WO2017110937A1

WO2017110937A1 - Adhesive sheet for conductive member, conductive member laminate, and image display device

Info

Publication number: WO2017110937A1
Application number: PCT/JP2016/088229
Authority: WO
Inventors: 亮太山本; かほる新美; 秀次郎吉川; 誠稲永; 内田　貴久
Original assignee: 三菱樹脂株式会社
Priority date: 2015-12-25
Filing date: 2016-12-21
Publication date: 2017-06-29
Also published as: TWI752000B; KR102598110B1; JP6969092B2; TW201736540A; CN108431158A; JP7143918B2; JP2017119857A; KR20180098359A; CN108431158B; JP2021127461A

Abstract

Provided are: an adhesive sheet for conductive members, which will not corrode a conductive member such as, for example, a transparent conductive layer, and which has forming resistance reliability and fine curing properties; a conductive member laminate; and an image display device. Particularly , the present invention provides an adhesive sheet for conductive members, which is preferable for bonding a conductive member such as a transparent conductive layer in an image display device using an image display panel such as a plasma display (PDP), a liquid crystal display (LCD), an organic EL display (OLED), or the like. The adhesive sheet for conductive members has an adhesive agent layer comprising an adhesive agent composition containing a (meth)acryl-based copolymer and 1,2,3-triazole.

Description

Adhesive sheet for conductive member, conductive member laminate, and image display device

The present invention relates to a pressure-sensitive adhesive sheet for a conductive member and a conductive member laminate using the pressure-sensitive adhesive sheet. In particular, in an image display device using an image display panel such as a plasma display (PDP), a liquid crystal display (LCD), an organic EL display (OLED), an inorganic EL display, an electrophoretic display (EPD), an interference modulation display (IMOD), etc. The present invention relates to a pressure-sensitive adhesive sheet for a conductive member suitable for bonding conductive members such as a transparent conductive layer.

Image display devices such as personal computers, mobile terminals (PDAs), game machines, televisions (TVs), car navigation systems, touch panels, pen tablets, for example, plasma displays (PDPs), liquid crystal displays (LCDs), organic EL displays (OLEDs) ), In an image display device using a flat or curved image display panel such as an inorganic EL display, an electrophoretic display (EPD), an interferometric modulation display (IMOD), etc. A gap is not provided between the constituent members, and the constituent materials are bonded and integrated with an adhesive sheet or a liquid adhesive.

For example, in an image display device having a configuration in which a touch panel is interposed between the viewing side of the liquid crystal module and the surface protection panel, an adhesive sheet or liquid adhesive is provided between the surface protection panel and the viewing side of the liquid crystal module. The touch panel and other constituent members, for example, the touch panel and the liquid crystal module, and the touch panel and the surface protection panel are bonded and integrated.

Touch panels are usually made of metal oxides such as tin-doped indium oxide (ITO), indium-gallium-zinc composite oxide (IGZO), and Ga-doped zinc oxide (GZO), and metal materials such as silver, copper, and molybdenum. And an upper electrode plate and a lower electrode plate having a transparent conductive layer formed of fine wiring, silver nanowires, carbon nanotubes, or the like. In addition, in order to collect and communicate positional information such as a finger and a touch pen detected by the transparent conductive layer, a conductor pattern (wiring pattern) formed of a metal material is interposed between the transparent conductive layer and a control means such as an IC. It is formed. The transparent conductive layer and conductor pattern formed from these various materials are usually fixed so that the surface is in contact with the adhesive. The transparent conductive layer and the conductive pattern are vulnerable to corrosion, and may corrode due to the outgas of the adhesive material or the acid component derived from the elution component in a high temperature or wet heat environment, possibly resulting in disconnection.

Thus, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet for metal sticking containing benzotriazole and / or a derivative thereof as a metal corrosion inhibitor.

Further, for example, Patent Document 2 discloses a pressure-sensitive adhesive composition comprising an acrylic polymer and a crosslinking agent, each of which includes an alkoxyalkyl acrylate and an acrylic monomer having a crosslinkable functional group as essential components. Discloses a pressure-sensitive adhesive composition substantially free of a carboxyl group-containing monomer. According to this pressure-sensitive adhesive composition, yellowing is suppressed by using a specific amount of an aliphatic isocyanate crosslinking agent and an amine compound containing a plurality of hydroxyl groups, and the acrylic polymer has a crosslinked structure. Accordingly, it is disclosed that even when a carboxyl group-containing monomer component is not included, the anti-foaming / peeling property under high temperature can be satisfied.

JP 2006-45315 A JP 2009-079203 A1

The constituent members used in the image display device include members that generate gas (also referred to as “outgas”) over time in a high-temperature or high-humidity environment. In the case of bonding with a sheet, the pressure-sensitive adhesive sheet also needs to have foaming reliability that can sufficiently resist the gas pressure of outgas.

The double-sided pressure-sensitive adhesive sheet containing the metal corrosion inhibitor of Patent Document 1 has a problem that the metal corrosion inhibitor is foamed in a durability test that is irradiated with ultraviolet rays, and optical properties are deteriorated.

According to the pressure-sensitive adhesive composition of Patent Document 2, it is said that even an acrylic polymer that does not contain a carboxyl group-containing monomer such as acrylic acid can satisfy the resistance to foaming and peeling at high temperatures. However, since it is impossible to prevent moisture from entering the pressure-sensitive adhesive, which is a cause of corrosion, it is not always satisfactory from the viewpoint of metal corrosion prevention.

Therefore, the problem to be solved by the present invention is to provide a pressure-sensitive adhesive sheet for a conductive member that does not corrode the conductive member and has foaming reliability and good curing characteristics. More specifically, even if directly bonded to the conductive layer surface of the transparent conductive layer or a conductor pattern (wiring pattern) formed of a metal material, these are not corroded and insulated from the conductive layer surface of the transparent conductive layer. It is to provide a pressure-sensitive adhesive sheet for a conductive member that does not corrode a transparent conductive layer even when bonded through a protective film (passivation film).

The main feature of the present invention is that it has a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer and 1,2,3-triazole.

The pressure-sensitive adhesive sheet for a conductive member of the present invention has corrosion resistance reliability with respect to a conductive member and can also have foaming reliability reliability and good curing characteristics as a pressure-sensitive adhesive sheet. Therefore, the pressure-sensitive adhesive sheet for a conductive member of the present invention is a pressure-sensitive adhesive sheet suitable for bonding various conductive members such as a conductive member having a conductive pattern formed of a transparent conductive layer and / or a metal material containing copper or silver. Can be used. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.

BRIEF DESCRIPTION OF THE DRAWINGS In the Example mentioned later, it is a figure for demonstrating the evaluation test method of corrosion resistance reliability, (A) is the top view of the ITO pattern of the ITO glass substrate for oxidation deterioration prevention evaluation, or copper for corrosion resistance reliability evaluation The top view of the copper pattern of a glass substrate, (B) is a top view showing a state where an adhesive sheet is coated on an ITO glass substrate for evaluating oxidation resistance, or an adhesive sheet on a copper glass substrate for evaluating corrosion resistance The top view which showed the coat | covered state, (C) is sectional drawing of the sample for oxidation deterioration prevention evaluation, (D) is sectional drawing of the sample for corrosion resistance reliability evaluation.

Hereinafter, an example of an embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiment.

<Pressure sensitive adhesive sheet>
An adhesive sheet for a conductive member according to an example of an embodiment of the present invention (hereinafter also referred to as “the present adhesive sheet”) includes a (meth) acrylic (co) polymer and 1,2,3-triazole. It has the adhesive layer which consists of an adhesive composition to contain.

The pressure-sensitive adhesive layer may be a single layer or a multilayer, and in the case of a multilayer, other layers such as a so-called base material layer may be interposed. When the pressure-sensitive adhesive layer has a multilayer structure having other layers, the surface layer of the pressure-sensitive adhesive sheet is preferably a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition.
When the pressure-sensitive adhesive sheet is a multilayer, the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is not limited, but is preferably 10% or more, more preferably 30% or more with respect to the total thickness of the pressure-sensitive adhesive sheet. More preferably, it is 50% or more. If the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is in the above range, it is preferable because corrosion resistance, foaming reliability, and curing characteristics with respect to the conductive member are improved.
In the present invention, “(co) polymer” includes a homopolymer and a copolymer, and “(meth) acrylate” includes an acrylate and a methacrylate.

