene.

Example 1
(Adjustment of acrylic adhesive composition)
With respect to 100 parts of the solid content of the solution (solid concentration 30% by weight) containing the acrylate copolymer (A-1) obtained in Production Example 3, as a crosslinking agent, hexamethylene diisocyanate with trimethylolpropane 0.1 part adduct (trade name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.), 0.3 part dibenzoyl peroxide, acid phosphate ester, phosphanol SM-172 (trade name, acid Value: 219 mg KOH / g, manufactured by Toho Chemical Industry Co., Ltd.) 0.07 parts, and γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent ) As a phenolic antioxidant and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate manufactured (IRGANAOX 1010, BASF Japan Ltd.) were blended 0.3 part, to obtain an acrylic pressure-sensitive adhesive composition.

(Preparation of base film with adhesive layer)
The acrylic pressure-sensitive adhesive composition is uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes. A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. Subsequently, the separator which formed the adhesive layer was transferred to the surface which does not have a protective film of a base film (1), and the base film with an adhesive layer was produced.

Examples 2-4
A base film with an adhesive layer was produced in the same manner as in Example 1 except that the addition amount of the acidic phosphate ester was changed from 0.07 parts to the number of parts shown in Table 3.

Example 5
Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.07 parts, Phosphanol RS-410 (trade name, acid value: 105 mg KOH / g, manufactured by Toho Chemical Industry Co., Ltd.) 0 A base film with an adhesive layer was produced in the same manner as in Example 1 except that the content was changed to 0.07 parts.

Example 6
Except for changing 0.07 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) to 0.05 part of phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.) In the same manner as in Example 1, a base film with an adhesive layer was produced.

Examples 7-11
The solutions containing the acrylic ester copolymer (A-1) obtained in Production Example 3 were used as the acrylic acid ester copolymers (A-2) to (A-) obtained in Production Examples 4 to 7, respectively. 5), and in Example 8, a base film with an adhesive layer was produced in the same manner as in Example 1 except that dibenzoyl peroxide was not added.

Examples 12-14
In Example 1 (Preparation of base film with pressure-sensitive adhesive layer), base film (1) was prepared by using base film (2) obtained in Production Example 2, base film (3) (thickness of 38 μm). Except for changing to polyethylene terephthalate (PET) film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.), base film (4) (100 μm thick polyethylene terephthalate (PET) film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.), In the same manner as in Example 1, a base film with an adhesive layer was produced.

Example 15
Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.3 parts was changed to MP-4 (acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.08 parts. Except having done, it carried out similarly to Example 1, and produced the base film with an adhesive layer.

Examples 16, 17
The solution containing the acrylate copolymer (A-1) obtained in Production Example 3 was changed to a solution containing the acrylate copolymer (A-9) obtained in Production Example 11, In addition, the same procedure as in Example 15 was conducted except that the addition amount of MP-4 (acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) was changed from 0.08 part to the addition amount shown in Table 3. Thus, a base film with an adhesive layer was produced.

Example 18
In Example 17 (Preparation of base film with pressure-sensitive adhesive layer), except that base film (1) was changed to base film (2) obtained in Production Example 2, it was the same as Example 17. Thus, a base film with an adhesive layer was produced.

Example 19
MP-4 (acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.05 parts, phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.08 parts and MP-4 (Acid value: 671 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.02 part (phosphoric acid: MP-4 = 4: 1 (weight ratio)) A base film with an adhesive layer was prepared.

Examples 20-22
In the same manner as in Example 1, except that the type of acrylic ester copolymer-containing solution, the type and addition amount of phosphoric acid and / or phosphate ester were changed to the types and addition amounts shown in Table 3, adhesion was performed. A base film with an agent layer was produced.

Comparative Example 1
A base film with an adhesive layer was produced in the same manner as in Example 1 except that the addition amount of the acidic phosphate ester was changed from 0.07 part to 5 parts.

Comparative Example 2
A base film with an adhesive layer was produced in the same manner as in Example 1 except that the addition amount of the acidic phosphate ester was changed from 0.07 part to 0.002 part.

Comparative Examples 3-5
The solutions containing the acrylate copolymer (A-1) obtained in Production Example 3 were used as the acrylate ester copolymers (A-6) to (A-) obtained in Production Examples 8 to 10, respectively. 8), and in Comparative Examples 3 and 5, a base film with an adhesive layer was produced in the same manner as in Example 1 except that the acidic phosphate was not added.

