KR101219327B1 - Pressure-sensitive adhesive composition for conductive member and laminate using the same - Google Patents

Abstract

Urethane urea resin (A) having a weight average molecular weight (Mw) of 50,000 to 200,000, obtained by reacting a polyamino compound (c) with a urethane prepolymer obtained by reacting a polyol (a) with a polyisocyanate (b),
Pressure sensitive adhesive composition for conductive members containing 0.1 to 3 parts by weight of a curing agent (B) based on 100 parts by weight of the urethane urea resin (A).

Description

Pressure-sensitive adhesive composition for a conductive member, and a laminate produced using the same TECHNICAL FIELD

The present invention relates to a pressure-sensitive adhesive composition for a conductive member, and more particularly, to a pressure-sensitive adhesive composition for a conductive member used for adhesion of a conductive member used in a touch panel and the like, and a pressure-sensitive adhesive sheet for a conductive member manufactured using the same. The present invention relates to a laminate, and a sheet for a touch panel.

BACKGROUND ART Liquid crystal displays are widely used in various products such as computers and televisions. In particular, miniaturization is increasingly used in electronic notebooks, mobile phones, and the like, and is widely used as display devices of all electronic devices. Such a liquid crystal display device or the like has a so-called touch panel module in which the display screen functions as a sheet for a touch panel and an operator touches with a finger to designate an operation at a predetermined point on the display screen.

In the configuration of the touch panel, a glass substrate or a transparent resin substrate and a conductive member including a transparent conductive film such as ITO or a metal circuit are joined by a pressure-sensitive adhesive layer. When the laminate of the glass substrate or the transparent resin substrate / pressure sensitive adhesive layer / transparent electrode (conductive member) is placed under high temperature or under high temperature and high humidity conditions, bubbles are generated on the adhesive interface between the pressure sensitive adhesive layer and the adherend (foaming). ), The film may be peeled off from the adherend. Accordingly, attempts have been made to improve the pressure-sensitive adhesive to be used so that foaming, lifting and peeling do not occur even under severe environments.

Further, the pressure-sensitive adhesive layer is required to have a high adhesive force that does not peel off when a strong force is applied in the peeling direction.

Until now, the use of the pressure-sensitive adhesive mainly based on acrylic resin has been studied as the pressure-sensitive adhesive layer (Patent Documents 1 and 2).

When a pressure-sensitive adhesive based on acrylic resin was used, it was necessary to introduce an acid group into the base resin in order to improve the adhesiveness with the conductive member. However, the introduced acid group corrodes the conductive member, which is the adherend, causing malfunction or the like.

In addition, applications to various applications of pressure-sensitive adhesives based on urethane urea resins have been studied. However, studies on the development of such high adhesiveness and application to the conductive member have not been made so far (Patent Documents 3, 4 and 5).

Japanese Patent Laid-Open No. 2006-45315 Japanese Patent Laid-Open No. 2008-120864 Japanese Patent Application Laid-Open No. 2002-121256 Japanese Patent Application Laid-Open No. 2002-38119 Japanese Patent Application Laid-Open No. 2003-137963

An object of the present invention is to prevent foaming or peeling even under conditions of high temperature or high temperature and high humidity without causing malfunctions due to corrosion in conductive members such as transparent conductive films or metal circuits, including ITO, and good plasticizer resistance. In addition, the present invention provides a pressure-sensitive adhesive composition for a conductive member having good workability and further having high adhesiveness.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said objective can be achieved by the pressure-sensitive adhesive composition shown below, and came to complete this invention.

That is, 1st this invention is urethane urea whose weight average molecular weights (Mw) formed by making a polyamino compound (c) react with the urethane prepolymer obtained by making a polyol (a) and a polyisocyanate (b) react. It relates to a pressure-sensitive adhesive composition for conductive members comprising a resin (A) and 0.1 to 3 parts by weight of a curing agent (B) based on 100 parts by weight of the urethane urea resin (A).

According to a second aspect of the present invention, the amount of the polyisocyanate (b) is 8 to 23% by weight in 100% by weight of the synthetic raw material of the urethane urea resin (A), and the amount of the polyamino compound (c) is It relates to the pressure-sensitive adhesive composition for conductive members of the first invention, which is 0.5 to 8% by weight in 100% by weight of the synthetic raw material of the urethane urea resin (A).

3rd this invention relates to the pressure-sensitive adhesive composition for conductive members of 1st or 2nd this invention in which a polyol (a) contains the polyol which has a polypropylene glycol skeleton.

In the fourth aspect of the present invention, the curing agent (B) is a hexamethylene diisocyanate trimethylolpropane adduct, a hexamethylene diisocyanate isocyanurate body, a hexamethylene diisocyanate biuret body, and a xylene diisocyanate trimethylolpropane It relates to the pressure-sensitive adhesive composition for conductive members of any one of the first to the third, including at least one selected from the group consisting of a duct body.

The fifth aspect of the present invention consists of a silane coupling agent having 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and an imidazole group based on 100 parts by weight of the urethane urea resin (A). The pressure sensitive adhesive composition for conductive members of any one of 1st-4th containing 0.1-1.0 weight part of any 1 or more types chosen from a group is mentioned.

A sixth present invention includes a sheet-like base material and a pressure-sensitive adhesive layer formed on one or both surfaces of the sheet-shaped base material, wherein the pressure-sensitive adhesive layer is for the conductive member of any one of the first to fifth aspects of the present invention. It is related with the pressure-sensitive adhesive sheet for conductive members formed from the pressure-sensitive adhesive composition. That is, 6th this invention is the pressure-sensitive adhesive for conductive members formed by forming the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for conductive members of any one of 1st-5th this invention on one or both surfaces of a sheet-like base material. Relates to a castle sheet.

The seventh invention includes a conductive member or a transparent optical member and a pressure-sensitive adhesive layer laminated on the conductive member or the transparent optical member,

The said pressure-sensitive adhesive layer is related with the laminated body formed from the pressure-sensitive adhesive composition for conductive members of any one of 1st-5th this invention. That is, 7th this invention relates to the laminated body by which the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for conductive members of any one of 1st-5th is laminated | stacked on the conductive member.

8th this invention relates to the laminated body of 7th this invention whose conductive member is a transparent conductive film or a metal circuit.

9th and 10th invention are related with the sheet for touch panels which have a laminated body of 7th or 8th this invention, respectively.

According to the present invention, in conductive members such as transparent conductive films and metal circuits, including ITO, without causing malfunctions due to corrosion, etc., they are excellent in heat resistance and moisture and heat resistance, and have good plasticizer resistance and good workability. A pressure-sensitive adhesive composition (hereinafter, simply referred to as a "pressure sensitive adhesive composition" or "adhesive composition") for a conductive member having high adhesiveness can be provided.

First, urethane urea resin (A) is demonstrated. The urethane urea resin (A) is a resin having a weight average molecular weight (Mw) of 50,000 to 200,000 formed by reacting a polyamino compound (c) with a urethane prepolymer obtained by reacting a polyol (a) with a polyisocyanate (b). .

As a polyol (a) to be used, a well-known thing can be used, A polyether polyol, polyester polyol, polycarbonate polyol, these copolymers, other glycols, etc. are mentioned. The specific compound mentioned below can also be used in combination of multiple types.

As polyether polyol, a well-known polyether polyol can be used. For example, polymers, copolymers, and graft copolymers of alkylene oxides such as propylene oxide, tetrahydrofuran, ethylene oxide and butylene oxide;

What has two or more hydroxyl groups, such as polyether polyol by condensation of hexanediol, methylhexanediol, heptanediol, octanediol, or a mixture thereof, can be used.

Moreover, the glycol which added alkylene oxides, such as ethylene oxide, to bisphenols, such as bisphenol A and bisphenol F, can be used.

As polyester polyols, well-known polyester polyol can be used. As a polyester polyol, there exists a polyester polyol in which the polyfunctional alcohol component and the dibasic acid component condensed.

As the polyfunctional alcohol component, for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, octanediol, butylethylpentanediol, 2-ethyl-1,3 The compound which has two hydroxyl groups, such as -hexanediol, cyclohexanediol, bisphenol A, bisphenol F, is mentioned, Furthermore, the compound which has three or more hydroxyl groups, such as glycerin, trimethylol propane, pentaerythritol, is mentioned.

Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid and trimellitic acid.

Further, β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanollactone, and α- Polyester polyol obtained by ring-opening polymerization of cyclic ester compounds, such as lactones, such as methyl (beta)-propiolactone, can also be used.

The polycarbonate polyols have a structure represented by the following general formula [1] in the molecule thereof, and known polycarbonate polyols can be used.