[Adhesive composition]
The pressure-sensitive adhesive composition used for the pressure-sensitive adhesive sheet (hereinafter abbreviated as “the present composition”) contains a (meth) acrylic (co) polymer and 1,2,3-triazole.
The present composition may further contain a phosphite compound, a crosslinking agent, a photopolymerization initiator, an antioxidant, and other components.
The composition is preferably a photocurable composition.

((Meth) acrylic (co) polymer)
Examples of (meth) acrylic (co) polymers include, for example, copolymers obtained by polymerizing alkyl (meth) acrylate homopolymers and copolymerizable monomer components. More preferably, among alkyl (meth) acrylates and carboxyl group-containing monomers, hydroxyl group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, amide group-containing monomers, and other vinyl monomers copolymerizable therewith. Examples thereof include a copolymer containing any one or more selected monomers as a structural unit.
The (meth) acrylic (co) polymer can be produced by a conventional method using the following monomers or the like, if necessary, using a polymerization initiator.

When the (meth) acrylic (co) polymer is a copolymer containing a carboxyl group-containing monomer as a constituent unit, the (meth) acrylic (co) polymer contains a carboxyl group from the viewpoint of obtaining excellent adhesive properties. The monomer content is preferably 1.2 to 15% by mass, more preferably 1.5% by mass or more and 10% by mass or less, and most preferably 2.0% by mass or more or 8% by mass or less.

As an example of a more specific (meth) acrylic (co) polymer, a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain (hereinafter also referred to as “copolymerizable monomer A”). And a copolymer composed of any one or more monomer components selected from the following group copolymerizable therewith.

Carboxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer B”)
Macromonomer (hereinafter also referred to as “copolymerizable monomer C”)
(Meth) acrylate having 1 to 3 carbon atoms in the side chain (hereinafter also referred to as “copolymerizable monomer D”)
Hydroxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer E”)
Other vinyl monomers (hereinafter also referred to as “copolymerizable monomer F”)

Further, as an example of a (meth) acrylic (co) polymer, (a) a copolymer composed of a monomer component containing a copolymerizable monomer A and a copolymerizable monomer B and / or copolymerizable monomer C And a monomer component including (b) a copolymerizable monomer A, a copolymerizable monomer B and / or a copolymerizable monomer C, and a copolymerizable monomer D and / or a copolymerizable monomer E. A copolymer can also be mentioned as a particularly preferred example.

Examples of the straight chain or branched alkyl (meth) acrylate (copolymerizable monomer A) having 4 to 18 carbon atoms in the side chain include, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) Acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, 3,5,5-trimethylcyclohexane (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( A meth) acrylate, a benzyl (meth) acrylate, etc. can be mentioned. These may be used alone or in combination of two or more.

The copolymerizable monomer A is preferably contained in the total monomer components of the copolymer in an amount of 30% by mass or more and 90% by mass or less, particularly 35% by mass or more and 88% by mass or less, and especially 40% by mass. More preferably, it is contained in the range of 85% by mass or less.

Examples of the carboxyl group-containing monomer (copolymerizable monomer B) include (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2 -(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxy Mention may be made of ethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid and itaconic acid. These may be used alone or in combination of two or more. “(Meth) acryl” means to include acrylic and methacrylic. Similarly, “(meth) acryloyl” means acryloyl and methacryloyl.

The copolymerizable monomer B is 1.2% by mass or more and 15% by mass or less in all monomer components of the copolymer, and from the viewpoint of obtaining excellent adhesive physical properties, 1.5% by mass or more or 10% by mass or less, In particular, it is preferably contained in the range of 2% by mass or more or 8% by mass or less.

The macromonomer (copolymerizable monomer C) is a monomer having 20 or more carbon atoms in the side chain when it becomes a (meth) acrylic (co) polymer by polymerization. By using the copolymerizable monomer C, a (meth) acrylic (co) polymer can be used as a graft copolymer. Therefore, the characteristics of the main chain and side chain of the graft copolymer can be changed depending on the selection and blending ratio of the copolymerizable monomer C and other monomers.

As the macromonomer (copolymerizable monomer C), the skeleton component is preferably composed of an acrylic polymer or a vinyl polymer. Examples of the skeleton component of the macromonomer include those exemplified by the copolymerizable monomer A, the copolymerizable monomer B, the copolymerizable monomer D described below, and the copolymerizable monomer E described below. Can be used alone or in combination of two or more.

The macromonomer has a radical polymerizable group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, or a thiol group. As the macromonomer, those having a radical polymerizable group copolymerizable with other monomers are preferable. One or two or more radically polymerizable groups may be contained, and one of them is particularly preferred. When the macromonomer has a functional group, one or two or more functional groups may be contained, and one of them is particularly preferable. Further, either one of the radical polymerizable group and the functional group may be contained.

The number average molecular weight of the copolymerizable monomer C is preferably 500 to 20,000, more preferably 800 or more and 8000 or less, and particularly preferably 1000 or more and 7000 or less.
As the macromonomer, a generally produced one (for example, a macromonomer manufactured by Toa Gosei Co., Ltd.) can be appropriately used.
The copolymerizable monomer C is 5% by mass or more and 30% by mass or less, more preferably 6% by mass or more and 25% by mass or less, and particularly preferably 8% by mass or more or 20% by mass or less in the total monomer components of the copolymer. It is preferable to contain in the range.

Examples of the (meth) acrylate (copolymerizable monomer D) having 1 to 3 carbon atoms in the side chain include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) ) Acrylate and the like. These may be used alone or in combination of two or more.

The copolymerizable monomer D is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass to 70% by mass, more preferably 3% by mass or 65% by mass, and particularly preferably 5% by mass or more. Or it is further more preferable to contain in the range of 60 mass% or less.

Examples of the hydroxyl group-containing monomer (copolymerizable monomer E) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc. And hydroxyalkyl (meth) acrylates. These may be used alone or in combination of two or more.

The copolymerizable monomer E is preferably contained in an amount of 0% by mass or more and 30% by mass or less in all monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and more preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.

Examples of the other vinyl monomer (copolymerizable monomer F) include compounds having a vinyl group in the molecule, excluding the copolymerizable monomers A to E. Such compounds include functional monomers having functional groups such as amide groups and alkoxylalkyl groups in the molecule, and polyalkylene glycol di (meth) acrylates, and vinyls such as vinyl acetate, vinyl propionate and vinyl laurate. Examples include ester monomers and aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene and other substituted styrenes. These may be used alone or in combination of two or more.

The copolymerizable monomer F is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass to 30% by mass, more preferably 0% by mass or more or 25% by mass or less, and particularly preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.

In addition to those listed above, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, etc. Epoxy group-containing monomers; amino group-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, Nt-butyl (meth) acrylamide, N- Monomers containing amide groups or imide groups such as methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic acid amide, maleimide; vinyl pyrrolidone , Vinyl Jin, can be appropriately used depending or the like need heterocyclic basic monomers such as vinyl carbazole.

The most typical examples of (meth) acrylic (co) polymers include, for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isostearyl (meth) acrylate, butyl ( Monomer component (a) such as (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate and the like, (meth) acrylic acid having a carboxyl group, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( (Meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxy Propyl maleic acid, 2- (meth) Monomer component (b) such as acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, and hydroxyethyl (meth) acrylate having an organic functional group , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, monomethyl maleate, monomethyl itaconate, vinyl acetate, glycidyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, fluorination Mention may be made of (meth) acrylic acid ester copolymers obtained by copolymerizing monomer components (c) such as (meth) acrylates and silicone (meth) acrylates.

The mass average molecular weight of the (meth) acrylic (co) polymer is preferably 100,000 or more and 1.5 million or less, more preferably 150,000 or more and 1.3 million or less, and particularly preferably 200,000 or more or 1,200,000 or less.

