JP5521689B2 - Pressure-sensitive adhesive composition for conductive member and laminate using the same - Google Patents

Description

  The present invention relates to a pressure-sensitive adhesive composition for conductive members, and more specifically, a pressure-sensitive adhesive composition for conductive members used for bonding conductive members used in touch panels and the like, and a conductive material using the same. The present invention relates to a pressure-sensitive adhesive sheet for members, a laminate, and a touch panel sheet.

  Liquid crystal display devices have been widely used in various products such as personal computers and televisions. Especially, electronic notebooks, mobile phones, and the like have been increasingly miniaturized, and all of them are widely used as display devices for electronic devices. Such a liquid crystal display device or the like includes a so-called touch panel module in which a display screen functions as a touch panel sheet and an operator designates an operation by touching a predetermined position on the display screen with a finger. .

  In the configuration of the touch panel, a glass substrate or a transparent resin substrate and a conductive member such as a transparent conductive film such as ITO or a metal circuit are bonded by a pressure-sensitive adhesive layer. The laminate composed of this glass substrate or transparent resin substrate / pressure-sensitive adhesive layer / transparent electrode is placed under high temperature or high-temperature and high-humidity conditions, and at the bonding interface between the pressure-sensitive adhesive layer and the adherend. Bubbles are generated (foaming), and the film is lifted from the adherend and peeled off. Therefore, as a pressure-sensitive adhesive used, attempts have been made in the past to prevent foaming, floating and peeling even under harsh environments.

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

  So far, pressure sensitive adhesives mainly based on acrylic resins have been studied as the pressure sensitive adhesive layer (Patent Documents 1 and 2).

  However, when a pressure sensitive adhesive based on an acrylic resin is used, it is necessary to introduce an acid group into the base resin in order to improve the adhesion to the conductive member. However, the introduced acid group corroded the conductive member as the adherend, causing malfunction and the like.

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

JP 2006-45315 A JP 2008-120864 A JP 2002-121256 A JP 2002-38119 A JP 2003-137963 A

  The object of the present invention is not to cause corrosion to transparent conductive films such as ITO and conductive members such as metal circuits, and does not cause foaming or peeling even under high temperature or high temperature and high humidity conditions. An object of the present invention is to provide a pressure-sensitive adhesive composition for a conductive member having good processability and further having high adhesiveness.

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

That is, in the first invention, the weight average molecular weight (Mw) obtained by reacting the polyamino compound (c) with the urethane prepolymer obtained by reacting the polyol (a) and the polyisocyanate (b) is 50, For 100 parts by weight of urethane urea resin (A) that is 000 to 200,000,
The present invention relates to a pressure-sensitive adhesive composition for conductive members containing 0.1 to 3 parts by weight of a curing agent (B).

  In the second invention, the amount of polyisocyanate (b) used is 8 to 23% by weight in 100% by weight of urethane urea resin (A), and the amount of polyamino compound (c) used is urethane urea resin. (A) It is related with the pressure sensitive adhesive composition for electrically-conductive members of 1st invention which is 0.5-8 weight% in 100 weight%.

  The third invention relates to the pressure-sensitive adhesive composition for conductive members of the first or second invention, wherein the polyol (a) contains a polyol having a polypropylene glycol skeleton.

  In the fourth invention, the curing agent (B) is at least selected from a hexamethylene diisocyanate trimethylolpropane adduct, a hexamethylene diisocyanate isocyanurate, a hexamethylene diisocyanate burette, and a xylylene diisocyanate trimethylolpropane adduct. The present invention relates to a pressure-sensitive adhesive composition for a conductive member according to any one of the first to third inventions.

  Further, the fifth invention provides a silane coupling agent having 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, or imidazole group with respect to 100 parts by weight of the urethane urea resin (A). The present invention relates to a pressure-sensitive adhesive composition for a conductive member according to any one of the first to fourth inventions containing 0.1 to 1.0 part by weight.

  Moreover, 6th invention is the electroconductivity formed by forming the pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition for electrically-conductive members of any one of 1st-5th invention on the one or both surfaces of a sheet-like base material. The present invention relates to a pressure-sensitive adhesive sheet for members.

  The seventh invention relates to a laminate in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for a conductive member of any one of the first to fifth inventions is laminated on a conductive member.