Formula [1]:

-[-OR ¹ -O-CO-] _m-

(Wherein, R ¹ represents a divalent organic residue and m represents an integer of 1 or more)

The polycarbonate polyol is obtained through, for example, reaction of (1) glycol or bisphenol and carbonate ester, (2) reaction of phosgene in the presence of alkali in glycol or bisphenol, and the like.

 Specific examples of the carbonate ester used in the production method of (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

 As glycol or bisphenol used by the manufacturing method of (1) and (2), for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5 -Pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1 , 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol; Or bisphenols such as bisphenol A and bisphenol F; Bisphenol which added alkylene oxides, such as ethylene oxide and a propylene oxide, to bisphenol; Etc. can also be used. These compounds can be used as 1 type or in mixture of 2 or more types.

As a commercial item of a polycarbonate polyol, KURARAY POLYOL C series of KURARAY CO., LTD. Can be used. Among them, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, C-2015N are flexible and are polypropylene as a raw material of urethane urea resin (A). It can use together preferably with the polyol which has a glycol skeleton.

Examples of other glycols include compounds having two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6-hexanediol, neopentyl glycol, and cyclohexanedimethanol.

In addition, compounds having three or more hydroxyl groups, such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol and methylglucoside, can also be used as the polyol (a).

As other glycols, polyols containing at least one ionic functional group can be used. Examples of the ionic group include carboxyl group, phosphoric acid group, sulfonic acid group, primary to tertiary amino group, quaternary ammonium group, phosphonium group, and quaternary sulfonium group.

The polyol containing at least one ionic functional group has the point of making the urethane urea resin (A) included in the present invention aqueous, increasing the reaction rate in synthesizing a urethane prepolymer, and further improving the film formability. Although it is used suitably, since an ionic group is introduce | transduced into urethane urea (A), especially when an ionic group is an acidic group, there exists a possibility of corrosive a transparent conductive film and a metal circuit. Therefore, although the polyol containing at least 1 ionic functional group is used as needed, it is preferable not to use more than a required amount also in this case, and it is especially preferable not to use all.

For example, when a polyol having a carboxyl group is used as the polyol containing at least one ionic functional group, a carboxyl group can be introduced into the urethane urea resin (A), and the carboxyl group can be used as a reaction point with a curing agent (B) described later. Can be.

As a polyol containing at least 1 ionic functional group, dioxycarboxylic acid, such as dimethylol propionic acid and dimethylol butanoic acid, etc. are mentioned, for example.

As a polyol (a) of the urethane urea resin (A), it is preferable to use a polyol having a polypropylene glycol skeleton in terms of transparency of the pressure-sensitive adhesive layer and the like, and in 100% by weight of the total polyol (a) to be used. It is preferable that it is 50 weight% or more from a viewpoint of ensuring sufficient adhesiveness, 50-100 weight% is preferable, and, as for the quantity of the polyol which has a polypropylene glycol skeleton, 100 weight% is more preferable.

The number average molecular weight of the polyol (a) is preferably 800 or more from the viewpoint of securing the adhesive force of the pressure-sensitive adhesive, and preferably 4,000 or less from the viewpoint of securing the heat resistance of the pressure-sensitive adhesive, and more preferably 1,000 to 3,000. If the number average molecular weight of the polyol (a) is too small, it may cause an increase in the urethane and urea bond concentrations in the resin, which may lower the adhesive force, while when too large, the decrease in the urethane bond and the urea bond which adds cohesive force to the pressure-sensitive adhesive. May cause damage to the heat resistance of the pressure-sensitive adhesive.

Since the said polyol (a) satisfies the performance as a pressure-sensitive adhesive composition, it is preferable to select suitably so that the glass transition temperature (Tg) of a urethane urea resin (A) may be 0-80 degreeC. In addition, glass transition temperature is the value calculated | required using DSC (differential scanning calorimeter).

As a polyisocyanate (b), a conventionally well-known thing can be used, For example, aromatic polyisocyanate, aliphatic polyisocyanate, an aliphatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned. The specific compound mentioned below can also be used in combination of multiple types.

As an aromatic polyisocyanate, 1, 3- phenylene diisocyanate, 4, 4'- diphenyl diisocyanate, 1, 4- phenylene diisocyanate, 4, 4'- diphenylmethane diisocyanate, 2, 4- toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'- diphenyl ether Diisocyanate, 4,4 ', 4' '-triphenylmethanetriisocyanate, and the like.

As aliphatic polyisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (nickname: HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2, 3- butylene diisocyanate, 1, 3- Butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. are mentioned.

Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethyl Benzene, 1,4-tetramethyl xylene diisocyanate, 1,3-tetramethyl xylene diisocyanate, etc. are mentioned.

As alicyclic polyisocyanate, isophorone diisocyanate (nickname: IPDI), 1, 3- cyclopentane diisocyanate, 1, 3- cyclohexane diisocyanate, 1, 4- cyclohexane diisocyanate, methyl-2, 4- cyclo Hexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4,4'- methylenebis (cyclohexyl isocyanate), 1, 4-bis (isocyanate methyl) cyclohexane, etc. are mentioned.

Moreover, the trimethylolpropane adduct of the said polyisocyanate (b), the trimer which has an isocyanurate ring, etc. can be used together at one part. Polyphenylmethane polyisocyanate (nickname: PAPI), naphthylene diisocyanate, these polyisocyanate modified products, etc. can also be used. Moreover, as a polyisocyanate modified substance, the modified | denatured which has a carbodiimide group, a uretdione group, a uretonimine group, the biuret group which reacted with water, the group of any one of isocyanurate groups, or two or more of these groups is mentioned. Water can be used. The reactant of a polyol and diisocyanate can also be used as a polyisocyanate (b).

In the present invention, as the polyisocyanate (b), 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate (nickname: IPDI), xylene diisocyanate, 4,4'- methylene bis ( It is preferable from the viewpoint of weather resistance to use a polyisocyanate-modified or egg yolk-modified polyisocyanate compound such as cyclohexyl isocyanate) (alias: hydrogenated MDI).

Moreover, it is preferable to use isophorone diisocyanate (nickname: IPDI) from the viewpoint of controlling transparency and reactivity of the adhesive composition as the polyisocyanate (b).

The amount of the polyisocyanate (b) used, i.e., the prepared amount, is preferably 8% by weight or more from the viewpoint of maintaining the cohesive force of the pressure-sensitive adhesive and adding durability in 100% by weight of the urethane urea resin (A), and the flexibility of the resin It is preferable that it is 23 weight% or less from a viewpoint of preventing a fall and ensuring sufficient adhesive force, More preferably, it is 10-21 weight%. Here, "in 100 weight% of urethane urea resins (A)" means "in 100 weight% of synthetic raw materials of a urethane urea resin (A)", and the polyol (a) used for synthesis | combination of a urethane urea resin (A) ), Polyisocyanate (b), polyamino compound (c), and in 100% by weight of the reaction terminator (d) to be used as necessary, means (the same also in the following description). That is, the amount of polyisocyanate (b) in the total 100% by weight of the polyol (a), the polyisocyanate (b), the polyamino compound (c), and the reaction terminator (d) when using the reaction terminator (d) It is preferable that (use amount or preparation amount) is 8-23 weight%.

Next, the polyamino compound (c) used for this invention is demonstrated. As this polyamino compound (c), a well-known thing can be used as a compound which has two or more amino groups. By using the compound which has two or more amino groups, the adhesive force of a pressure-sensitive adhesive agent can be added, and compatibility with durability can be attained. The specific compound mentioned below can also be used in combination of multiple types.

Specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2- Hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) Aliphatic polyamines such as diamine, (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine and piperazine;

Alicyclic polyamines such as isophorone diamine and dicyclohexyl methane-4,4'-diamine;

Phenylenediamine, xylylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4 ' Aromatic diamines such as -bis- (sec-butyl) diphenylmethane;

 And the dimer diamine which converted the carboxyl group of dimer acid to an amino group, the dendrimer which has a primary or secondary amino group at the terminal, etc. can be illustrated.

Moreover, as a polyamino compound (c), the polyoxyalkylene glycol diamine etc. which have propoxyamine at both terminals and are represented by following General formula [2] can also be used.

General formula [2]:

H ₂ N-CH ₂ -CH ₂ -CH ₂ -O- (C _m H _2m -O) _n -CH ₂ -CH ₂ -CH ₂ -NH ₂

(Wherein m represents an arbitrary integer of 2 to 4, n represents an arbitrary integer of 2 to 50)

As a polyamino compound (c) used by this invention, the compound (c3) which made Michael addition-react the ethylenically unsaturated compound (c2) to the compound (c1) which has 2 or more primary amino groups especially from a viewpoint of controlling reaction. This is preferable, and as ethylenically unsaturated compound (c2), it is preferable to use the ethylenically unsaturated compound which has a hydroxyl group from the viewpoint of the crosslinking point introduction into a urethane urea resin (A).