In order to obtain a pressure-sensitive adhesive composition having a high cohesive force, the mass average molecular weight of the (meth) acrylic (co) polymer is 700,000 to 1,500,000 from the viewpoint of obtaining cohesive force due to entanglement of molecular chains as the molecular weight increases. In particular, it is particularly preferably 800,000 or more or 1.3 million or less. On the other hand, when it is desired to obtain an adhesive composition having high fluidity and stress relaxation properties, the mass average molecular weight is preferably 100,000 or more and 700,000 or less, particularly 150,000 or more or 600,000 or less.
On the other hand, when a solvent is not used when forming an adhesive sheet or the like, it is difficult to use a polymer having a large molecular weight, and therefore the (meth) acrylic (co) polymer has a mass average molecular weight of 100,000 or more and 700,000. In particular, 150,000 or more or 600,000 or less is preferable, and 200,000 or more or 500,000 or less is particularly preferable.

(Metal corrosion inhibitor)
The composition contains 1,2,3-triazole.
1,2,3-triazole has a function as a metal corrosion inhibitor for the conductive layer of the conductive member. Since 1,2,3-triazole is excellent in copper corrosion resistance against copper and foaming reliability as a pressure-sensitive adhesive sheet, the present composition containing 1,2,3-triazole contains a transparent conductive layer and copper. It can be suitably used as a conductive member having a conductor pattern (wiring pattern) formed of a metal material containing. The reason is to prevent corrosion by forming a protective film in which copper atoms and 1,2,3-triazole molecules are chemically bonded to the surface of the conductor pattern made of a metal material containing copper. It is because it is guessed. In addition, the effect of the protective film by 1,2,3-triazole can be similarly achieved in a conductive member having a conductor pattern formed of a metal material containing silver.

In addition, 1,2,4-triazole exists as an isomer of 1,2,3-triazole. The 1,2,4-triazole is a solid having a melting point of about 120 ° C., whereas 1,2,3-triazole has a melting point of about 20 ° C. and is almost in a liquid state at room temperature. Therefore, 1,2,3-triazole has excellent advantages such as excellent dispersibility when mixed into the pressure-sensitive adhesive composition, uniform mixing, and easy masterbatch formation.

In this composition, from the viewpoint of bleeding out of the metal corrosion inhibitor and the effect of preventing metal corrosion, 1,2,3-triazole is added in an amount of 0.1 to 100 parts by mass of the (meth) acrylic (co) polymer. It is preferably contained in a proportion of 01 parts by mass or more and 5 parts by mass or less, especially 0.1 parts by mass or more or 1 part by mass or less, and among them, it is contained in a proportion of 0.2 parts by mass or more or 0.5 parts by mass or less Even more preferably.

In the present composition, 1,2,4-triazole may be used in combination with 1,2,3-triazole.

(Phosphite compound)
The present composition can further contain a phosphite compound.
The phosphite compound is not itself corrosive and can stabilize acid components such as carboxyl groups. Therefore, by blending a phosphite compound with this composition containing a predetermined (meth) acrylic (co) polymer, the conductive member which is an adherend even if this composition contains an acid component Oxidative degradation of the conductive member as an adherend can be prevented as well as the present composition of course when the composition does not contain an acid component.
Therefore, if an adhesive sheet is formed from the present composition containing a phosphite compound, a conductive member (typically a conductive pattern formed of a transparent conductive layer containing ITO and / or a metal material containing copper or silver) In addition, the conductive member can be prevented from being oxidized and deteriorated. Therefore, for example, it can be suitably used as an adhesive sheet for an image display device having a touch panel.

The phosphite compound that can be contained in the composition is not limited. Among these, a phosphite compound represented by the following formula (1) is preferable.

Formula (1) ··· P [-OR] ₃
(In the formula, R is a hydrocarbon, and specific examples include a substituted or unsubstituted aromatic group, an alicyclic ring, and an alkyl group. The plurality of R may be the same or different from each other, and are adjacent to each other. A plurality of R may be bonded to each other to form a saturated or unsaturated ring structure.)
Further, it may be a compound containing two or more structural units represented by the above formula (1).

As a result of blending various phosphite compounds represented by the above formula (1) with the present composition containing a predetermined (meth) acrylic (co) polymer and 1,2,3-triazole, It was confirmed that the phosphoric acid ester compound also showed an effect of preventing oxidative degradation, and in particular, it was confirmed that the phosphoric acid ester compound was excellent in the oxidative degradation preventive effect for the transparent conductive layer containing ITO.

Examples of the phosphite compound contained in the composition include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, tristearyl phosphite, triethyl phosphite, tris phosphite ( 2-ethylhexyl), tridecyl phosphite, trilauryl phosphite, tris phosphite (tridecyl), trioleyl phosphite, diphenyl phosphite (2-ethylhexyl), diphenyl monodecyl phosphite, diphenyl phosphite Mono (tridecyl), tetraphenyldipropylene dipropylene glycol diphosphite, tetraphenyl (tetratridecyl) pentaerythritol tetraphosphite, tetra (C12-C15 alkyl) -4,4-isopropylidene diphenyl diphosphite, phosphorous Acid Tris (2, -Di-t-butylphenyl), tris (4-nonylphenyl) phosphite, 3,9-bis (nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] Undecane, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (decyloxy) -2,4,8 , 10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (tridecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (stearyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (2,6-di-tert-butyl- 4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (2,4-di-tert-butylphenoxy) -2,4 8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis {2,4-bis (1-methyl-1-phenylethyl) phenoxy} -2,4,8,10- Tetraoxa-3,9-diphosphaspiro [5,5] undecane, 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) phosphite, 4,4′-isopropylidenediphenol C12- 15 alcohol phosphite, distearyl pentaerythritol diphosphite, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6-{(2- Tilhexyl) oxy} -12H-dibenzo [d, g] [1,3,2] dioxaphosphine, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6- (tridecyloxy) ) -12H-dibenzo [d, g] [1,3,2] dioxaphosphine, 1,1′-biphenyl-4,4′-diylbis [bis (2,4-di-t-phosphite) Butylphenyl)], hydrogenated bisphenol A / pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, diethyl phosphite, bis (2-ethylhexyl) phosphite, dilauryl phosphite, dioleyl phosphite, And diphenyl phosphate.

Among these, as the phosphite compound contained in the composition, for example, considering compatibility with the composition, an aliphatic phosphite ester (for example, a phosphite compound of Example 2-2 as a phosphite compound) is used. Tridecyl phosphate and 3,9-bis (decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane of Example 2-3) are preferred. In consideration of hydrolysis resistance, aromatic phosphite esters (for example, tris (2,4-di-t-butylphenyl) phosphite as the phosphite compound of Example 2-1) Is preferred. In consideration of the balance between solubility and hydrolysis resistance, a phosphite having both an aliphatic ester group such as diphenyl phosphite mono (tridecyl) and an aromatic ester group is preferable.

In the present composition, the content ratio of the phosphite compound does not impair the adhesive performance, and from the viewpoint of more effectively suppressing the oxidative deterioration of the conductive member such as ITO, (meth) acrylic (co) The phosphite compound is preferably contained in an amount of 0.0001 (1 × 10 ⁻⁴ ) parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the polymer, and more preferably 0.0005 parts by mass or more. Or 0.8 parts by mass or less, more preferably 0.001 parts by mass or more or 0.7 parts by mass or less, particularly preferably 0.01 parts by mass or more or 0.6 parts by mass or less. .

(Other metal corrosion inhibitors)
In addition to 1,2,3-triazole and phosphite compounds, the composition may contain other metal corrosion inhibitors such as 1,2,4-triazole, benzotriazole and derivatives thereof.

(Crosslinking agent)
This composition may contain a crosslinking agent as needed.
For example, as a method of crosslinking the above-mentioned (meth) acrylic (co) polymer, crosslinking capable of chemically bonding with a reactive group such as a hydroxyl group or a carboxyl group introduced into the (meth) acrylic (co) polymer. Add reaction agent, react by heating or curing, add reaction initiator such as polyfunctional (meth) acrylate having 2 or more (meth) acryloyl groups as crosslinking agent and photopolymerization initiator, UV irradiation The method of bridge | crosslinking by etc. can be mentioned. Among these, a crosslinking method by irradiation with light such as ultraviolet rays is preferred from the viewpoint that polar functional groups such as carboxyl groups in the present composition are not consumed by the reaction and high cohesive force derived from polar components and adhesive properties can be maintained.