  Moreover, 8th invention is related with the laminated body of 7th invention whose conductive member is a transparent conductive film or a metal circuit.

  Moreover, 9th invention is related with the sheet | seat for touchscreens which has the laminated body of 7th or 8th invention.

  According to the present invention, it does not cause corrosion to conductive members such as ITO and other transparent conductive films and metal circuits, does not cause foaming or peeling even under high temperature or high temperature and high humidity conditions, and has good plasticizer resistance and good It was possible to provide a pressure-sensitive adhesive composition for a conductive member having workability and further having high adhesiveness.

  The urethane urea resin (A) used in the present invention will be described. The urethane urea resin (A) of the present invention has a weight average molecular weight (Mw) obtained by reacting a polyamino compound (c) with a urethane prepolymer obtained by reacting a polyol (a) and a polyisocyanate (b). 50,000-200,000 resin.

  As the polyol (a) used in the present invention, known polyols can be used, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, copolymers thereof, and other glycols.

Known polyether polyols can be used as the polyether polyols. For example, polymers, copolymers, and graft copolymers of alkylene oxides such as propylene oxide, tetrahydrofuran, ethylene oxide, butylene oxide;
Those having two or more hydroxyl groups such as polyether polyols by condensation of hexanediol, methylhexanediol, heptanediol, octanediol or a mixture thereof can be used. Furthermore, glycols obtained by adding alkylene oxides such as ethylene oxide to bisphenols such as bisphenol A and bisphenol F can be used.

  Known polyester polyols can be used as the polyester polyols. Examples of the polyester polyol include a polyester polyol obtained by condensation reaction of a polyfunctional alcohol component and a dibasic acid component. Examples of the polyfunctional alcohol component include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3 ′. -Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexane Examples include compounds having two hydroxyl groups such as diol, cyclohexanediol, bisphenol A, and bisphenol F, and three or more hydroxyl acids such as glycerin, trimethylolpropane, and pentaerythritol. Compounds having the like.

  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.

  Β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, α-methyl-β-propiolactone, etc. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones can also be used.

  The polycarbonate polyol has a structure represented by the following general formula [1] in its molecule, and a known polycarbonate polyol can be used.

General formula [1]
− [— O—R ¹ —O—CO—] _m —
(In the formula, R ¹ represents a divalent organic residue, and m represents an integer of 1 or more.)

  The polycarbonate polyol can be obtained, for example, by (1) a reaction between glycol or bisphenol and a carbonate ester, or (2) a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

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

  Examples of the glycol or bisphenol used in the production methods (1) and (2) include 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, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, or Scan bisphenols such as bisphenol A, bisphenol F, ethylene oxide bisphenol, bisphenol obtained by adding alkylene oxide such as propylene oxide or the like can also be used. These compounds can be used as one kind or a mixture of two or more kinds.

  Specifically, the Kuraray polyol C series of Kuraray Co., Ltd. can be used in the polycarbonate polyol. Among them, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, and C-2015N are flexible, and polypropylene is used as a raw material for the urethane urea resin (A). A polyol having a glycol skeleton can be preferably used in combination.

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

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

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

  The polyol containing at least one ionic functional group can make the urethane urea resin (A) of the present invention aqueous, increase the reaction rate during the synthesis of the urethane prepolymer, and improve the film formability. However, the ionic group is introduced into the urethane urea resin (A). Especially when the ionic group is an acid group, the transparent conductive film or the metal circuit is corroded. Therefore, it is preferable not to use more than necessary, and it is particularly preferable not to use at all.

  For example, when a polyol having a carboxyl group is used as a 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 converted into a curing agent (C) described later. It can be used as a reaction point. Examples of the polyol containing at least one ionic functional group include dioxycarboxylic acids such as dimethylolpropionic acid and dimethylolbutanoic acid.

  As the polyol (a) of the urethane urea resin (A) in terms of transparency and adhesive strength of the pressure-sensitive adhesive layer, it is preferable to use a polyol having a polypropylene glycol skeleton, and a total of 100 weights of the polyol (a). %, The amount of the polyol having a polypropylene glycol skeleton is preferably 50 to 100% by weight, more preferably 100% by weight. If it is less than 50% by weight, the adhesion may be insufficient.