As a compound (c1) which has 2 or more primary amino groups, the compound which has said 2 or more amino groups can be used, Especially isophorone diamine, 2,2,4-trimethylhexamethylenediamine, and hexamethylenediamine are Michael It is preferable at the point which is easy to control addition reaction, and is excellent in transparency of the urethane urea resin (A) obtained using compound (c3) obtained by making Michael addition reaction.

As an ethylenically unsaturated compound which has a hydroxyl group in an ethylenically unsaturated compound (c2), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl alcohol;

DAICEL CHEMICAL INDUSTRIES, LTD. Unsaturated compounds having a polyester chain having a hydroxyl group at the terminal, such as PLACCEL FA, PLACCEL FA2D, PLACCEL FA3, PLACCEL FA5, PLACCEL FA10L, PLACCEL FM1D, PLACCEL FM2D, PLACCEL FM3, PLACCEL FM3X, PLACCEL FM5, PLACCEL FM5L, etc .;

Unsaturated compounds having a polyether chain having a hydroxyl group at the terminal, such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, and hexaethylene glycol (meth) acrylate ; Can be mentioned.

Although the said compound can be used individually or in combination of 2 or more types, it is preferable to use 4-hydroxybutylacrylate especially from a viewpoint of the reactivity with the hardening | curing agent (B) mentioned later, the optical characteristic of a pressure-sensitive adhesive, etc. Do.

Examples of the ethylenically unsaturated compound (c2) having no hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) Acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate Alkyl having 1 to 22 carbon atoms, such as octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, and docosyl (meth) acrylate (Meta) acrylic It can be the root. When aiming at the adjustment of polarity, C2-C10 is preferable, More preferably, the alkyl group containing acrylate which has a C2-C8 alkyl group, or the corresponding methacrylate is mentioned. When aiming at adjustment of leveling property etc., carbon number 6 or more is preferable.

Moreover, as ethylenic unsaturated compound (c2), methoxy polyethyleneglycol (meth) acrylate, ethoxy polyethyleneglycol (meth) acrylate, propoxy polyethyleneglycol (meth) acrylate, n-butoxy polyethyleneglycol (meth) Acrylate, n-pentoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polytetramethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, methoxy Alkoxy polyalkylene glycol mono (meth) acrylates, such as hexaethylene glycol (meth) acrylate, or phenoxy polyalkylene glycol mono (meth) acrylate;

Fatty acid vinyls such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl lauryl acid, vinyl palmitate, and vinyl stearate;

 Vinyl ethers such as butyl vinyl ether and ethyl vinyl ether;

 Α-olefins such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene;

Maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β Carboxyl group-containing unsaturated compounds such as-(meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid;

Nitrogen-containing unsaturated compounds such as amide group-containing unsaturated compounds, dialkylamino group-containing unsaturated compounds, and quaternary ammonium base-containing unsaturated compounds;

 You can use together.

Examples of the amide group-containing unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-pro Foxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol- N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acryl Amide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N -Di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pen Methoxymethyl) methacrylamide, etc. are mentioned.

Examples of the dialkylamino group-containing unsaturated compound include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, and methylethylamino Ethyl (meth) acrylate, dimethylamino styrene, diethylamino styrene, etc. are mentioned.

A quaternary ammonium base containing unsaturated compound is obtained by quaternary ammoniumization of the said dialkylamino group containing unsaturated compound. Counterions as Cl ^-, Br ^-, I ^- halogen ion or QSO ₃ of: ^- As the quaternary ammonium salt group-containing unsaturated compound having a (Q alkyl group having a carbon number of 1 to 12) (meth) acrylate, dimethylaminoethyl chloride salt, Trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidepropyl) ammonium chloride, and trimethyl-3- (1- (meth) ) Acrylamide-1,1-dimethylethyl) ammonium chloride, etc. are mentioned.

Moreover, as ethylenically unsaturated compound (c2), perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluoro butylethyl (meth) acrylate, and 2-perfluoro Rohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2 -Perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluorooctylounde Perfluoroalkyl (meth) acrylate which has a C1-C20 perfluoroalkyl group, such as a thread (meth) acrylate;

Perfluoroalkyl group-containing unsaturated compounds such as perfluoroalkylalkylenes such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene;

Unsaturated compounds having an alkoxysilyl group such as vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane, and derivatives thereof;

Epoxy group-containing unsaturated compounds such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate;

Allyl compounds such as allyl acetate, allyl benzene and allyl cyanide;

Vinyl compounds such as vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, and chlorostyrene;

Ethynyl compounds such as acetylene, ethynyl benzene and ethynyl toluene;

Etc. can also be used together.

In Michael addition reaction of the compound (c1) which has 2 or more primary amino groups, and ethylenically unsaturated compound (c2), 1 mol of active hydrogens of the amino group in the compound (c1) which have 2 or more primary amino groups, and ethylene 1 mol of ethylenically unsaturated groups in a sex unsaturated compound (c2) react. Since the amino group in the compound (c1) having two or more primary amino groups easily reacts with the ethylenically unsaturated group of the compound having an electron withdrawing group, the (meth) acrylic compound is preferable as the ethylenically unsaturated compound (c2). In particular, an acrylate compound is most preferable in view of the efficiency of the Michael addition reaction.

As a synthesis method of the compound (c3) which Michael addition-reacted the ethylenically unsaturated compound (c2) to the compound (c1) which has two or more primary amino groups, the well-known method regarding Michael addition reaction can be used as it is. When ethylenically unsaturated compound (c2) is a (meth) acrylic-type compound, especially an acrylate-type compound etc., reaction advances at 10-100 degreeC under catalysts, such as alcohol, as needed. Although depending on the kind of ethylenically unsaturated compound (c2) to be used, the reaction temperature of 40-80 degreeC is preferable. Too high a reaction temperature is undesirable because an esteramide exchange reaction occurs.

In the case where the ethylenically unsaturated compound (c2) does not have an electron withdrawing group, the reaction is possible in the presence of a metal catalyst, and in this case, the reaction is carried out at 60 to 100 ° C. while heating in the presence of a catalyst.

The solvent for synthesis may or may not be used, and the kind thereof is not particularly limited, and known solvents such as methyl ethyl ketone, toluene, acetone, benzene and the like may be used. The solution concentration in the case of using a solvent becomes like this. Preferably it is 20 weight% or more, More preferably, it is 50 weight% or more. If it is thinner than this, the reaction is difficult to proceed and is not preferable.

Although reaction time changes with kinds of ethylenically unsaturated compound (c2) to be used, it ends in 30 minutes-5 hours.

About the ratio of the ethylenically unsaturated compound (c2) which adds to the compound (c1) which has two or more primary amino groups, so that at least 2 primary or secondary amino groups remain in the compound (c3) which Michael addition-reacted, The ethylene in the ethylenically unsaturated compound (c2) is preferably 0.1 to 1.0 mol, more preferably 0.2 to 1.0 mol with respect to 1 mol of the primary amino group of the compound (c1) having two or more primary amino groups. It is preferable to react the unsaturated unsaturated group. If the amount of the ethylenically unsaturated group is smaller than this, the effect of introducing the ethylenically unsaturated compound (c2) may not be obtained, and the storage stability is also low, which is not preferable, but on the other hand, it does not contribute to the reaction.

It is preferable that the usage-amount of a polyamino compound (c) is 0.5 weight% or more from a viewpoint of maintaining the cohesion force of a pressure-sensitive adhesive and adding durability in 100 weight% of urethane urea resins (A), and prevents the softness of resin from falling. It is preferably 8% by weight or less, more preferably 2 to 5% by weight from the viewpoint of ensuring sufficient adhesive strength. That is, the polyamino compound (c) of the total 100% by weight of the polyol (a), the polyisocyanate (b), the polyamino compound (c), and the reaction terminator (d) when the reaction terminator (d) is used It is preferable that quantity (consumption amount or preparation amount) is 0.5-8 weight%.

The urethane urea resin (A) is obtained by reacting a urethane prepolymer having an isocyanate group with a polyamino compound (c), but can further react a monoamino compound as a reaction terminator (d), if necessary. That is, in the synthesis of the urethane urea resin (A), the reaction stopping agent (d) for controlling the molecular weight or reacting with the isocyanate group remaining in the unreacted end of the urethane urea resin (A) to stabilize the reaction activity of the resin (d) ) Can be used. In this case, the urethane urea resin (A) is made by reacting a polyamino compound (c) with a reaction terminator (d) with a urethane prepolymer formed by reacting a polyol (a) with a polyisocyanate (b).