Examples of the crosslinking agent include (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, amide group, and N-substituted. The crosslinking agent which has at least 1 sort (s) of crosslinkable functional group chosen from a (meth) acrylamide group and an alkoxy silyl group can be mentioned, You may use 1 type or in combination of 2 or more types. The crosslinkable functional group may be protected with a deprotectable protecting group.

Among these, polyfunctional (meth) acrylate is preferable from the viewpoint of easy control of the crosslinking reaction.
Examples of such polyfunctional (meth) acrylates include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, poly Alkylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri In addition to UV-curable polyfunctional monomers such as pentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tris (acryloxyethyl) isocyanurate, polyester (meth ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, or polyfunctional acrylic oligomers of the polyether (meth) acrylate, may be mentioned polyfunctional acrylamide.

Examples of the cross-linking agent having two or more cross-linkable functional groups include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, 3,4-epoxybutyl (meth) acrylate, 4-hydroxybutyl ( Epoxy group-containing monomers such as (meth) acrylate glycidyl ether; 2-isocyanatoethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, (meth) acrylic acid 2- (0- [ Monomers containing isocyanate groups or blocked isocyanate groups such as 1′-methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate; vinyltrimethoxysilane, Vinyltriethoxysilane, 3-glycidoxypro Rutrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-isocyanatopropyl Examples include various silane coupling agents such as triethoxysilane.

The crosslinking agent having two or more kinds of crosslinkable functional groups has a structure in which one functional group is reacted with a (meth) acrylic (co) polymer and bonded to the (meth) acrylic (co) polymer. Good. By taking such a structure, it is possible to chemically bond a double bondable crosslinkable functional group such as a (meth) acryloyl group or a vinyl group to the (meth) acrylic (co) polymer. Moreover, it exists in the tendency which can suppress the bleeding out of a crosslinking agent and the unexpected plasticization of this adhesive sheet because a crosslinking agent is couple | bonded with a (meth) acrylic-type (co) polymer. Moreover, since the reaction efficiency of the photocrosslinking reaction is promoted by bonding the crosslinking agent to the (meth) acrylic (co) polymer, a cured product having a higher cohesive force tends to be obtained. .

The present composition may further contain a monofunctional monomer that reacts with the crosslinkable functional group of the crosslinking agent. Examples of such monofunctional monomers include alkyl (meth) acrylates such as methyl acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyalkylene glycol (meth) acrylate, and the like. Hydroxyl group-containing (meth) acrylate; (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, Carboxyl group-containing monomers such as rotonic acid, fumaric acid, maleic acid, and itaconic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; tetrahydrofurfuryl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, etc. Ether group-containing (meth) acrylate: (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylmorpholine, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, phenyl (meth) Examples include (meth) acrylamide monomers such as acrylamide, N-methoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
Among these, from the viewpoint of improving the adhesion to the adherend and the effect of suppressing the moist heat whitening, it is preferable to use a hydroxyl group-containing (meth) acrylate or a (meth) acrylamide monomer.

The content of the crosslinking agent is a ratio of 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer, from the viewpoint of balancing the flexibility and cohesion of the composition. In particular, it is preferably 0.05 parts by mass or more and 8 parts by mass or less, and particularly preferably 0.1 parts by mass or more or 5 parts by mass or less.
In addition, when this adhesive sheet is a multilayer, about the layer used as an intermediate | middle layer and a base material among the layers which comprise an adhesive sheet, content of a crosslinking agent may exceed the said range. The content of the crosslinking agent in the intermediate layer or the layer serving as the base material is preferably blended at a ratio of 0.01 to 40 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer. Especially, it is particularly preferably 1 part by mass or more and 30 parts by mass or less, and particularly preferably 2 parts by mass or more or 25 parts by mass or less.

(Photopolymerization initiator)
When performing crosslinking by light irradiation, it is preferable to contain a photopolymerization initiator.
Radical generation mechanisms by photopolymerization initiators are broadly classified into two types: α-cleavage type that cleaves and decomposes its own single bond to generate radicals, and hydrogen abstraction that excites hydrogen from compounds in the system to generate radicals. There is a type. Among these, it is preferable to use a hydrogen abstraction type photocrosslinking initiator.

Among these, when an organic crosslinking agent having a (meth) acryloyl group is used as the crosslinking agent, it is particularly preferable to further add a photopolymerization initiator. This is because radicals are generated by light irradiation and become the starting point of the polymerization reaction in the system.

As the photopolymerization initiator, those currently known can be used as appropriate. Among these, a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
On the other hand, a photopolymerization initiator sensitive to light having a wavelength longer than 380 nm is preferable in that high photoreactivity can be obtained and sensitive light can easily reach the deep part of the pressure-sensitive adhesive sheet.

Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage-type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself to generate a radical, and a photoexcited initiator. It is roughly classified into a hydrogen abstraction type photopolymerization initiator which can form an exciplex with a hydrogen donor in the system and transfer hydrogen of the hydrogen donor.

Of these, the cleavage type photopolymerization initiator decomposes to generate another compound when generating radicals by light irradiation, and once excited, it does not function as a crosslinking initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
On the other hand, a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product like a cleavage type photopolymerization initiator during radical generation reaction by irradiation with active energy rays such as ultraviolet rays, so it is difficult to become a volatile component after the reaction is completed. This is useful in that damage to the body can be reduced.

As the cleavage type photopolymerization initiator, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,4 is high in sensitivity to light and dissociates as a decomposition product after the reaction. Acylphosphine oxides such as 6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide Photoinitiators are preferred.

Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meta ) Acryloyloxybenzophenone, 4- [2-((meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4′-methoxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2- Phenyl-2-oxoacetic acid) oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2 , 4-Dimethylthioxanthone And anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, camphorquinone and derivatives thereof.
Among these, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meth) acryloyloxybenzophenone, 4- [ 2-((Meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4′-methoxybenzophenone, methyl 2-benzoylbenzoate and methyl benzoylformate are preferred.

In addition, the photoinitiator mentioned above may use any 1 type or its derivative (s), and may use them in combination of 2 or more type.
Furthermore, it is also possible to use a sensitizer in addition to the photopolymerization initiator. The sensitizer is not particularly limited, and any sensitizer that can be used as a photopolymerization initiator can be used without any problem. Examples include aromatic amines, anthracene derivatives, anthraquinone derivatives, coumarin derivatives, thioxanthone derivatives, phthalocyanine derivatives, aromatic ketones such as benzophenone, xanthone, thioxanthone, Michler ketone, 9,10-phenanthraquinone, and derivatives thereof. be able to.
In addition, the photoinitiator and the sensitizer may be contained in a state of being bonded to the (meth) acrylic (co) polymer. As a method for bonding a photopolymerization initiator or a sensitizer to a (meth) acrylic (co) polymer, the same method as that for bonding the crosslinking agent to a (meth) acrylic (co) polymer is adopted. can do.

The content of the photopolymerization initiator is not particularly limited, and is typically 0.1 to 10 parts by mass, and particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer. It is particularly preferable to adjust at a ratio of 2 parts by mass or more or 5 parts by mass or less, and among them, 0.5 parts by mass or more or 3 parts by mass or less. However, this range may be exceeded in balance with other elements.

(Antioxidant)
In addition to the above, the present composition may contain an antioxidant as necessary.
Examples of the antioxidant include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), hexamethylene glycol-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene, n-octadecyl-3- (4′-hydroxy-3 ′, 5 '-Di-t-butylphenol) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidene-bis- (6-t Butyl-3-methyl - phenol) and hindered phenol antioxidants such as, sulfur-based, include various antioxidants amine and the like.

(Other ingredients)
Furthermore, the present composition may appropriately contain known components blended in a normal pressure-sensitive adhesive composition. For example, light stabilizers, UV absorbers, metal deactivators, rust inhibitors (excluding metal corrosion inhibitors described above), anti-aging agents, antistatic agents, hygroscopic agents, foaming agents, antifoaming agents, inorganic Various additives such as particles, viscosity modifiers, tackifier resins, photosensitizers, fluorescent agents, and reaction catalysts (tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, etc.) are appropriately added. It is possible.