  The number average molecular weight of the polyol (a) used in the present invention is preferably 800 to 4,000, more preferably 1,000 to 3,000. If it is less than 800, the urethane and urea bond density | concentration in resin may be increased and the adhesive force may be reduced. If it exceeds 4,000, urethane bonds and urea bonds that impart cohesive force to the pressure-sensitive adhesive may be reduced, and the heat resistance of the pressure-sensitive adhesive may be impaired.

  In order to satisfy the performance as the pressure-sensitive adhesive composition, the polyol (a) described above is appropriately selected so that the glass transition temperature (Tg) of the urethane urea resin (A) is 0 to -80 ° C. preferable. The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

  As the polyisocyanate (b) used in the present invention, conventionally known ones can be used, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. It is done.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate etc. can be mentioned.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  As the alicyclic polyisocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2 , 6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane and the like.

  Further, a trimethylolpropane adduct of the above polyisocyanate (b), a trimer having an isocyanurate ring, etc. can be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as the polyisocyanate (b).

  Examples of the polyisocyanate (b) used in the present invention include 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate (also known as IPDI), xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) ( It is preferable from the viewpoint of weather resistance to use a non-yellowing type or hardly yellowing type polyisocyanate compound such as another name: hydrogenated MDI).

  Further, as the above-described polyisocyanate (b), it is preferable to use isophorone diisocyanate (also known as IPDI) in terms of controlling transparency and reactivity of the pressure-sensitive adhesive composition.

  Polyisocyanate (b) is used in an amount of 100% by weight of urethane urea resin (A) [polyol (a), polyisocyanate (b), polyamino compound (c) used in the synthesis of urethane urea resin (A), and A proportion of 8 to 23% by weight is preferable, among the total of 100% by weight of the reaction terminator (d) used as necessary], and more preferably 10 to 21% by weight. If it is less than 8% by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, and it may be difficult to impart durability. Moreover, since the softness | flexibility of resin will fall when it exceeds 23 weight%, it may become difficult to obtain sufficient adhesive force.

  Next, the polyamino compound (c) used in the present invention will be described. The polyamino compound (c) of the present invention is a compound having two or more amino groups, and known compounds can be used. By using a compound having two or more amino groups, the adhesive strength of the pressure-sensitive adhesive can be imparted, and further, compatibility with durability can be achieved.

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) diamine, (2-hydroxypropylethylene) diamine Aliphatic polyamines such as (di-2-hydroxypropylethylene) diamine and piperazine;
Cycloaliphatic polyamines such as isophoronediamine and dicyclohexylmethane-4,4′-diamine;
Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-bis- ( sec-butyl) aromatic diamines such as diphenylmethane;
And dimer diamine obtained by converting the carboxyl group of dimer acid into an amino group, a dendrimer having a primary or secondary amino group at the terminal, and a propoxyamine at both terminals, and represented by the following general formula [2] Etc. 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
(In the formula, m represents an arbitrary integer of 2 to 4, and n represents an arbitrary integer of 2 to 50.)

  The polyamino compound (c) used in the present invention is a compound (c3) obtained by Michael addition reaction of an ethylenically unsaturated compound (c2) with a compound (c1) having two or more primary amino groups, particularly from the viewpoint of reaction control. In addition, as the ethylenically unsaturated compound (c2), an ethylenically unsaturated compound having a hydroxyl group is preferably used from the viewpoint of introducing a crosslinking point into the urethane urea resin (A).

  As the compound (c1) having two or more primary amino groups, the above-mentioned compounds having two or more amino groups can be used, and in particular, isophoronediamine, 2,2,4-trimethylhexamethylenediamine, hexamethylene Diamine is preferable because it is easy to control the Michael addition reaction, and the urethane urea resin (A) obtained using the resulting Michael addition-reacted compound (c3) is excellent in transparency.

  Examples of the ethylenically unsaturated compound having a hydroxyl group in the ethylenically unsaturated compound (c2) include 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 Plaxel FA, Plaxel FA2D, Plaxel FA3, Plaxel FA5, Plaxel FA10L, Plaxel FM1D, Plaxel FM2D, Unsaturated compounds having a polyester chain terminated with a hydroxyl group, such as PLACCEL FM3, PLACCEL FM3X, PLACCEL FM5, PLACCEL FM5L, polyethylene glycol (meth) acrylate Over DOO, polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, an unsaturated compound having a polyether chain having a hydroxyl group such as hexaethylene glycol (meth) acrylate at the terminal thereof.