The phosphate ester used in Examples and Comparative Examples was analyzed as follows. The results are shown in Table 2.
(Analysis method)
The composition of the phosphate ester used in the examples and comparative examples was calculated based on the measurement results of ³¹ P-NMR (acetone-d6, room temperature). After calculating mol% from the integrated value of the peak obtained by measurement, the content ratio (% by weight) was calculated from the alkyl chain of the alcohol component of the ester.
⁽³¹ P-NMR measurement conditions)
Measuring apparatus: Bruker Biospin, AVANCE III-400
Observation frequency: 160 MHz ( ³¹ P)
Flip angle: 30 °
Measuring solvent: Acetone-d6 (heavy acetone)
Measurement temperature: room temperature chemical shift standard: P = (OCH ₃ ) ₃ in Acetone-d6 ( ³¹ P; 140 ppm external standard)

In Table 2, the phosphoric acid monoester has 1 to 18 carbon atoms in which ^one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. It is a compound that is a hydrocarbon residue (in the case of general formula (2), a compound in which R ¹ is a hydrogen atom), and a phosphoric acid diester is a compound in which R ¹ and R ^{2 in} general formula (1) are oxygen atoms A compound that is a hydrocarbon residue having 1 to 18 carbon atoms (in the case of the general formula (2), R ¹ may contain an oxygen atom and a hydrocarbon having 1 to 18 carbon atoms) Compound that is a residue). For example, in the case of phosphanol SM-172, “monoester” is a compound of the general formula (2) in which R ¹ = H, R ³ = C ₈ H ₁₇ , n = 0, and “diester” The compound in which R ¹ = R ³ = C ₈ H ₁₇ and n = 0 in (2) is shown.

<Gel fraction>
The acrylic pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were subjected to a crosslinking reaction at 155 ° C. for 2 minutes to obtain a pressure-sensitive adhesive layer. After 2 hours from completion of the crosslinking reaction, 0.2 g of the pressure-sensitive adhesive layer was taken. The film was wrapped in a fluororesin film (TEMISH NTF-1122, manufactured by Nitto Denko Corporation) (weight: Wa), the weight of which was measured in advance, and was bound so that the acrylic pressure-sensitive adhesive composition did not leak. This is a measurement sample. The measurement sample was weighed (weight: Wb) and placed in a sample bottle. 40 cc of ethyl acetate was added to the sample bottle and left for 7 days. Thereafter, a measurement sample (fluororesin film + acrylic pressure-sensitive adhesive composition) was taken out, and the measurement sample was dried on an aluminum cup at 130 ° C. for 2 hours. The weight (Wc) of the measurement sample was measured, and the gel fraction was determined by the following formula.

<Corrosion resistance test>
15 mm of conductive film (trade name: ELECRYSTA (P400L), manufactured by Nitto Denko Corporation, hereinafter sometimes referred to as “transparent conductive substrate (E-1)”) having an amorphous ITO layer formed on the surface After cutting to × 15 mm and bonding the base film with the adhesive layer obtained in Examples and Comparative Examples to 8 mm × 8 mm at the central part on this conductive film and bonding them together, 50 ° C., 5 atm The sample subjected to autoclaving for 15 minutes was used as a sample for measuring corrosion resistance. The resistance value of the obtained measurement sample was measured using a measuring device described later, and this was set as the “initial resistance value”.
Thereafter, the resistance value measured after putting the measurement sample in an environment of temperature 60 ° C. and humidity 90% for 500 hours was defined as “resistance value after wet heat”. In addition, said resistance value was measured using HL5500PC by Accent Optical Technologies. From the “initial resistance value” and “resistance value after wet heat” measured as described above, the resistance value change rate (%) was calculated by the following equation, and evaluated according to the following evaluation criteria.

(Evaluation criteria)
A: Resistance value change rate is less than 150% (small increase in resistance value due to wet heat (corrosion resistance is good))
○: Resistance value change rate is 150% or more and less than 300% Δ: Resistance value change rate is 300% or more and less than 400% ×: Resistance value change rate is 400% or more Corrosive failure))

Further, in the base film with the pressure-sensitive adhesive layer of Example 1, in addition to the transparent conductive substrate (E-1), a corrosion resistance test was conducted using the following transparent conductive substrate.
Transparent conductive substrate (E-2): a film on which a crystalline ITO layer is formed (trade name: V150-G5Y, manufactured by Nitto Denko Corporation)
Transparent conductive substrate (E-3): Glass on which an amorphous ITO layer is formed Transparent conductive substrate (E-4): Glass on which a crystalline ITO layer is formed

In addition, the manufacturing method of a transparent conductive base material (E-3) and a transparent conductive base material (E-4) is as follows.

(Preparation of transparent conductive substrate (E-3) and transparent conductive substrate (E-4))
An ITO film is formed on one surface of the alkali-free glass by a sputtering method, a transparent conductive substrate (E-4) having a crystallized ITO thin film, and a transparent conductive substrate (E-4) having a non-crystallized ITO film (E -3) was produced. Each substrate was heat-treated at 140 ° C. for 30 minutes before being bonded to the adhesive layer-attached substrate film obtained in Examples and Comparative Examples. The Sn ratio of the crystalline ITO thin film was 10% by weight. The Sn ratio of the amorphous ITO thin film was 3% by weight. The method for calculating the Sn ratio of the ITO thin film is as described above.