(Adjustment of adhesive composition)
The pressure-sensitive adhesive composition used in the pressure-sensitive adhesive sheet (the present composition) comprises a (meth) acrylic (co) polymer, 1,2,3-triazole and other components as necessary, such as a phosphite compound, It can be obtained by mixing a predetermined amount of a crosslinking agent or the like.
These mixing methods are not particularly limited, and the order of mixing the components is not particularly limited. In addition, a heat treatment step may be performed at the time of producing the present composition. In this case, it is desirable to perform heat treatment after previously mixing the components of the present composition. You may use what concentrated various mixing components into the masterbatch.

Also, the apparatus for mixing is not particularly limited, and for example, a universal kneader, a planetary mixer, a Banbury mixer, a kneader, a gate mixer, a pressure kneader, three rolls, and two rolls can be used. You may mix using a solvent as needed. Moreover, this composition can be used as a solvent-free system which does not contain a solvent. By using it as a solvent-free system, the solvent does not remain, and there can be provided the advantages that the heat resistance and light resistance are enhanced.

Further, the present composition is a composition containing a monomer component constituting the (meth) acrylic (co) polymer, 1,2,3-triazole, a photopolymerization initiator, and other optional components, which is electrically conductive. When used as a pressure-sensitive adhesive sheet for members, it can be used in such a way that a (meth) acrylic (co) polymer is produced by light irradiation to cause a polymerization reaction to proceed.

<Form of adhesive sheet for conductive member>
In addition to directly applying the composition to an adherend and forming it into a sheet, this pressure-sensitive adhesive sheet can be used as a single-layer or multi-layer sheet on a release film. It can also be.
Examples of the material of the release film include a polyester film, a polyolefin film, a polycarbonate film, a polystyrene film, an acrylic film, a triacetyl cellulose film, and a fluororesin film. Among these, a polyester film and a polyolefin film are particularly preferable.

The thickness of the release film is not particularly limited. Among them, for example, from the viewpoint of processability and handling properties, it is preferably 25 μm to 500 μm, more preferably 38 μm or more and 250 μm or less, and particularly preferably 50 μm or more or 200 μm or less.

The pressure-sensitive adhesive sheet may employ a method of directly extruding the composition or a method of molding by pouring into a mold without using an adherend or a release film as described above. I can do it. Furthermore, it can also be set as the aspect of an adhesive sheet by directly filling this composition between members, such as an electrically-conductive member.

<Physical properties of adhesive sheet for conductive member>
(Corrosion prevention effect on conductive layer of conductive member)
This pressure-sensitive adhesive sheet has corrosion resistance to conductive members, particularly conductive patterns formed of metal materials including a transparent conductive layer and copper. Therefore, the change rate [((Ω / Ω0) -1) × 100] of the ITO resistance value measured by the following methods (1) to (2) can be made less than 5%, particularly less than 3%. Also, the rate of change in copper resistance [((Ω / Ω0) -1) × 100] measured by the following methods (3) to (4) is less than 20%, particularly less than 10%, and even less than 5%. In particular, it can be less than 3%.

(1) Evaluation in which an adhesive wiring for conductive member (this composition) is formed into a 150 μm thick sheet to form an adhesive sheet, and an ITO wiring made of indium oxide (ITO) is formed on a glass substrate. The said adhesive sheet is bonded to the ITO glass substrate for manufacture, and an ITO wiring with an adhesive sheet is produced.

(2) The resistance value (Ω0) at room temperature of the ITO wiring in the ITO wiring with the adhesive sheet is measured in advance, and the ITO wiring with the adhesive sheet is stored in an environment of 65 ° C. and 90% RH for 500 hours. The resistance value (Ω) after the storage of the ITO wiring in the ITO wiring with the adhesive sheet is measured.

(3) The adhesive composition for conductive member (this composition) is formed into a sheet having a thickness of 150 μm to form an adhesive sheet, and the copper wiring substrate for evaluation formed by forming a copper wiring on the glass substrate is A pressure sensitive adhesive sheet is bonded to produce a copper wiring with a pressure sensitive adhesive sheet.

(4) The resistance value (Ω0) at room temperature of the copper wiring in the copper wiring with the adhesive sheet is measured in advance, and the copper wiring with the adhesive sheet is stored in an environment of 65 ° C. and 90% RH for 500 hours. The resistance value (Ω) after the storage of the copper wiring in the copper wiring with the adhesive sheet is measured.

(transparency)
The pressure-sensitive adhesive sheet is preferably optically transparent. That is, it is preferably a transparent adhesive sheet. Here, “optically transparent” means that the total light transmittance is 80% or more, preferably 85% or more, and more preferably 90% or more.

(thickness)
The thickness of the pressure-sensitive adhesive sheet is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more or 400 μm or less, and particularly preferably 20 μm or more or 350 μm or less.

<Use of adhesive sheet for conductive members>
This adhesive sheet is, for example, an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, such as a plasma display (PDP), a liquid crystal display (LCD). In an image display device using an image display panel such as an organic EL display (OLED), an inorganic EL display, an electrophoretic display (EPD), and an interferometric modulation display (IMOD), each component member, particularly a conductive member, particularly a transparent conductive member It is suitable for laminating a conductive member having a conductor pattern formed of a metal material including a layer and / or copper. It is also suitable for bonding a conductive member including a transparent conductive layer containing ITO or IGZO and / or a transparent conductive layer having a conductor pattern formed of a metal material containing copper or silver.

<Conductive member laminate>
The conductive member laminate of the present invention (hereinafter abbreviated as “the present laminate”) can be obtained by laminating the pressure-sensitive adhesive sheet and a conductive member, for example, a conductive layer surface of a transparent conductive layer. .
This laminated body should just have the structure which the adhesive layer surface of any one of this adhesive sheet and the conductive layer surface of a transparent conductive layer bonded together.
In the case where the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, the laminate may have a structure in which both the pressure-sensitive adhesive layer surfaces of the pressure-sensitive adhesive sheet and the conductive layer surface of the transparent conductive layer are bonded together.

The transparent conductive layer has an insulating protective film (passivation film) made of olefin polymer, urethane polymer, epoxy polymer, acrylic polymer, silicone polymer, or inorganic glass so as to cover the conductive layer surface of the conductive film. May be.
In this case, the pressure-sensitive adhesive sheet is not directly bonded to the transparent conductive layer surface (not directly in contact with the transparent conductive layer surface). The adhesive sheet corrodes the transparent conductive layer by the action of 1,2,3-triazole even if the component derived from the composition (particularly the acid component) penetrates and reaches the transparent conductive layer from the insulating film. This can be prevented. In particular, 1,2,3-triazole is highly water-soluble and can easily move to the transparent conductive layer when the pressure-sensitive adhesive sheet absorbs moisture in a moist heat environment, so that an excellent metal corrosion prevention effect can be achieved.
Thus, according to the present pressure-sensitive adhesive sheet, not only the presence or absence of an insulating protective film, but also an excellent metal corrosion prevention effect on the adherend is exhibited as well as discoloration and alteration of the pressure-sensitive adhesive layer due to metal ions on the adherend. Can do.

The laminate obtained by bonding to the conductive layer surface can be suitably used for a touch panel. Examples of the touch panel include a resistance film method, a capacitance method, and an electromagnetic induction method, and a capacitance method is preferable.

The transparent conductive layer only needs to have a conductive layer on at least one surface, and examples thereof include a transparent conductive layer in which a conductive material is provided on the surface of a transparent substrate by vapor deposition, sputtering, coating, or the like.
The conductive material used for the conductive layer of the transparent conductive layer is not particularly limited. Specifically, indium oxide, indium / gallium / zinc composite oxide, tin-doped indium oxide (ITO), zinc oxide, gallium oxide, titanium oxide In addition to metal oxides such as, metal materials such as silver, copper, molybdenum, and aluminum can be given. Among them, tin-doped indium oxide (ITO) and indium / gallium / zinc composite oxide (IGZO), which are excellent in transparency, are preferably used. Moreover, copper and silver can also be used suitably from a viewpoint which is excellent in electroconductivity. In the transparent conductive layer, the substrate on which the conductive substance is patterned is not particularly limited, and examples thereof include glass and a resin film.