  Although the above compounds can be used alone or in combination of two or more, 4-hydroxybutyl acrylate is particularly preferred from the standpoint of reactivity with the curing agent (B) described later and optical properties of the pressure-sensitive adhesive. Is preferably used.

  Examples of ethylenically unsaturated compounds (c2) that do not have a hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 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, octadecyl (meth) acrylate Nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkyl (meth) acrylates having 1 to 22 carbon atoms such as docosyl (meth) acrylate. In the case of adjusting the polarity, an alkyl group-containing acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, or a corresponding methacrylate is exemplified. When aiming at adjustment of leveling property, etc., it is preferable to have 6 or more carbon atoms.

Furthermore, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, propoxypolyethyleneglycol (meth) acrylate, n-butoxypolyethyleneglycol (meth) acrylate, n-pentoxypolyethyleneglycol (meth) acrylate, phenoxypolyethyleneglycol Alkoxypolyalkylene glycol mono (meth) acrylates such as (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, or phenoxypolyalkylene glycol mono (Meth) acrylates;
Fatty acid vinyls such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, 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, 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 carboxyl group-containing unsaturated compounds such as β- (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, quaternary ammonium base-containing unsaturated compounds;
Can be used in combination.

  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-propoxymethyl- (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-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) Acrylic net N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) Examples include acrylamide and N-methoxymethyl-N- (pentoxymethyl) methacrylamide.

  Dialkylamino group-containing unsaturated compounds include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate , Dimethylaminostyrene, diethylaminostyrene and the like.

The quaternary ammonium base-containing unsaturated compound can be obtained by quaternizing the dialkylamino group-containing unsaturated compound. Examples of the quaternary ammonium base-containing unsaturated compound having a Cl ⁻ , Br ⁻ , I ⁻ halogen ion or QSO ₃ ⁻ (Q: an alkyl group having 1 to 12 carbon atoms) as a counter ion include dimethylaminoethyl (meth) acrylate. Methyl chloride salt, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, and trimethyl-3- (1- (Meth) acrylamide-1,1-dimethylethyl) ammonium chloride and the like.

Furthermore, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meta ) Acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl Perfluoro having a C 1-20 perfluoroalkyl group such as (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Alkyl (meth) acrylates; perfluorobutyl ethylene, perfluorohexylethylene, perfluorooctylethylene, perfluoroalkyl group-containing unsaturated compound of the perfluoroalkyl alkylene, and the like, such as perfluorodecyl ethylene;
Unsaturated compounds having an alkoxysilyl group such as vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, 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, allylbenzene, allyl cyanide;
Vinyl compounds such as vinyl cyanide, vinylcyclohexane, vinylmethylketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene;
Ethynyl compounds such as acetylene, ethynylbenzene, ethynyltoluene;
Can also be used in combination.

  In the Michael addition reaction between the compound (c1) having two or more primary amino groups and the ethylenically unsaturated compound (c2), 1 mol of active hydrogen of the amino group in the compound (c1) having two or more primary amino groups Reacts with 1 mol of ethylenically unsaturated groups in the ethylenically unsaturated compound (c2). Since the amino group in the compound (c1) having two or more primary amino groups is easily Michael-added to the ethylenically unsaturated group of the compound having an electron-withdrawing group, the ethylenically unsaturated compound (c2) Is preferably a (meth) acrylic compound, and particularly preferably an acrylate compound from the viewpoint of the efficiency of the Michael addition reaction.