<Durability test of adhesive (peeling and foaming)>

The separator of the base film with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, and bonded to the ITO surface of the glass (transparent conductive base material (E-4)) on which crystalline ITO was formed, and 50 ° C. After performing an autoclave treatment at 5 atm for 15 minutes, it was put into a heating oven at 80 ° C. and 100 ° C. and a constant temperature and humidity chamber at 60 ° C./90% RH and 85 ° C./85% RH. The peeling and foaming of the base film after 500 hours were visually observed and evaluated according to the following evaluation criteria. Further, after 300 cycles of 85 ° C. and −40 ° C. for 1 hour per cycle (heat shock test (HS test)), peeling and foaming of the polarizing film were visually observed and evaluated according to the following evaluation criteria. .
A: No peeling or foaming was observed.
○: Exfoliation or foaming to the extent that it cannot be visually confirmed was observed.
(Triangle | delta): The small peeling or foaming which can be confirmed visually was recognized.
X: Clear peeling or foaming was recognized.

Abbreviations in Table 3 are as follows.
(Acid phosphate ester)
B-1: Phosphanol SM-172, acid value: 219 mg KOH / g, mono-di mixture, manufactured by Toho Chemical Industry Co., Ltd. B-2: Phosphanol RS-410, acid value: 105 mg KOH / g, mono- Dimix, B-3 manufactured by Toho Chemical Industry Co., Ltd .: Phosphoric acid (special grade reagent), B-4: MP-4 manufactured by Wako Pure Chemical Industries, Ltd., acid value: 670 mgKOH / g, mono / di mixture, large B-5 manufactured by Hachi Chemical Industry Co., Ltd .: Mono-N-butyl phosphate (O = P (OH) ₂ (OC ₄ H ₉ ), Product Nomber: CDS001281), manufactured by SIGMA-ALDRICH

(Crosslinking agent)
Peroxide type: dibenzoyl peroxide isocyanate type: trimethylolpropane xylylene diisocyanate (trade name: Takenate D110N) (manufactured by Mitsui Chemicals, Inc.)

(Transparent conductive substrate)
E-1: Transparent conductive substrate (E-1)
E-2: Transparent conductive substrate (E-2)
E-3: Transparent conductive substrate (E-3)
E-4: Transparent conductive substrate (E-4)

DESCRIPTION OF SYMBOLS 1 Polarizing film 2 Adhesive layer 3 Antistatic layer 4 Glass substrate 5 Liquid crystal layer 6 Drive electrode 7 Antistatic layer and sensor layer 8 Drive electrode and sensor layer 9 Sensor layer

Claims

A pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer,
A carboxyl group-containing (meth) acrylic acid ester copolymer having a weight average molecular weight of 1,200,000 to 3,000,000, an isocyanate-based crosslinking agent, and the following general formula (1):

(Wherein R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom)
Containing a compound represented by
The pressure-sensitive adhesive characterized in that the content of the compound represented by the general formula (1) is 0.005 to 3 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer. Agent composition.
The carboxyl group-containing (meth) acrylic acid ester copolymer is obtained by polymerizing a monomer component containing a (meth) acrylic acid ester and a carboxyl group-containing monomer, and the carboxyl group-containing monomer is the carboxyl The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is 0.05 to 10 parts by weight with respect to 100 parts by weight of all monomer components forming the group-containing (meth) acrylic acid ester copolymer.
The pressure-sensitive adhesive composition contains phosphoric acid, and any one of R 1 and R 2 in the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. Phosphoric acid monoester which is a hydrocarbon residue having 1 to 18 and R 1 and R 2 in the general formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom. The pressure-sensitive adhesive composition according to claim 1, comprising one or more phosphate esters selected from the group consisting of a certain phosphate diester.
The pressure-sensitive adhesive composition according to claim 3, wherein the pressure-sensitive adhesive composition contains phosphoric acid and a phosphoric acid monoester.
5. The pressure-sensitive adhesive composition according to claim 1, wherein the hydrocarbon residue having 1 to 18 carbon atoms is a linear or branched alkyl group having 1 to 10 carbon atoms.
6. The isocyanate cross-linking agent is 0.01 to 10 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer. The pressure-sensitive adhesive composition described.
The pressure-sensitive adhesive composition according to any one of claims 1 to 6, further comprising a peroxide-based crosslinking agent.
The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the transparent conductive layer is formed of indium tin oxide.
The pressure-sensitive adhesive composition according to claim 8, wherein the indium tin oxide is amorphous indium tin oxide.
A pressure-sensitive adhesive layer for a transparent conductive layer, which is formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 9.
A transparent conductive substrate having a substrate film, a transparent conductive layer pressure-sensitive adhesive layer according to claim 10 and a transparent conductive layer in this order, wherein the transparent conductive layer pressure-sensitive adhesive layer is the transparent conductive substrate. A laminated body in contact with a transparent conductive layer.
The laminate according to claim 11, wherein the substrate film is an iodine-based polarizing film having a transparent protective film on at least one surface of an iodine-based polarizer containing iodine and / or iodine ions.
An image display device using the laminate according to claim 11 as a touch panel.