The transparent conductive layer typically has a conductive layer on at least one surface. Typically, a conductive pattern (wiring pattern) mainly composed of copper or silver is formed on the transparent conductive layer so as to route the peripheral portion. Since 1,2,3-triazole has particularly high resistance to corrosion resistance to copper, this pressure-sensitive adhesive sheet including this is particularly suitable for conductive members having a conductor pattern formed of a metal material containing copper. It can be preferably used.

Other specific examples of the laminate include, for example, a release film / this adhesive sheet / touch panel, a release film / this adhesive sheet / protective panel, a release film / this adhesive sheet / image display panel, and an image display panel / book. Adhesive sheet / touch panel, image display panel / main adhesive sheet / protection panel, image display panel / main adhesive sheet / touch panel / main adhesive sheet / protection panel, polarizing film / main adhesive sheet / touch panel, polarizing film / main adhesive sheet / touch panel / The composition of the present adhesive sheet / protective panel can be mentioned. Moreover, in said structure, all the structures which interpose the said conductive layer between members, such as this adhesive sheet and an adjacent touch panel, a protection panel, an image display panel, a polarizing film, can be mentioned. However, it is not limited to these lamination examples.
The touch panel includes a structure in which a touch panel function is included in the protective panel and a structure in which the touch panel function is included in the image display panel.

<Image display device>
The image display device of the present invention (hereinafter abbreviated as “this device”) includes at least the present laminate, the image display panel, and the surface protection panel as constituent members.

More specifically, an image display device having a configuration in which the laminate obtained by bonding the adhesive sheet to the conductive layer surface of the transparent conductive layer is interposed between the image display panel and the surface protection panel is mentioned. Can do. At this time, the pressure-sensitive adhesive sheet can also be used on the image display panel side.

As the material of the surface protection panel, in addition to glass, acryl-based polyolefin resin such as acrylic resin, polycarbonate resin, cycloolefin polymer, styrene resin, polyvinyl chloride resin, phenol resin, melamine resin, Plastics such as epoxy resins may be used.

The image display panel is composed of another optical film such as a polarizing film or other retardation film, a liquid crystal material, and a backlight system (usually, the adherend surface of the composition or the adhesive article to the image display panel is an optical film. There are STN method, VA method, IPS method, etc. depending on the control method of the liquid crystal material, but any method may be used.

As the present image display device, for example, an image display device such as a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, a plasma display, and a microelectromechanical system (MEMS) display can be configured.

<Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), “X is preferably greater than X” or “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.

“Sheet” generally refers to a product that is thin by definition in JIS and has a thickness that is small and flat for the length and width. In general, “film” is thicker than the length and width. A thin flat product with an extremely small thickness and an arbitrarily limited maximum thickness, usually supplied in the form of a roll (Japanese Industrial Standard JISK6900). However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.

<(Meth) acrylic (co) polymer>
The (meth) acrylic (co) polymer used the following.
A-1: A copolymer comprising 76 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 4 parts by mass of acrylic acid (mass average molecular weight 400,000)
A-2: A copolymer comprising 81 parts by mass of butyl acrylate, 15 parts by mass of methyl methacrylate and 4 parts by mass of acrylic acid (mass average molecular weight 200,000)

<Example 1>
[Example 1-1]
1 kg of (meth) acrylic (co) polymer (A-1), 3 g of 1,2,3-triazole (manufactured by Otsuka Chemical Co., Ltd.) as a metal corrosion inhibitor, and 4-methylbenzophenone as a photopolymerization initiator 15 g of a mixture of 2,4,6-trimethylbenzophenone (manufactured by Lamberti, trade name “Ezacure TZT”) was added and mixed uniformly to obtain a resin composition for an adhesive layer.

Two polyethylene terephthalate films (trade name “Diafoil MLV”, manufactured by Mitsubishi Plastics, Inc., 100 μm thick, and product name “Diafoil MRQ” manufactured by Mitsubishi Plastics, Inc.) The pressure-sensitive adhesive sheet was shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet was 150 μm, and a pressure-sensitive adhesive sheet laminate was produced. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.

[Example 1-2]
1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor, and UV curable resin propoxylated pentaerythritol triacrylate as a crosslinking agent (Shin Nakamura Kogyo Co., Ltd.) 20 g of company, trade name “ATM-4PL”), and 15 g of a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (trade name “Ezacure TZT”, manufactured by Lamberti) as a photopolymerization initiator were added uniformly. By mixing, a resin composition for an adhesive layer was obtained.

Next, the resin composition for the pressure-sensitive adhesive layer was molded into a sheet shape so as to have a thickness of 150 μm on a polyethylene terephthalate film (trade name “Diafoil MRV”, manufactured by Mitsubishi Plastics Co., Ltd., thickness: 100 μm) subjected to release treatment. Thereafter, a peeled polyethylene terephthalate film (manufactured by Mitsubishi Plastics, trade name “Diafoil MRQ”, thickness 75 μm) was coated to prepare an adhesive sheet laminate. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.

[Example 1-3]
A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 1-2 except that 5 g of 1,2,3-triazole was used as the metal corrosion inhibitor. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.

[Comparative Example 1-1]
A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 1-1 except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.

[Comparative Example 1-2]
A pressure-sensitive adhesive sheet laminate was prepared in the same manner as in Example 1-1, except that 5 g of benzotriazole (trade name “BT120” manufactured by Johoku Chemical Co., Ltd.) was used instead of 1,2,3-triazole as a metal corrosion inhibitor. did. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.

[Comparative Example 1-3]
5 g of tolyltriazole (mixture of 4-methylbenzotriazole and 5-methylbenzotriazole) (trade name “SEETEC TT-R” manufactured by Cypro Kasei Co., Ltd.) is used as a metal corrosion inhibitor instead of 1,2,3-triazole. A pressure-sensitive adhesive sheet laminate was produced in the same manner as Example 1-1 except for the above. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.

[Comparative Example 1-4]
Example 1-1 except that 5 g of 2,5-dimercapto-1,3,4-thiadiazole (trade name “MTD”, manufactured by Toyobo Co., Ltd.) was used in place of 1,2,3-triazole as a metal corrosion inhibitor. In the same manner, a pressure-sensitive adhesive sheet laminate was produced. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.

<Various evaluations>
(1) Corrosion resistance reliability On a glass substrate (60 mm x 45 mm), with a line width of 70 μm, a line length of 46 mm, and a line interval of 30 μm, 10.5 mm thick ITO and 3000 mm thick copper A metal film round-trip line is formed by laminating the films in this order, and 2 mm squares are formed at both ends of the round-trip line to form a copper pattern (about 97 cm in length) to evaluate corrosion resistance reliability. A copper glass substrate was prepared (see FIG. 1A).

The release film on one side of the pressure-sensitive adhesive sheet laminate (pressure-sensitive adhesive sheet thickness 150 μm) prepared in the above Examples and Comparative Examples was peeled off, and a polyethylene terephthalate (PET) film (trade name “COSMO SHINE A4100, manufactured by Toyobo Co., Ltd.” was applied to the exposed surface. ”, 125 μm) was attached with a hand roller. Next, after cutting out the pressure-sensitive adhesive sheet with the PET film to 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. The pressure-sensitive adhesive sheet was adhered to a copper glass substrate for evaluation with a hand roller, and the cumulative amount of light with a wavelength of 365 nm was 3000 mJ / in Example 1-1 and Comparative Examples 1-1 to 1-4 via a PET film. cm ^2, examples 1-2 and 1-3 irradiated with ultraviolet rays using a high-pressure mercury lamp so as to be 2000 mJ / cm ^2, by UV cross, corrosion reliability evaluation samples (copper wire with the pressure-sensitive adhesive sheet) It produced (refer FIG.1 (D)).

The resistance value (Ω0) at room temperature of the copper wiring in this corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) was measured in advance.

On the other hand, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) is stored in an environment of 65 ° C. and 90% RH for 500 hours, and after storage, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) The resistance value (Ω) of the copper wiring was measured.