  As a synthesis method of the compound (c3) obtained by subjecting the compound (c1) having two or more primary amino groups to the Michael addition reaction of the ethylenically unsaturated compound (c2), a known method relating to the Michael addition reaction can be used as it is. When the ethylenically unsaturated compound (c2) is a (meth) acrylic compound, particularly an acrylate compound, the reaction proceeds at 10 to 100 ° C. under a catalyst such as alcohol as necessary. Although depending on the type of the ethylenically unsaturated compound (c2) used, a reaction temperature of 40 to 80 ° C. is preferred. If the reaction temperature is too high, an ester amide exchange reaction occurs, which is not preferable. Further, when the ethylenically unsaturated compound (c2) does not have an electron-withdrawing group, the reaction becomes possible in the presence of a metal catalyst. In this case, if the reaction is performed at 60 to 100 ° C. while heating in the presence of the catalyst. A moderate reaction rate is preferable. The synthetic solvent may or may not be used, and the kind thereof is not particularly limited, but known solvents such as methyl ethyl ketone, toluene, acetone, and benzene can be used. The solution concentration in the case of using a solvent is preferably 20% by weight or more, more preferably 50% by weight or more. If it is more dilute than this, it is not preferable because the reaction hardly proceeds. The reaction time varies depending on the type of ethylenically unsaturated compound (c2) to be used, but is completed in 30 minutes to 5 hours.

  The ratio of ethylenically unsaturated compound (c2) to be added to compound (c1) having two or more primary amino groups is at least two primary or secondary amino groups in compound (c3) subjected to Michael addition reaction. Is preferably 0.1 to 1.0 mole, more preferably 0.2 to 1.0 mole, relative to 1 mole of the primary amino group contained in the compound (c1) having two or more primary amino groups. It is preferable to react the ethylenically unsaturated group in the ethylenically unsaturated compound (c2) at a molar ratio. If it is less than this, the effect of introducing the ethylenically unsaturated compound (c2) may not be obtained, and it is not preferable because the storage stability is low. More than this does not contribute to the reaction.

  The amount of the polyamino compound (c) used is 100% by weight of the urethane urea resin (A) [polyol (a), polyisocyanate (b), amino compound (c) used in the synthesis of the urethane urea resin (A), and The ratio of 0.5 to 8% by weight is preferable, among the total of 100% by weight of the reaction terminator (d) used as necessary], and more preferably 2 to 5% by weight. If it is less than 0.5% by weight, the cohesive force is lowered, and it may be difficult to impart durability. On the other hand, if it exceeds 8% by weight, the flexibility of the resin decreases, and it may be difficult to obtain sufficient adhesion.

  The urethane urea resin (A) of the present invention is obtained by reacting a urethane prepolymer having an isocyanate group at the end with a polyamino compound (c). If necessary, a monoamino compound can be used as a reaction terminator (d). Can be reacted.

  When synthesizing the urethane urea resin (A), a reaction terminator is used for the purpose of stabilizing the reaction activity of the resin by controlling the molecular weight or reacting with the unreacted isocyanate group at the end of the urethane urea resin (A). (D) can be used.

  Examples of the reaction terminator (d) used in the present invention include, for example, diethanolamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine, diisononylamine, monoethanolamine, diethanolamine, 2 -Monoamine having a hydroxyl group such as amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl-1,3-propanediol, monomethylhydrazine, 1,1-dimethylhydrazine, Alkyl hydrazines such as benzylhydrazine, hydrazides such as form hydrazide, acetohydrazide, lauric hydrazide, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine and the like Primary amino group and primary amino group Compounds, monoamino compound having an alkoxysilyl group such as γ- aminopropyltriethoxysilane can be used. Furthermore, amino compounds having only one primary or secondary amino group can also be used as a reaction terminator.

  Among the above reaction terminators (d), a monoamine compound having a hydroxyl group such as 2-amino-2-methyl-propanol can obtain a urethane urea resin excellent in storage stability whose terminal is a hydroxyl group. Furthermore, the urethane urea resin whose terminal is a hydroxyl group is preferable because it can be used as a reaction point with the curing agent (B) described later. In the case of a 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 reactivity of the amino group is higher, and it reacts preferentially with the isocyanate group. .

  Said reaction terminator (d) is 100% by weight of urethane urea resin (A) [polyol (a), polyisocyanate (b), polyamino compound (c) used in the synthesis of urethane urea resin (A), and The total amount of the reaction terminator (d) used as required is 100% by weight] is preferably 0.05% by weight to 2% by weight, and if it is less than 0.05% by weight, the reaction stability of the resin may be impaired. If it exceeds 2% by weight, the weight average molecular weight (Mw) of the resin may be lowered and the durability may be impaired.