As the reaction terminator (d), for example, in addition to dialkylamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine, diisononylamine,

Monoamines having hydroxyl groups such as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl-1,3-propanediol ;

Alkyl hydrazines such as monomethyl hydrazine, 1,1-dimethyl hydrazine, benzyl hydrazine, hydrazides such as form hydrazide, acetohydrazide and lauric acid hydrazide;

 Compounds having a tertiary amino group and a primary amino group such as N, N-dimethyl-1,3-propanediamine and N, N-diethyl-1,3-propanediamine;

monoamino compounds having an alkoxysilyl group such as γ-aminopropyltriethoxysilane; and the like can be used. Moreover, the amino compound which has only one primary or secondary amino group can also be used as a reaction terminator.

Among the above reaction terminators (d), when a monoamine compound having a hydroxyl group, such as 2-amino-2-methyl-propanol, is used, a urethane urea resin excellent in storage stability having a hydroxyl group at the terminal can be obtained. Moreover, the urethane urea resin whose terminal is a hydroxyl group is preferable at the point which can be used as a reaction point with the hardening | curing agent (B) mentioned later. In the case of the monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanate group of the urethane prepolymer, but the amino group has a high reactivity, and therefore preferentially reacts with the isocyanate group.

It is preferable that the usage-amount when using the said reaction terminator (d) is 0.05 weight% or more from the viewpoint of ensuring reaction stability of resin among 100 weight% of urethane urea resins (A), and the weight average molecular weight of resin ( It is preferable that it is 2 weight% or less from a viewpoint of controlling Mw) suitably and ensuring durability of a pressure-sensitive adhesive.

The cyclic ester compound and / or the cyclic ether compound can be ring-opened to modify the hydroxyl group of the thus-obtained urethane urea resin (A).

About the manufacturing method of the urethane urea resin (A) used for this invention, a polyol (a) and a polyisocyanate (b) are made to react first, and the urethane prepolymer which has at least 1 isocyanate group is produced. Then, the obtained urethane prepolymer, the polyamino compound (c), and the reaction terminator (d) can be reacted as necessary to produce a urethane urea resin (A).

In the synthesis of the urethane prepolymer, a known catalyst can be used. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (nickname: DBU), and the like, alone or two kinds. The above can be used in combination.

Examples of the organometallic compound include tin compounds and non-tin compounds.

Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (alias DBTDL), dibutyltin diacetate, and dibutyltin sulfide. , Tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, dioctyltin Dilaurate (nickname: DOTDL), 2-ethylhexanoic acid tin and the like.

Examples of the non-tin compound include titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, lead-based oleate, 2-ethylhexanoate, lead benzoate and lead naphthenate, and the like. Iron type such as iron ethyl hexanoate and iron acetylacetonate, cobalt type such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc type such as zinc naphthenate and zinc 2-ethylhexanoate, and naphthenate nitrate have.

Among the above catalysts, dibutyltin dilaurate (nickname: DBTDL), dioctyltin dilaurate (nickname: DOTDL), 2-ethylhexanoic acid tin and the like are preferable in view of reactivity and hygiene.

Catalysts such as tertiary amine compounds and organometallic compounds may be used alone, but may be used in combination. In particular, in the case of using polyester diols and polyether diols together as a polyol component, dibutyltin di It is preferable to use laurate and tin 2-ethylhexanoate in combination because it can stably obtain a uniform urethane prepolymer.

The organometallic compound catalyst used for the synthesis of the urethane prepolymer significantly promotes the reaction when the urethane prepolymer reacts with the polyamino compound (c). Although reaction of an isocyanate group and an amino group is originally very fast, in the presence of an organometallic compound catalyst, reaction may be accelerated and it may be difficult to control. At this time, if a chelate compound is present, the chelate compound forms a chelate with the organometallic compound catalyst so that the catalytic capacity of the organometallic compound catalyst can be adjusted, and the reaction with the polyamino compound (c) can be easily controlled.

Examples of the chelate compound include acetylacetone, dimethylglyoxime, auxin, dicyzone, polyaminooxy acid such as ethylenediamine tetraacetic acid (aka EDTA), oxycarboxylic acid such as citric acid, and condensed phosphoric acid. Among the chelate compounds, acetylacetone is preferable because it is soluble in organic solvents, has volatility, and is easily removed as necessary.

In particular, the chelate compound remains in the urethane urea resin (A) even after the reaction if not removed. Although the pressure-sensitive adhesive composition for conductive members of the present invention containing the urethane urea resin (A) contains a curing agent (B), at this time, the chelating compound is a reaction rate of the urethane urea resin (A) and the curing agent (B). As a result, the pressure-sensitive adhesive composition for conductive members excellent in storage stability can be provided as a result.

In the synthesis of the urethane prepolymer, a known solvent is suitably used. The use of a solvent serves to facilitate reaction control. As a solvent used for this purpose, for example, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrroli Toner, dimethylformamide, etc. are mentioned. Ethyl acetate, toluene, methyl ethyl ketone, or a mixed solvent thereof are particularly preferable in view of the solubility of the urethane urea resin (A), the boiling point of the solvent, and the solubility of the polyamino compound (c). The concentration in the urethane prepolymer reaction system in the case of using a solvent is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, and when the concentration is too low, the reactivity is too low, which is not preferable. not.

Although various methods can be used as a urethanation reaction which synthesize | combines a urethane prepolymer, it can be divided roughly into the following two methods.

 [i] A method of preparing and reacting a polyol (a), a polyisocyanate (b), a solvent, and a whole amount of the catalyst.

 [ii] A method of preparing a polyol (a) and a solvent in a flask, dropping the polyisocyanate (b), and then reacting by adding a catalyst as necessary.

In the case of precisely controlling the reaction, [ii] is preferable.

It is preferable that the temperature of the urethanation reaction which obtains a urethane prepolymer is 120 degrees C or less, More preferably, it is 50-110 degreeC. When the temperature is higher than 120 ° C, control of the reaction rate becomes difficult, and it becomes difficult to obtain a urethane prepolymer having a predetermined weight average molecular weight and a structure. Therefore, it is preferable to perform a urethanation reaction at 50-110 degreeC for 1 to 20 hours in presence of a catalyst.

The blending ratio of the polyol (a) and the polyisocyanate (b) greatly depends on the reactivity of the compound, the abundance of the trivalent or higher compound, the use of the resin obtained, and the like. In order for the urethane prepolymer to have at least one isocyanate group, the isocyanate group in the polyisocyanate (b) needs to be more than 1 mole with respect to 1 mole of the hydroxyl group in the polyol (a), preferably 1.01 to 4.00 moles, more preferably The range of 1.10-2.00 mol is suitable.

The urea reaction of the isocyanate group in the urethane prepolymer which is an isocyanate group-containing compound obtained as described above with the primary or secondary amino group of the polyamino compound (c) is largely divided into the following two methods.

 [iii] A method of preparing a urethane prepolymer in a flask and reacting by dropwise addition of the polyamino compound (c).

 [iv] A method for preparing a polyamino compound (c) in a flask, followed by dropwise addition of a urethane prepolymer.

If there is no problem in reaction, the method of [iii] which is easy to operate is preferable.

The temperature of the urea reaction is preferably 100 ° C. or lower, more preferably 70 ° C. or lower. 50 degreeC or less is more preferable at the time of 70 degreeC, when reaction rate is large and reaction cannot be controlled appropriately. When the temperature is higher than 100 ° C, control of the reaction rate becomes difficult, and it becomes difficult to obtain a urethane urea resin (A) having a predetermined weight average molecular weight and structure. In the case where an alcohol solvent is used as the synthetic solvent for the polyamino compound (c), the temperature in the reaction system is preferably set to 50 ° C or lower, more preferably 40 ° C or lower when the polyamino compound (c) is added dropwise. .

The amount of the reaction terminator (d) is different depending on the case where it is mixed with the polyamino compound (c) and when the compound is added lastly, but in the case of the mixture addition, 1 mole of isocyanate groups in the urethane prepolymer, The amino group in the reaction terminator (d) is preferably 0.5 mol or less, more preferably 0.3 mol or less. On the other hand, when the reaction terminator (d) is added last alone, it is preferable that the amino group in the reaction terminator (d) is 0.5 to 3.0 mol with respect to 1 mole of the isocyanate group finally present, particularly urethane urea resin When aiming at stabilization of (A), 1-3.0 mol is preferable. When the amount of the use of the reaction terminator (d) is out of the above range, there is a case that adverse effects such as deterioration in film formability or discoloration are observed.

The end point of the reaction is determined by the isocyanate% measurement by titration or the disappearance of the isocyanate peak by IR measurement.

The urethane urea resin (A) having a carboxyl group or a tertiary amino group may be ionized by a known method in order to disperse or dissolve in water.