Then, the change rate (%) [((Ω / Ω0) -1) × 100] of the copper resistance value, that is, the resistance value between the wire ends was calculated and shown in Table 1 as “resistance value change”.

Regarding corrosion resistance reliability, those with a resistance change rate of 20% or more were judged as “× (poor)”, and those with less than 20% were judged as “good”. The results are shown in Table 1.

(2) Anti-foaming reliability One side release film of the pressure-sensitive adhesive sheet laminate (thickness 150 μm) prepared in the examples and comparative examples is peeled off and hand rolls on a soda lime glass plate (150 × 200 mm, thickness 0.55 mm). And pasted. Furthermore, the remaining release film was peeled off, and bonded with a hand roll while deflecting the chemically strengthened glass plate (180 × 220 mm, thickness 0.6 mm).

Next, the bonded product was autoclaved at 60 ° C. in a 0.2 MPa environment for 20 minutes. Using this metal halide lamp irradiation device (Ushio Electric Co., Ltd., model UVC-0516S1, lamp UVL-8001M3-N), a belt conveyor so that the irradiation dose at a wavelength of 365 nm is 3000 mJ / cm ² per irradiation. After adjusting the speed and irradiance and irradiating 15 times, the appearance change was observed.

Regarding the anti-foaming reliability, when the appearance was observed, it was determined as “◯ (good)” when there was no change from before UV irradiation, and “× (poor)” when bubbles were generated. The results are shown in Table 1.

(3) UV curing characteristics (storage modulus G ′ before UV curing)
The storage elastic modulus before UV curing was measured using a rheometer (Eihiro Seiki Co., Ltd.) as a measurement sample obtained by punching the adhesive sheets prepared in Examples and Comparative Examples to a thickness of 1 to 2 mm and punching them into a circle with a diameter of 20 mm. Using a “MARS” manufactured by the company, adhesive jig: Φ25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: −50 to 200 ° C., heating rate: 3 ° C./min, −50 ° C. The dynamic storage elastic modulus G ′ up to 200 ° C. was measured, and the storage elastic modulus value at 125 ° C. was read. The results are shown in Table 1.

(Storage modulus G ′ after UV curing)
The storage elastic modulus after UV curing was measured as follows.
The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were UV-crosslinked by irradiating UV light with a high-pressure mercury lamp through a PET film. At this time, Example 1-1 and Comparative Examples 1-1 to 1-4 were irradiated so that the integrated light quantity with a wavelength of 365 nm was 3000 mJ / cm ^2, and Examples 1-2 and 1-3 were the laminates. Irradiation was performed so that the amount of light was 2000 mJ / cm ² . The pressure-sensitive adhesive sheet thus UV-crosslinked was laminated to a thickness of 1 to 2 mm, and punched into a circle having a diameter of 20 mm was used as a measurement sample.
Using a rheometer (trade name “MARS”, manufactured by Eiko Seiki Co., Ltd.), adhesive jig: Φ25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: −50 to 200 ° C., heating rate: 3 The storage elastic modulus after ultraviolet curing was determined by measuring the dynamic storage elastic modulus G ′ of the measurement sample from −50 ° C. to 200 ° C. at a rate of ℃ / min and reading the storage elastic modulus value at 125 ° C. . The results are shown in Table 1.

Compare the storage modulus G 'before UV curing and the storage modulus G' after UV curing for UV curing characteristics. The value after curing is significantly increased to "Good", almost changed to the value. Those without were judged as “× (poor)”. The results are shown in Table 1.

(Evaluation results)
The adhesive sheets of Examples 1-1 to 1-3 contain 1,2,3-triazole as a metal corrosion inhibitor, so that there is little change in the resistance value of the copper wiring and excellent corrosion resistance reliability. there were. In addition, the foaming resistance reliability and ultraviolet curing characteristics were also good.

On the other hand, Comparative Example 1-1 did not contain a metal corrosion inhibitor and was inferior in corrosion resistance reliability.
Comparative Example 1-2 contained benzotriazole as a metal corrosion inhibitor, but was poor in foaming reliability due to the characteristics of benzotriazole.
Comparative Example 1-3 contained tolyltriazole as a metal corrosion inhibitor, but was poor in foaming reliability due to the characteristics of tolyltriazole.
Comparative Example 1-4 contains dimercaptothiadiazole as a metal corrosion inhibitor. However, since dimercaptothiadiazole absorbs ultraviolet rays, the pressure-sensitive adhesive sheet was inferior in ultraviolet curing properties.

From the above results, 1,2,3-triazole has a melting point of about 20 ° C. and is almost liquid at room temperature. Therefore, it can be easily added to the main adhesive in the actual production process of the adhesive sheet. It was found to be excellent in dispersibility in the main agent.
In addition, 1,2,3-triazole is highly water-soluble and, when the pressure-sensitive adhesive sheet absorbs moisture in a moist heat environment, it easily moves to the surface of the metal layer (copper wiring), so it has an excellent metal corrosion prevention effect. It became clear that we could do it.
It has also been clarified that 1,2,3-triazole does not inhibit the UV curing property because it does not absorb at a spectrophotometer with a wavelength of 300 to 400 nm.
As described above, it has been found that 1,2,3-triazole has excellent characteristics as compared with conventional metal corrosion inhibitors and is particularly effective when used for an adhesive sheet for conductive members.

<Example 2>
[Example 2-1]
200 kg of propoxylated pentaerythritol polyacrylate (trade name “ATM-4PL”, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent for 1 kg of (meth) acrylic (co) polymer (A-1), photopolymerization started As an agent, 10 g of a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (Lamberti, trade name “Ezacure TZT”) was added and mixed uniformly to obtain an intermediate layer resin composition.

Two polyethylene terephthalate films (trade name “Diafoil MRF”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 μm and a product name “Diafoil MRT” manufactured by Mitsubishi Plastics, Inc. 38 μm) and shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet is 80 μm, to produce an intermediate layer resin sheet (α).

For 1 kg of the (meth) acrylic (co) polymer (A-1), 1.5 g of 1,2,3-triazole as a metal corrosion inhibitor and Tris phosphite (2,4 as a phosphite compound) -Di-t-butylphenyl) (BASF, trade name “Irgafos 168”) and a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone as a photopolymerization initiator (Lamberti, trade name “ Ezacure TZT ”) 15 g was added and mixed uniformly to obtain a resin composition for an adhesive layer.

Two polyethylene terephthalate films (trade name “Diafoil MRV”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 100 μm, and product name “Diafoil MRT” manufactured by Mitsubishi Plastics Co., Ltd.) were prepared by removing the oil composition for the adhesive layer. , 38 μm thick) and shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet is 35 μm, to produce a resin sheet (β) for the pressure-sensitive adhesive layer.

Further, two polyethylene terephthalate films (trade name “Diafoil MRQ”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 μm) and a product name “Diafoil” manufactured by Mitsubishi Plastics Co., Ltd. were peeled off from the above fat composition for the pressure-sensitive adhesive layer. MRT ”, thickness 38 μm), and shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet was 35 μm, to produce a resin sheet (β ′) for the pressure-sensitive adhesive layer.

The PET films on both sides of the intermediate layer sheet (α) are sequentially peeled and removed, and the PET films on one side of the adhesive layer resin sheets (β) and (β ′) are peeled off to place the exposed adhesive surface in the middle. Laminate bodies made of (β) / (α) / (β ′) were prepared by sequentially laminating on both surfaces of the layer sheet (β).

Irradiate ultraviolet rays with a high-pressure mercury lamp through the PET film remaining on the surfaces of (β) and (β ′) so that the integrated light quantity at a wavelength of 365 nm is 2000 mJ / cm ^2, and (α), (β) and (Β ′) was UV-crosslinked to prepare an adhesive sheet laminate (thickness 150 μm). The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.

[Example 2-2]
1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor, tridecyl phosphite as a phosphite compound (trade name, manufactured by Adeka) 3 g of “ADK STAB 3010”), 20 g of pentaerythritol tri and tetraacrylate (manufactured by Toagosei Co., Ltd., “Aronix M-306”) as a crosslinking agent, and 1-hydroxy-cyclohexyl phenyl ketone (manufactured by BASF, Irgacure as a photopolymerization initiator) 184) 10 g was added and mixed uniformly to obtain a resin composition for an adhesive layer.