  Furthermore, it can be modified by ring-opening addition of a cyclic ester compound and / or a cyclic ether compound to the hydroxyl group of the urethane urea resin (A) thus obtained.

  In the method for producing the urethane urea resin (A) used in the present invention, a polyol (a) and a polyisocyanate (b) are first reacted to produce a urethane prepolymer having at least one isocyanate group. Next, the urethane urea resin (A) can be produced by reacting the obtained urethane prepolymer, the polyamino compound (c) and a reaction terminator (d) as necessary.

  A known catalyst can be used for the synthesis of the urethane prepolymer. Examples thereof include tertiary amine compounds and organometallic compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), and may be used alone or in combination in some cases. it can.

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

  Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin Examples include acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, dioctyltin dilaurate (also known as DOTDL), and tin 2-ethylhexanoate.

  Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Examples include iron series such as iron ethylhexanoate and iron acetylacetonate, cobalt series such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc series such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate. It is done.

  Among the above catalysts, dibutyltin dilaurate (also known as DBTDL), dioctyltin dilaurate (also known as DOTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Catalysts such as tertiary amine compounds and organometallic compounds can be used alone in some cases, but can also be used in combination. Especially when polyester diols and polyether diols are used in combination as polyol components, Use of dibutyltin dilaurate and tin 2-ethylhexanoate in combination is preferable because a uniform urethane prepolymer can be obtained stably.

  The organometallic compound catalyst used when synthesizing the urethane prepolymer significantly accelerates the reaction when the urethane prepolymer reacts with the polyamino compound (c). The reaction between an isocyanate group and an amino group is very fast from the beginning, but in the presence of an organometallic compound catalyst, the reaction may be further promoted and may be difficult to control. At this time, if a chelate compound is present, a chelate is formed with the organometallic compound catalyst, the catalytic ability is adjusted, and the reaction with the polyamino compound (c) is easily controlled.

  Examples of the chelate compound include acetylacetone, dimethylglyoxime, oxine, dithizone, polyaminooxyacids such as ethylenediaminetetraacetic acid (also known as EDTA), oxycarboxylic acids such as citric acid, and condensed phosphoric acid. Among the chelate compounds, acetylacetone is soluble in an organic solvent, has volatility, and is preferably easy to remove if necessary.

  The chelate compound remains in the urethane urea resin (A) even after the reaction. The pressure-sensitive adhesive composition for a conductive member containing the urethane urea resin (A) of the present invention contains a curing agent (B). At this time, the chelate compound comprises the urethane urea resin (A) and the curing agent (B ) And the pressure-sensitive adhesive composition for conductive members having excellent storage stability as a result.

  A known solvent is suitably used for the synthesis of the urethane prepolymer of the present invention. The use of a solvent serves to facilitate reaction control. Examples of the solvent used for such purpose include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide and the like. It is done. In view of the solubility of the urethane urea resin (A), the boiling point of the solvent, the solubility of the polyamino compound (c), etc., ethyl acetate, toluene, methyl ethyl ketone or a mixed solvent thereof is particularly preferable. The concentration in the urethane prepolymer reaction system when using a solvent is preferably 50 to 95% by weight, more preferably 60 to 90% by weight of the resin solid content, and if the concentration is too low, the reactivity decreases. It is not preferable because it is too much.

  The urethanization reaction for synthesizing the urethane prepolymer in the present invention can be carried out in various ways, but is roughly classified into the following two methods. [I] A method in which the polyol (a), the polyisocyanate (b), a solvent, and a catalyst are all charged. [Ii] A method in which a polyol (a) and a solvent are charged into a flask, a polyisocyanate (b) is dropped, and then a catalyst is added as necessary. [Ii] is preferable when the reaction is precisely controlled. The reaction temperature for obtaining the urethane prepolymer is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 120 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined weight average molecular weight and structure cannot be obtained. The urethanization reaction is preferably performed in the presence of a catalyst at 50 to 110 ° C. for 1 to 20 hours.

  The blending ratio of the polyol (a) and the polyisocyanate (b) greatly depends on the reactivity of the compound, the abundance ratio of the trivalent or higher compound, the use of the obtained resin, and the like. In order for the urethane prepolymer to have at least one isocyanate group, it is necessary that the number of isocyanate groups in the polyisocyanate (b) be greater than 1 mole relative to 1 mole of hydroxyl groups in the polyol (a). The amount is preferably in the range of 1.01 to 4.00 mol, more preferably 1.10 to 2.00 mol.