The molecular weight of urethane urea resin (A) needs to be 50,000-200,000 by the weight average molecular weight of standard polystyrene conversion by GPC (gel permeation chromatography). Preferably it is 70,000-180,000, More preferably, it is 80,000-150,000. If this weight average molecular weight is less than 50,000, the balance between the durability as a pressure-sensitive adhesive and the optical function retention property will deteriorate. On the other hand, when this weight average molecular weight exceeds 200,000, adhesive force falls or a viscosity is too high and it becomes difficult to handle.

The solution viscosity of the obtained urethane urea resin (A) is not particularly limited and is selected according to the use of the resin. Preferably, the solution viscosity of the urethane urea resin (A) is 3000 to 25000 mPa · s (25 ° C.) at 50% by weight of solids. If the solution viscosity of the urethane urea resin (A) is too high, the coating process of the adhesive composition may become difficult, and if too low, the resin of sufficient molecular weight may not be obtained.

Next, a hardening | curing agent (B) is demonstrated. The pressure sensitive adhesive composition of this invention contains 0.1-3 weight part of hardening | curing agents (B) with respect to 100 weight part of said urethane urea resins (A). Moreover, an adhesive composition may contain a plurality of types of urethane urea resins (A), and may also contain a plurality of types of curing agents (B).

As a reactive functional group which exists in the said urethane urea resin (A), a hydroxyl group, a carboxyl group, etc. are mentioned. Therefore, an isocyanate group, an epoxy group, an alkoxy silyl group, a methylol group, an aziridine group, a carbodiimide group etc. are mentioned as a functional group which has a hardening | curing agent (B) used for this invention.

Examples of the curing agent (B) include polyisocyanate compounds, polyfunctional epoxy compounds, high molecular weight polycarbodiimides, N-methylol group-containing compounds, polyfunctional aziridine compounds, metal chelates, and the like. In order to act effectively as a curing agent, a compound having two or more functional groups in the molecule capable of reacting with the hydroxyl group of the urethane urea resin (A) is preferably used. In particular, the polyisocyanate compound is preferably used because it is excellent in adhesiveness after crosslinking reaction and adhesion to a coating layer.

The polyisocyanate compound may be any compound having a plurality of isocyanate groups in a molecule, and is not particularly limited. Examples of the polyisocyanate compound include triylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xyl Polyisocyanate compounds, such as rendiisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes of these polyisocyanate compounds, Isocyanurates, furthermore, these polyisocyanate compounds and known polyether polyols, polyester polyols, acryl polyols, polybutadiene polyols, and polyisoprene polyols There may be mentioned air duct member such as.

The polyfunctional epoxy compound may be a compound having a plurality of epoxy groups in a molecule, and is not particularly limited. Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A epichlorohydrin type epoxy resin, and N. , N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N And N-diglycidyl toluidine and the like.

As high molecular weight polycarbodiimide, the CARBODILITE series of NISSHINBO CHEMICAL INC. Is mentioned. Especially, CARBODILITE V-01, 03, 05, 07, 09 is more preferable because it is excellent in compatibility with an organic solvent.

Examples of the polyfunctional aziridine compound include 2,2'-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate] and 4,4'-bis (ethyleneiminocarbonylamino ) Diphenylmethane and the like.

Examples of the metal chelate include coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and acetylacetone and ethyl acetoacetate. Can be mentioned.

The said hardening | curing agent (B) can be used individually or in combination. As said hardening | curing agent (B), a polyisocyanate compound is preferable from a viewpoint of reactivity and a pot life, Furthermore, from the optical characteristic of a pressure-sensitive adhesive layer, Furthermore, foam release peelability etc., In particular, hexamethylene diisocyanate trimethylol The propane adduct body, the hexamethylene diisocyanate isocyanurate body, the hexamethylene diisocyanate biuret body, or the xylene diisocyanate trimethylol propane adduct body is preferable.

The pressure-sensitive adhesive composition according to the present invention contains 0.1 to 3 parts by weight of the curing agent (B) based on 100 parts by weight of the urethane urea resin (A). Moreover, it is more preferable to contain 0.2-1.5 weight part of hardening | curing agents (B). When the amount of the curing agent (B) exceeds 3 parts by weight, the crosslinked structure of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition becomes dense, and the adhesiveness of the pressure-sensitive adhesive layer tends to decrease, and the adhesion to the adherend is lowered. On the other hand, if the amount of the curing agent (B) is less than 0.1 part by weight, a sufficient crosslinked structure cannot be obtained, so that the cohesive force is lowered, and the heat resistance and the heat and moisture resistance are lowered.

By the reaction of the reactive functional group of the urethane urea resin (A) with the functional group in the curing agent (B), the urethane urea resin (A) is three-dimensionally crosslinked to ensure adhesion to various substrates and adherends, Furthermore, under extreme conditions, heat resistance and heat and humidity resistance can be improved. Therefore, the adhesive composition which concerns on this invention can be used especially suitably for electrically conductive members.

The pressure-sensitive adhesive composition of the present invention may contain a silane coupling agent having an alkoxysilyl group for the purpose of improving the heat and moisture resistance. In the pressure-sensitive adhesive layer, the silane coupling agent is particularly easy to form an inclined structure, is localized on the surface of the adhesive layer, and is considered to be particularly effective in improving the moisture-resistant heat resistance and adhesive strength.

As a silane coupling agent, a well-known thing can be used. For example, γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxy Silane compounds having a (meth) acryloxy group and an alkoxy group such as propyltributoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, and γ- (meth) acryloxypropylmethyldiethoxysilane;

Alkoxysilanes having vinyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane and vinylmethyldimethoxysilane;

Alkoxysilanes such as 5-hexenyltrimethoxysilane, 9-decenyltrimethoxysilane and styryltrimethoxysilane;

silanes having aminoalkyl groups and alkoxy groups, such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane;

γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptomethylphenylethyltrimethoxysilane Compounds having a mercapto group such as mercaptomethyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, and 10-mercaptodecyltrimethoxysilane;

Compounds having imidazole groups such as IS-1000, IA-100A, IM-1000, and SP-10 (manufactured by NIPPON MINING & METALS CO., LTD.);

Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane;

3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3- Chloropropyltrimethoxysilane, phenyltrimethoxysilane, hexamethylsilazane, diphenyldimethoxysilane, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, vinyltris (2- Methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-isocyanatepropyltriethoxy Silane and the like.

Any 1 or more types of these can be used individually or in mixture of multiple types.

Among the silane coupling agents, it is preferable to use a silane coupling agent having 3-isocyanate propyl triethoxy silane, 3-glycidoxy propyl trimethoxy silane, or an imidazole group from the viewpoint of improving the heat and moisture resistance properties. desirable. In particular 3-isocyanatepropyltriethoxysilane or IM-1000 (imidazol group-containing silane; 3- (imidazol-1-yl) -2-methylpropanoic acid 3- (trimethoxysilyl) propyl and its partial hydrolysis When a mixture of the reaction product) is used, workability, plasticizer resistance, heat resistance, and heat resistance can be significantly improved, and a pressure-sensitive adhesive composition having a particularly high adhesion to the conductive member can be obtained.

In the case of using the silane coupling agent, it is preferable to use at least 0.1 part by weight in order to obtain sufficient moisture resistance and adhesion improvement effect against 100 parts by weight of the urethane urea resin (A). Not only can the effect not be obtained, but the adhesive strength may be lowered. desirable.

As the pressure-sensitive adhesive composition according to the present invention, other resins such as acrylic resins, polyester resins, amino resins, epoxy resins, and polyurethane resins may be used in combination as necessary. Moreover, additives, such as an organic / inorganic pigment, a filler, a coloring agent, a ultraviolet absorber, antioxidant, an antifoamer, a light stabilizer, can also be mix | blended according to a use.

The conductive member (conductive member) to which the pressure-sensitive adhesive composition of the present invention is used is not particularly limited as long as it is a conductive member, and a conductive metal circuit formed of a transparent conductive film such as ITO or ATO, a metal deposition film, or metal particles can be used. Can be mentioned.

Using the pressure-sensitive adhesive composition according to the present invention, a laminated product (hereinafter referred to as "pressure-sensitive adhesive sheet for conductive member" or "pressure-sensitive adhesive sheet") containing a pressure-sensitive adhesive layer and a sheet-like base material can be obtained. For example, the pressure-sensitive adhesive sheet for conductive members can be obtained by coating, drying, and curing the pressure-sensitive adhesive composition of the present invention on one or both surfaces of various sheet-shaped base materials. The pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet has adhesiveness at about room temperature because it is "pressure sensitive".