Next, the pressure-sensitive adhesive layer resin composition was formed into a sheet shape having a thickness of 150 μm on a peeled polyethylene terephthalate film (Mitsubishi Resin, Diafoil MRV, thickness 100 μm), and then peeled. A polyethylene terephthalate film (trade name “Diafoil MRQ”, thickness 75 μm, manufactured by Mitsubishi Plastics, Inc.) was coated. A pressure-sensitive adhesive sheet laminate is obtained by irradiating ultraviolet rays with a high-pressure mercury lamp through an exfoliated polyethylene terephthalate film so that the integrated light quantity at a wavelength of 365 nm is 1000 mJ / cm ² to cross-link the adhesive layer resin composition with ultraviolet rays. Was made. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.

[Example 2-3]
3,9-bis (decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (trade name “JPE-10” manufactured by Johoku Chemical Co., Ltd.) as a phosphite compound A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-2 except that 3 g was used. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.

[Comparative Example 2-1]
1,2,3-triazole as a metal corrosion inhibitor and tris (2,4-di-t-butylphenyl) phosphite as a phosphite compound (trade name “Irgaphos 168” manufactured by BASF) Except not being added, in the same manner as in Example 2-1, the pressure-sensitive adhesive sheet laminate in which the pressure-sensitive adhesive sheet laminate was produced was subjected to various evaluations described below. The results are shown in Table 2.

[Comparative Example 2-2]
A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-1, except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.

[Comparative Example 2-3]
As a metal corrosion inhibitor, except that 1.5 g of benzotriazole (manufactured by Johoku Chemical Co., Ltd., trade name “BT120”) is added in place of 1,2,3-triazole, and the phosphite compound is not added. A pressure-sensitive adhesive sheet laminate was produced in the same manner as Example 2-1. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.

<Various evaluations>
(1) Oxidation degradation prevention property Indium oxide (ITO) reciprocation on a glass substrate (60 mm x 45 mm) so as to reciprocate 10.5 with a thickness of 150 to 200 mm, a line width of 70 μm, a line length of 46 mm, and a line interval of 30 μm. In addition to forming a line, 2 mm squares made of ITO were formed at both ends of the reciprocating line to form an ITO pattern (length of about 97 cm) to produce an ITO glass substrate for evaluating oxidation resistance (see FIG. 1 (A)).

Peel off the release film on one side of the adhesive sheet laminate (thickness 150 μm) prepared in the above examples and comparative examples, and hand the PET film (trade name “COSMO SHINE A4100”, 125 μm, manufactured by Toyobo Co., Ltd.) on the exposed surface. Sticking with a roller. Next, after cutting out the pressure-sensitive adhesive sheet with the PET film to 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. The pressure-sensitive adhesive sheet was attached to an ITO glass substrate for use with a hand roller to produce a sample for evaluating oxidation resistance (ITO wiring with pressure-sensitive adhesive sheet) (see FIG. 1C).

The resistance value (Ω0) at room temperature of the ITO wiring in this oxidation deterioration prevention evaluation sample (ITO wiring with adhesive sheet) was measured in advance.

On the other hand, the oxidation degradation prevention evaluation sample (ITO wiring with adhesive sheet) is stored in an environment of 65 ° C. and 90% RH for 500 hours, and after storage, the oxidation degradation resistance evaluation sample (ITO wiring with adhesive sheet) is stored. ) Was measured for the resistance value (Ω) of the ITO wiring.

Then, the change rate (%) [((Ω / Ω0) -1) × 100] of the ITO resistance value, that is, the resistance value between line ends was calculated, and shown in Table 2 as “resistance value change”.

As for the oxidative degradation prevention property, a resistance value change rate of 5% or more was judged as “× (poor)”, and less than 5% was judged as “good”. The results are shown in Table 2.

(2) Corrosion resistance reliability On a glass substrate (60 mm x 45 mm), with a line width of 70 µm, a line length of 46 mm, and a line interval of 30 µm, 10.5 mm thick ITO and 3000 mm thick copper A metal film round-trip line is formed by laminating the films in this order, and 2 mm squares are formed at both ends of the round-trip line to form a copper pattern (about 97 cm in length) to evaluate corrosion resistance reliability. A copper glass substrate was prepared (see FIG. 1A).

Peel off the release film on one side of the adhesive sheet laminate (thickness 150 μm) prepared in the above examples and comparative examples, and hand the PET film (trade name “COSMO SHINE A4100”, 125 μm, manufactured by Toyobo Co., Ltd.) on the exposed surface. Sticking with a roller. Next, after cutting out the pressure-sensitive adhesive sheet with the PET film to 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. A pressure-sensitive adhesive sheet was attached to a copper glass substrate for evaluation with a hand roller to prepare a corrosion resistance reliability evaluation sample (copper wiring with pressure-sensitive adhesive sheet) (see FIG. 1D).

Then, the change rate (%) [((Ω / Ω0) -1) × 100] of the copper resistance value, that is, the resistance value between the wire ends was calculated and shown in Table 2 as “resistance value change”.

Regarding corrosion resistance reliability, those with a resistance change rate of 20% or more were judged as “× (poor)”, and those with less than 20% were judged as “good”. The results are shown in Table 2.

(Evaluation results)
The adhesive sheets of Examples 2-1 to 2-3 contain 1,2,3-triazole as a metal corrosion inhibitor, and further contain a phosphite, so that the resistance value of both ITO wiring and copper wiring changes. There were few, and it was excellent in corrosion resistance reliability and oxidation deterioration prevention property.

On the other hand, Comparative Example 2-1 contained neither a phosphite compound nor a metal corrosion inhibitor, and was inferior in corrosion resistance reliability and oxidation deterioration prevention properties.
Since Comparative Example 2-2 did not contain a metal corrosion inhibitor, corrosion of copper wiring was particularly remarkable.
Comparative Example 2-3 did not contain a phosphite compound and was inferior in the ability to prevent oxidative deterioration of the ITO wiring.

The pressure-sensitive adhesive sheet for a conductive member of the present invention has corrosion resistance and reliability against a conductive member (typically a conductive member having a conductive pattern formed of a transparent conductive layer and / or a metal material containing copper or silver). Since it can have foaming reliability, it can be used as an adhesive sheet suitable for bonding various conductive members. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.

Claims

A pressure-sensitive adhesive sheet for a conductive member having a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer and 1,2,3-triazole.
The pressure-sensitive adhesive sheet for conductive members according to claim 1, wherein the pressure-sensitive adhesive composition contains a phosphite compound.
The phosphite compound comprises at least one selected from aliphatic phosphites, aromatic phosphites, and phosphites having an aliphatic ester group and an aromatic ester group. The adhesive sheet for conductive members according to claim 1 or 2.
The pressure-sensitive adhesive sheet for a conductive member according to any one of claims 1 to 3, wherein the (meth) acrylic copolymer contains a carboxyl group-containing monomer as a structural unit.
The pressure-sensitive adhesive sheet for conductive members according to claim 4, wherein the (meth) acrylic copolymer contains 1.2 to 15% by mass of a carboxyl group-containing monomer.
The pressure-sensitive adhesive sheet for conductive members according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive composition is a photocurable composition.
The pressure-sensitive adhesive sheet for conductive members according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive composition contains a crosslinking agent.
The pressure-sensitive adhesive sheet for a conductive member according to any one of claims 1 to 7, wherein the conductive member has a transparent conductive layer.
The pressure-sensitive adhesive sheet for a conductive member according to claim 8, wherein the transparent conductive layer has an insulating protective film.
The conductive member according to any one of claims 1 to 9, wherein the conductive member has a conductive pattern formed of a transparent conductive layer containing tin-doped indium oxide and / or a metal material containing copper. Adhesive sheet.
A conductive member laminate having a structure in which the conductive member pressure-sensitive adhesive sheet according to any one of claims 1 to 10 is bonded to a conductive member.
An image display device comprising the conductive member laminate according to claim 11, an image display panel, and a surface protection panel as constituent members.
A pressure-sensitive adhesive composition for conductive members containing a (meth) acrylic copolymer and 1,2,3-triazole.