  Moreover, the urea reaction of the isocyanate group in the urethane prepolymer which is an isocyanate group-containing compound obtained as described above and the primary or secondary amino group of the polyamino compound (c) has the following two types. Broadly divided into methods. [Iii] A method in which a urethane prepolymer is charged into a flask and the polyamino compound (c) is dropped. [Iv] A method in which the polyamino compound (c) is charged into a flask and a urethane prepolymer is dropped. If there is no problem in the reaction, the method [iii] that is easy to operate is preferred. The temperature of the urea reaction of the present invention is preferably 100 ° C. or lower. More preferably, it is 70 degrees C or less. Even at 70 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a urethane urea resin (A) having a predetermined weight average molecular weight and structure. When an alcohol solvent is used as the synthesis solvent for the polyamino compound (c), the temperature in the reaction system should be 50 ° C. or lower, more preferably 40 ° C. or lower when the polyamino compound (c) is dropped. Is preferred.

  The amount of the reaction terminator (d) used differs depending on whether it is mixed with the polyamino compound (c) or when it is added alone at the end, but in the case of mixing addition, 1 mol of isocyanate group in the urethane prepolymer is added. On the other hand, it is desirable to use an amount in which the amino group in the reaction terminator (d) is preferably 0.5 mol or less, more preferably 0.3 mol or less. Is 0.5 to 3.0 mol with respect to 1 mol of the isocyanate group finally present, and 1 to 3.0 mol is preferable particularly for the purpose of stabilizing the urethane urea resin (A). Outside this range, adverse effects such as a decrease in film formability or discoloration may be observed.

  The end point of the reaction is judged from the disappearance of the isocyanate peak by the measurement of isocyanate% due to titration and IR measurement.

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

  The molecular weight of the urethane urea resin (A) needs to be 50,000 to 200,000 as a weight average molecular weight in terms of standard polystyrene by GPC (gel permeation chromatography). Preferably, it is 80,000-150,000. When the weight average molecular weight is less than 50,000, the balance between the durability as a pressure-sensitive adhesive and the optical function maintaining property is deteriorated. On the other hand, if it exceeds 200,000, the adhesive strength is lowered, or the 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 depending on the use of the resin, but is preferably 3000 to 25000 mPa · s (25 ° C.) at a solid content of 50% by weight. If the viscosity is too high, coating may be difficult. If the viscosity is too low, a resin having a sufficient molecular weight may not be formed.

  Next, the curing agent (B) will be described. The pressure-sensitive adhesive composition for conductive members of the present invention is characterized by containing 0.1 to 3 parts by weight of the curing agent (B) with respect to 100 parts by weight of the urethane urea resin (A). Examples of the reactive functional group present in the urethane urea resin (A) include a hydroxyl group and a carboxyl group. Accordingly, examples of the functional group of the curing agent (B) used in the present invention include an isocyanate group, an epoxy group, an alkoxysilyl group, a methylol group, an aziridine group, and a carbodiimide group. Examples of the curing agent (B) include polyisocyanate compounds, polyfunctional epoxy compounds, high molecular weight polycarbodiimides, N-methylol group-containing compounds, polyfunctional aziridine compounds, and metal chelates. Among these, curing In order to act as an agent, a compound having two or more functional groups capable of reacting with the hydroxyl group of the urethane urea resin (A) in the molecule is preferably used. In particular, polyisocyanate compounds are preferably used because they are excellent in adhesion after the crosslinking reaction and adhesion to the coating layer.

  The polyisocyanate compound is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule. Examples of polyisocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane trisene. Polyisocyanate compounds such as isocyanate and polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and further these polyisocyanate compounds Known polyether polyols and polyesters Ether polyols, acrylic polyols, polybutadiene polyols, adducts, etc. and polyisoprene polyol and the like.

  The polyfunctional epoxy compound is not particularly limited as long as it is a compound having a plurality of epoxy groups in the molecule. 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, N, N, N ′, N Examples include '-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, and the like.

  Examples of the high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.