In coating the adhesive composition, an appropriate liquid medium, for example, an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, isopropyl alcohol, other hydrocarbon solvents, or water may be further added to adjust the viscosity. The viscosity can also be reduced by heating the adhesive composition. However, when a large amount of water or alcohol is added, it is possible to cause a reaction inhibition between the urethane urea resin (A) and the curing agent (B).

Although it does not specifically limit as a sheet-shaped base material, It is a flat form, such as an optical film, such as a cellophane, various plastic sheets, rubber | gum, foam, a cloth, rubberized cloth, resin impregnation cloth, glass plate, a metal plate, wood, and a polarizing plate. It can be mentioned. In addition, various base materials may be used independently, and what exists in the multilayered state which laminated | stacked several things can also be used. Moreover, what peeled the surface or the antistatic treatment can also be used.

Various plastic sheets are also called various plastic films, Film of polyolefin resin, such as a polyvinyl alcohol film, a triacetyl cellulose film, a polypropylene, polyethylene, a polycycloolefin, ethylene-vinyl acetate copolymer; Films of polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Film of polycarbonate resin, film of polynorbornene resin, film of polyarylate resin, film of acrylic resin, film of polyphenylene sulfide resin, film of polystyrene resin, film of vinyl resin, polyamide resin A film, a film of polyimide-type resin, an epoxy resin, the film of cycloolefin resin, etc. are mentioned.

After applying the adhesive composition to the sheet-like substrate in a suitable manner according to a conventional method, when the adhesive composition contains a liquid medium such as an organic solvent or water, the liquid medium is removed or the pressure-sensitive adhesive composition is volatilized. If it does not contain a liquid medium to be formed, the adhesive layer in the molten state may be cooled and solidified, thereby forming an adhesive layer on the sheet-like substrate. It is preferable that it is 0.1 micrometer-250 micrometers, and, as for the thickness of a pressure-sensitive adhesive layer, it is more preferable that it is 20 micrometers-200 micrometers. If it is less than 0.1 micrometer, sufficient adhesive force may not be obtained, and even if it exceeds 250 micrometers, characteristics, such as adhesive force, may not improve any more.

There is no restriction | limiting in particular as a method of coating an adhesive composition on a sheet-like base material, Various types, such as a Mayer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a lip coater, a comma coater, a knife coater, a river coater, a spin coater, etc. Coating method is mentioned. There is no restriction | limiting in particular in the drying method of an adhesive bond layer, The thing using hot air drying, an infrared ray, or the pressure reduction method is mentioned. As dry conditions, although it changes with the hardening | curing form of a adhesive composition, film thickness, and the solvent chosen, it is good to carry out by hot air heating about 60-180 degreeC normally.

The pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition according to the present invention is laminated on a transparent optical member including a PET film, glass, or the like, or a conductive member such as a transparent conductive film such as ITO, a metal circuit, or the like. Can be formed. In the laminate according to the present invention, a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition according to the present invention is laminated on any conductive member or transparent optical member. The structure in which a pressure-sensitive adhesive layer is laminated on a conductive member such as a transparent conductive film such as ITO or a metal circuit is particularly effective from the viewpoint of corrosion resistance. On the other side of the pressure-sensitive adhesive layer, a sheet-like base material whose surface is peeled off can be laminated so as to be easily peeled off during use.

This laminated body coats and dries a pressure-sensitive adhesive composition on the peeling process surface of the sheet-like base material with which (A) peeling process was carried out, for example, and pressure-sensitive-sensitive transparent optical members or sheet-like conductive members including PET films, glass, etc. Laminated onto the surface of the adhesive layer (transfer coating), or (b) a pressure-sensitive adhesive composition is coated and dried on a transparent optical member or sheet-like conductive member including PET film or glass, and then peeled off on the surface of the pressure-sensitive adhesive layer. It can obtain by laminating | stacking (direct coating) the peeling process surface of a sheet-like base material.

For example, the peeled sheet-like base material covering the surface of the pressure-sensitive adhesive layer is peeled off from the laminate having the structure of “peeled sheet-like base material / pressure sensitive adhesive layer / transparent optical member”, and the pressure-sensitive adhesive layer is formed into a sheet-like shape. By adhering to a conductive member (a conductive member such as a transparent conductive film such as ITO or a metal circuit), a sheet for a touch panel having a configuration of "transparent optical member / pressure sensitive adhesive layer / conductive member" can be obtained. Moreover, the peeled sheet | seat which covered the surface of a pressure-sensitive adhesive layer from the laminated body of the structure called "a peeled sheet / pressure-sensitive adhesive layer / sheet-shaped conductive member (conductive member, such as a transparent conductive film, such as ITO, and a metal circuit)). By peeling a shape base material and adhering a pressure sensitive adhesive layer to a transparent optical member, the sheet for touch panels of a structure called "transparent optical member / pressure sensitive adhesive layer / conductive member" can be obtained.

In addition, the use of the pressure-sensitive adhesive sheet or laminate for the conductive member of the present invention is not particularly limited, but in addition to the touch panel, it is also adapted to various electronic-related members such as liquid crystal displays, plasma displays, electrode peripheral members, and protective film applications. You can.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples do not limit the scope of the invention in any way. In addition, "part" and "%" in an Example mean "weight part" and "weight%" except a special case.

The weight average molecular weight (Mw) of each resin obtained through the synthesis examples 4-25 was calculated | required by the following method.

<Measurement of weight average molecular weight (Mw)>

The measurement of Mw used GPC (gel permeation chromatography) "HPC-8020" by TOSOH CORPORATION. GPC is liquid chromatography in which the substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantitatively determined by the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

Synthesis of Polyamino Compound (c)

Synthesis Example 1

25.0 parts of isophorone diamine (IPDA) and 25.0 parts of toluene were prepared in the four neck flask equipped with the stirrer, the reflux cooling tube, the nitrogen introduction tube, the thermometer, and the dropping funnel, and 19.1 parts of 4-hydroxybutyl acrylate and 18.8 butyl acrylate. Part was added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at 80 ° C for 2 hours, and then 37.9 parts of toluene was added. Ethyl acetate was further added to this and the solid content was adjusted to 50% as the compound (1) solution.

Synthesis Example 2

40.0 parts of isophorone diamine (IPDA) and 40.0 parts of toluene were prepared to the four neck flask equipped with the stirrer, the reflux cooling tube, the nitrogen introduction tube, the thermometer, and the dropping funnel, and 67.8 parts of 4-hydroxybutyl acrylate were dripped at room temperature. After completion of the dropwise addition, the mixture was reacted at 80 ° C for 2 hours, and then 67.8 parts of toluene were added. Ethyl acetate was further added to this and the solid content was adjusted to 50% as the compound (2) solution.

Synthesis Example 3

30.0 parts of isophorone diamine (IPDA) and 30.0 parts of toluene were prepared in the four necked flask equipped with the stirrer, the reflux cooling tube, the nitrogen introduction tube, the thermometer, and the dropping funnel, and 18.4 parts of 2-hydroxyethyl acrylate and 17.6 parts of ethyl acrylate. Part was added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at 80 ° C for 2 hours, and then 36.0 parts of toluene was added. Ethyl acetate was further added and the solid content was adjusted to 50% as the compound (3) solution.

 <Synthesis of urethane urea resin (A)>

Synthesis Example 4

790 parts of SUNNIX PP-2000 (bifunctional polypropylene glycol, manufactured by SANYO CHEMICAL INDUSTRIES CO., LTD.) In a four-necked flask equipped with a stirrer, reflux cooling tube, nitrogen introduction tube, thermometer, and dropping funnel, isophorone diisocyanate 110 225 parts of toluene and 0.075 parts of dioctyl tin dilaurate were prepared as a catalyst, and gradually heated up to 100 degreeC, and reaction was performed for 2 hours. After cooling to 40 ° C, 787 parts of ethyl acetate and 2.5 parts of acetylacetone were added, 48.7 parts of the solution of Compound (1) were added dropwise for 1 hour, and further aged for 1 hour. After checking the remaining amount of isocyanate group by titration, 2.3 parts of 2-amino-2-methyl-propanol and 100 parts of ethyl acetate were added to confirm that the NCO characteristic absorption (2,270 cm ^-1 ) of the IR chart was lost. The weight average molecular weight Mw of this urethane urea resin (A-1) was 115,000.

<Synthesis of Urethane Urea Resin>

Synthesis Example 5 ~ 21

According to the mixing | blending shown in Table 1, urethane urea resin (A-2)-(A-18) were obtained by the method similar to the synthesis example 4.

[Table 1]

[Table 1-1]

[Table 1-2]

The symbol of Table 1 shows the following, respectively.

PP600: SUNNIX PP-600 (bifunctional polypropylene glycol, manufactured by SANYO CHEMICAL INDUSTRIES CO., LTD., Number average molecular weight: 587)

PP1000: SUNNIX PP-1000 (bifunctional polypropylene glycol, manufactured by SANYO CHEMICAL INDUSTRIES CO., LTD., Number average molecular weight: 1020)

PP2000: SUNNIX PP-2000 (bifunctional polypropylene glycol, manufactured by SANYO CHEMICAL INDUSTRIES CO., LTD., Number average molecular weight: 1996)

PP3000: SUNNIX PP-3000 (bifunctional polypropylene glycol, manufactured by SANYO CHEMICAL INDUSTRIES CO., LTD., Number average molecular weight: 3032)

PP4000: SUNNIX PP-4000 (bifunctional polypropylene glycol, manufactured by SANYO CHEMICAL INDUSTRIES CO., LTD., Number average molecular weight: 4007)

PE-62: NEWPOL PE-62 (copolymer of propylene glycol and ethylene glycol, manufactured by SANYO CHEMICAL INDUSTRIES CO., LTD., Number average molecular weight: 2550)

PTMG: PTMG-3000 (bifunctional polytetramethylene glycol, manufactured by HODOGAYA CHEMICAL CO., LTD., Number average molecular weight: 2921)

P-2010: KURARAY POLYOL P-2010 (bifunctional polyester polyol, manufactured by KURARAY CO., LTD., Number average molecular weight: 1962)

C-2090: KURARAY POLYOL C-2090 (bifunctional polycarbonate polyol, manufactured by KURARAY CO., LTD., Number average molecular weight: 2011)

IPDI: isophorone diisocyanate

HMDI: hexamethylene diisocyanate

DOTDL: Dioctyl Tin Dilaurate

DBTDL: Dibutyltin Dilaurate

IPDA: isophoronediamine

AMP: 2-amino-2-methyl-propanol

<Synthesis of Urethane Resin>

Synthesis Example 22

68 parts of polyester polyol P-1010 (bifunctional polyester polyol, manufactured by KURARAY CO., LTD.) In a four-necked flask equipped with a stirrer, reflux cooling tube, nitrogen introduction tube, thermometer, and dropping funnel, polyether polyol G- 265 parts of 3000B (trifunctional polyol, manufactured by ASAHI DENKA CO., LTD.), 125 parts of toluene, 0.03 parts of 2-ethylhexanoate and 0.04 parts of lead naphthenate as a catalyst were prepared, and after the liquid became sufficiently uniform, hexamethylene 24 parts of diisocyanate (made by SUMITOMO BAYER CO., LTD.) Was dripped at 1 hour, and reaction was performed at 90 degreeC for 3 hours. The reaction was terminated after confirming that the NCO absorption (2,270cm- ¹ ) of the IR chart was lost. 115 parts of toluene was added and the urethane resin (A-19) was obtained. The weight average molecular weight Mw of this urethane resin (A-19) was 50,000.

<Synthesis of acrylic resin>

Synthesis Example 23

In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping funnel, 98.5 parts of butyl acrylate, 1.5 parts of acrylic acid, and 150 parts of ethyl acetate were prepared, heated to 70 ° C. under nitrogen substitution, and then azobis 0.15 parts of isobutyronitrile was added to initiate polymerization. After the initiation of the polymerization, 0.15 parts of azobisisobutyronitrile were added at intervals of 3 hours to 5 hours after 1 hour, and polymerization was further performed for 2 hours. Thereafter, 150 parts of ethyl acetate was added to terminate the polymerization, to obtain an acrylic resin (A-20). The weight average molecular weight of this acrylic resin (A-20) was 790,000.

<Synthesis of acrylic resin>

Synthesis Example 24

In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping funnel, 97.7 parts of butyl acrylate, 1.5 parts of 2-hydroxyethyl acrylate, and 150 parts of ethyl acetate were prepared, and then replaced with nitrogen at 70 ° C. After heating, 0.15 parts of azobisisobutyronitrile was added to initiate polymerization. After the initiation of the polymerization, 0.15 parts of azobisisobutyronitrile were added at intervals of 3 hours to 5 hours after 1 hour, and polymerization was further performed for 2 hours. Thereafter, 150 parts of ethyl acetate was added to terminate the polymerization, to obtain an acrylic resin (A-21). The weight average molecular weight of this acrylic resin (A-21) was 840,000.

<Synthesis of acrylic resin>

Synthesis Example 25

89.9 parts of butyl acrylate, 10.0 parts of acrylic acid, 0.1 parts of 4-hydroxybutyl acrylate, 63 parts of ethyl acetate, and 100 parts of acetone were prepared in a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel. The mixture was heated to 65 DEG C under nitrogen substitution, and then 0.03 parts of azobisisobutyronitrile was added to initiate polymerization. After the start of the polymerization, after 6 hours, 0.2 part of azobisisobutyronitrile was added, and polymerization was further performed for 6 hours. Thereafter, 45 parts of ethyl acetate was added to terminate the polymerization, to obtain an acrylic resin (A-22). The weight average molecular weight of this acrylic resin (A-22) was 910,000.

Examples 1-23

A hardening | curing agent and a silane coupling agent were mix | blended according to Table 2 with respect to 100 parts of solid content of resin (A-1)-(A-16) obtained through the synthesis examples 4-19, and the pressure-sensitive adhesive composition for electrically conductive members was obtained.

Comparative Examples 1-9

A hardening | curing agent, a metal inactivator, and a silane coupling agent are mix | blended according to Table 3 with respect to 100 parts of solid content of resin (A-1) and (A-17)-(A-22) obtained by the synthesis examples 4 and 20-25. To obtain a pressure-sensitive adhesive composition for a conductive member.

The pressure-sensitive adhesive composition was coated on a peeled polyester film (hereinafter referred to as "peel film") so as to have a thickness of 50 μm after drying, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. After drying, a 100 µm thick polyethylene terephthalate film (PET film) was bonded to the pressure-sensitive adhesive layer. Next, the obtained laminate was aged (dark reaction) for 1 week under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the adhesive layer was performed to obtain a pressure-sensitive adhesive sheet for conductive members.

<Evaluation method of adhesive force>

The pressure-sensitive adhesive sheet was cut to a width of 25 mm, the peeling film was peeled off, and the exposed pressure-sensitive adhesive layer was placed on a PET film having a thickness of 100 μm, a polycarbonate (PC) plate, a glass plate, and an ITO transparent conductive film, respectively, at 23 ° C. After bonding to 50% RH and performing roll crimping according to JIS Z 0237, a pressure of 0.5 MPa was applied under an atmosphere of 50 ° C and held for 15 minutes to obtain a laminate test piece. After 24 hours of pressing, the pressure-sensitive adhesive sheet was peeled from each adherend at 180 degrees peeling and a tensile speed of 300 mm / min using a peel tester under an atmosphere of 23 ° C.-50% RH, and then adhesive strength was measured.

The evaluation criteria are as follows.

 6: Adhesive force is 35 N / 25 mm or more.

 5: The adhesive force is less than 35N / 25mm and 25N / 25mm or more.

 4: The adhesive force is less than 25N / 25mm and 15N / 25mm or more.

 3: The adhesive force is less than 15N / 25mm and 5N / 25mm or more.

 2: The adhesive force is less than 5N / 25mm and 1N / 25mm or more.

1: The adhesive force is less than 1N / 25mm.

<Method for Evaluating Heat and Moisture Resistance>

For evaluation of heat and moisture resistance, the pressure-sensitive adhesive sheet was cut to a width of 100 mm x length of 100 mm, the peeling film was peeled off, bonded to a glass plate, and fixed, and a pressure of 0.5 MPa was applied under a 50 ° C. atmosphere for 20 minutes. After that, a test piece having a layer structure of a PET film / pressure sensitive adhesive layer / glass plate was produced. Flesh peeling and foaming after leaving for 500 hours at 80 ° C-relative humidity 0% (heat resistance) or 60 ° C-relative humidity 95% (humidity heat resistance) were observed visually.

The heat and moisture resistance were evaluated based on the following three evaluation criteria.

 (Circle): Since peeling and foaming are not seen at all, there is no problem practically.

 (Triangle | delta): Although peeling and foaming are seen slightly, there is no problem in practical use.

X: Since the peeling and foaming are all over, it is not practical.

<Evaluation method of foam resistance peeling>

As evaluation of foam resistance peelability, the said pressure-sensitive adhesive sheet was cut to width 100mm x length 100mm, the peeling film was peeled off, adhered to a polycarbonate (PC) plate and fixed, and a pressure of 0.5 MPa under an atmosphere of 50 ° C. After adding and maintaining for 20 minutes, the test piece which has the layer structure of PET film / pressure sensitive adhesive layer / PC board was produced. The said test piece was heat-processed (heat resistance test) for 24 hours in 80 degreeC oven.

After the heat resistance test, the adhesion interface (the interface between the pressure-sensitive adhesive layer and the PC plate) of the sample piece was visually observed to show that "bubble" and "floating" were not found at all. It was judged as "x" that what was seen a little "△", "bubble", and "floating" was remarkable. If evaluation is more than (triangle | delta), there is no practical problem.

<Evaluation Method of Corrosion>

As a corrosive evaluation, the peeling film was peeled off the said pressure-sensitive adhesive sheet cut | disconnected by width 40mm and length 100mm on the ITO transparent conductive film of PET film (40mm width, 160mm length) which has an ITO transparent conductive film with a film thickness of 5 micrometers. After bonding, fixing, and holding at a pressure of 0.5 MPa for 50 minutes under an atmosphere of 50 ° C., a test piece (sheet for touch panel) having a layer structure of PET film / pressure sensitive adhesive layer / ITO film was prepared. Electrodes were connected to both ends of this test piece, and the initial electric resistance value was measured [manufactured by MITSUBISHI CHEMICAL CORPORATION, Laresta-GP MCP-T600]. Again, after leaving the test piece at 85 ° C. for 90% relative humidity for 500 hours, the electrical resistance value after aging was measured in the same manner as above.

The electrical resistance change rate (electrical resistance value after initial stage / initial electrical resistance value) was less than 1.2 "(circle)", and 1.2 or more and less than 1.5 was made into "(triangle | delta)" and 1.5 or more as "x". If the evaluation was Δ or more, there was no practical problem, and it was judged that no malfunction occurred in the conductive member.

In addition, evaluation of the corrosiveness with respect to the metal circuit using the Ag powder filler containing conductive paste instead of the ITO transparent conductive film was performed similarly.

<Evaluation method of plasticizer>

As the evaluation of plastic resistance, the pressure-sensitive adhesive sheet was cut into a width of 100 mm x a length of 100 mm, the peeling film was peeled off, adhered and fixed to a polycarbonate (PC) plate, and a pressure of 0.5 MPa was applied under an atmosphere of 50 ° C. After holding for 20 minutes, a test piece having a layer structure of PET film / pressure sensitive adhesive layer / PC plate was produced. After immersing the test piece in a plasticizer (oleic acid) and taking it out, visual observation of the adhesive interface (interface between the pressure-sensitive adhesive layer and the PC plate) of the sample piece after the test piece was left for 24 hours at 85 ° C-90% relative humidity. Was observed, and evaluation was carried out according to the evaluation criteria of 5 (no lifting or peeling was observed at all)-1 (lifting or peeling was remarkably observed). That is, when evaluating as follows, if evaluation is three or more (the area | region where lifting or peeling is observed is less than 10% of the whole), there is no practical problem.

 5: No lifting or peeling was observed.

 4: Lifting and peeling are observed in less than 5% of the area, but there is no practical problem.

 3: Although floating or peeling is observed in 5% or more and less than 10% of the whole, there is no practical problem.

 2: Since lifting or peeling is observed in the area | region of 10% or more and less than 20% of the whole, there exists a practical problem.

1: Since lifting or peeling is observed in 20% or more of the area, there is a problem in practical use.

<Evaluation method of workability>

As evaluation of workability, when the pressure-sensitive adhesive sheet was cut into a width of 100 mm × length of 100 mm, and pressed for 1 hour at 40 ° C. 60 Kg / cm ² , the adhesive layer was pushed out 5 (the adhesive layer was not pushed out. No evaluation) was evaluated based on the evaluation criteria of 1 to 1 (the remarkable sticking out of the adhesive layer was observed). That is, when it evaluates as follows, if evaluation is two or more (the extent which an adhesive layer pushed out is less than 0.5 mm), there is no practical problem.

5: No sticking of the adhesive layer was observed.

4: The adhesive layer of less than 0.1 mm was pushed out, but there is no practical problem.

3: It is observed that the adhesive layer of 0.1 mm or more and less than 0.3 mm was pushed out, but there is no practical problem.

2: It is observed that the adhesive layer of 0.3 mm or more and less than 0.5 mm was pushed out, but there is no practical problem.

1: Since the adhesive layer of 0.5 mm or more was pushed out, there exists a practical problem.

[Table 2]

[Table 3]

The symbol of Table 2 and Table 3 shows the following, respectively.

B-1: hexamethylene diisocyanate trimethylolpropane adduct

B-2: Hexamethylene diisocyanate isocyanurate body

B-3: hexamethylene diisocyanate burette

B-4: Xylene Diisocyanate Trimethylol Propane Adduct

B-5: toluene diisocyanate trimethylolpropane adduct

B-6: epoxy curing agent (TETRAD X, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

C-1: 3-glycidoxypropyltrimethoxysilane

C-2: 3-isocyanatepropyltriethoxysilane

C-3: IM-1000 (imidazole group-containing silane coupling agent, manufactured by NIPPON MINING & METALS CO., LTD.)

BTZM: Metal Deactivator (manufactured by KYODO CHEMICAL COMPANY LIMITED)

ITO / PET: PET film with ITO transparent conductive film

As shown in Examples 1 to 23 of Table 2, the pressure-sensitive adhesive composition for a conductive member of the present invention has high adhesion, heat resistance, moisture heat resistance, plasticizer resistance, and workability, and is applied to an ITO transparent conductive film or a metal circuit. It has been found that it has excellent corrosion resistance. On the other hand, the comparative examples 1-9 of Table 3 did not have the balance of each physical property, and it was seen that especially causing a problem to corrosion property. In particular, it is important as a property which can be implement | achieved by this invention that it is excellent in heat resistance and corrosion resistance, having high adhesive force with respect to various to-be-adhered bodies, including a conductive member.

Claims (10)

Urethane urea resin (A) having a weight average molecular weight (Mw) of 50,000 to 200,000 formed by reacting a polyamino compound (c) with a urethane prepolymer obtained by reacting a polyol (a) with a polyisocyanate (b),
It contains 0.1-3 weight part of hardening | curing agent (B) with respect to 100 weight part of said urethane urea resins (A),
The polyamino compound (c) is an aliphatic polyamine, an alicyclic polyamine, an aromatic diamine, a dimerdiamine obtained by converting a carboxyl group of a dimer acid into an amino group, a dendrimer having a primary or secondary amino group at the terminal, and represented by the following general formula. Polyoxyalkylene glycol diamine,
H ₂ N-CH ₂ -CH ₂ -CH ₂ -O- (C _m H _2m -O) _n -CH ₂ -CH ₂ -CH ₂ -NH ₂
(Wherein m represents an arbitrary integer of 2 to 4, n represents an arbitrary integer of 2 to 50)
And at least one member selected from the group consisting of a compound (c3) obtained by Michael addition reaction of an ethylenically unsaturated compound (c2) to a compound (c1) having two or more primary amino groups,
The usage-amount of the said polyisocyanate (b) is 8 to 23 weight% in 100 weight% of synthetic raw materials of the said urethane urea resin (A), and the usage-amount of the said polyamino compound (c) is the said urethane urea resin (A) Pressure-sensitive adhesive composition for conductive members of 0.5 to 8% by weight in 100% by weight of the synthetic raw material. delete The method of claim 1,
The pressure-sensitive adhesive composition for conductive members, wherein the polyol (a) comprises a polyol having a polypropylene glycol skeleton. The method of claim 1,
The curing agent (B) is selected from the group consisting of hexamethylene diisocyanate trimethylolpropane adduct, hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate biuret, and xylene diisocyanate trimethylolpropane adduct Pressure sensitive adhesive composition for a conductive member comprising at least one. The method of claim 1,
Any 1 selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, or a silane coupling agent having an imidazole group based on 100 parts by weight of the urethane urea resin (A). Pressure-sensitive adhesive composition for conductive members containing 0.1 to 1.0 parts by weight or more. A sheet-shaped base material and a pressure-sensitive adhesive layer formed on one or both surfaces of the sheet-shaped base material,
The pressure-sensitive adhesive layer for the conductive member, wherein the pressure-sensitive adhesive layer is formed of the pressure-sensitive adhesive composition for the conductive member according to any one of claims 1 and 3 to 5. A conductive member or a transparent optical member, and a pressure-sensitive adhesive layer laminated on the conductive member or the transparent optical member,
The said pressure sensitive adhesive layer is a laminated body formed from the pressure-sensitive adhesive composition for electrically conductive members of any one of Claims 1-5. The method of claim 7, wherein
The laminated body whose said conductive member is a transparent conductive film or a metal circuit. The touch panel sheet which has a laminated body of Claim 7. The touch panel sheet which has a laminated body of Claim 8.