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

  Examples of metal chelates 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. It is done.

  The said hardening | curing agent (B) can be used individually or in combination. As the curing agent (B), a polyisocyanate compound is preferable from the viewpoint of reactivity and pot life, and hexamethylene diisocyanate trimethylolpropane adduct is particularly preferable from the viewpoint of optical characteristics of the pressure-sensitive adhesive layer and resistance to foaming. , Hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate burette, or xylylene diisocyanate trimethylolpropane adduct.

  The pressure-sensitive adhesive composition for conductive members of the present invention is characterized by containing 0.1 to 3 parts by weight of the curing agent (B) with respect to 100 parts by weight of the urethane urea resin (A). In particular, the content is more preferably 0.2 to 1.5 parts by weight. If it exceeds 3 parts by weight, the cross-linked structure of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for conductive members becomes dense, the tack of the pressure-sensitive adhesive layer tends to decrease, and the adhesion to the adherend Decreases. On the other hand, if the amount is less than 0.1 parts by weight, a sufficient cross-linked structure cannot be obtained. By the reaction between the reactive functional group of the urethane urea resin (A) and the functional group in the curing agent (B), the resin composition is three-dimensionally cross-linked to ensure adhesion with various substrates and adherends. In addition, since heat resistance and heat-and-moisture resistance under severer conditions than before can be improved, it can be preferably used for a conductive member.

  In the pressure-sensitive adhesive composition for a conductive member of the present invention, a silane coupling agent having an alkoxysilyl group may be added for the purpose of improving heat and humidity resistance. It is considered that the silane coupling agent is particularly easy to form an inclined structure in the pressure-sensitive adhesive layer of the present invention, and is unevenly distributed on the surface of the adhesive layer, and is particularly effective for improving the heat and moisture resistance property and the adhesive force.

A well-known thing can be used as a silane coupling agent. For example, γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltributoxysilane, Silane compounds having a (meth) acryloxy group and an alkoxy group such as γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane;
Alkoxysilanes having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane;
Alkoxysilanes such as 5-hexenyltrimethoxysilane, 9-decenyltrimethoxysilane, styryltrimethoxysilane;
Silanes having aminoalkyl groups and alkoxy groups such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane;
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptomethylphenylethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6 A compound having a mercapto group such as mercaptohexyltrimethoxysilane, 10-mercaptodecyltrimethoxysilane;
Compounds having an imidazole group such as IS-1000, IA-100A, IM-1000, SP-10 (manufactured by Nikko Metal Co., Ltd.);
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, 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)- Examples include 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane. Any one or more of these can be used alone or in combination.

  Among the above silane coupling agents, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, or a silane coupling agent having an imidazole group is used from the viewpoint of improving heat and moisture resistance. Is preferred. In particular, when 3-isocyanatopropyltriethoxysilane or IM-1000 is used, the processability, plasticizer resistance, heat resistance, and heat and humidity resistance can be remarkably improved, and the adhesive member has a particularly high adhesive force. A pressure sensitive adhesive composition can be obtained.

  The silane coupling agent is preferably used in an amount of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the urethane urea resin (A). The effect may not be obtained. Further, even if an amount exceeding 1.0 part by weight is used, not only the effect can be obtained, but the adhesive force may be lowered.

  In the pressure-sensitive adhesive composition for conductive members according to the present invention, other resins such as an acrylic resin, a polyester resin, an amino resin, an epoxy resin, and a polyurethane resin can be used in combination as necessary. Furthermore, additives such as organic / inorganic pigments, fillers, colorants, ultraviolet absorbers, antioxidants, antifoaming agents, light stabilizers and the like may be blended depending on the application.

  The conductive member of the present invention is not particularly limited as long as it is a conductive member, and examples thereof include transparent conductive films such as ITO and ATO, metal vapor deposited films, and conductive metal circuits formed of metal particles.

  Using the pressure-sensitive adhesive composition for conductive members of the present invention, a laminated product composed of a pressure-sensitive adhesive layer and a sheet-like substrate (hereinafter referred to as “pressure-sensitive adhesive sheet for conductive members”) is obtained. be able to. For example, a pressure-sensitive adhesive sheet for a conductive member can be obtained by coating, drying and curing the pressure-sensitive adhesive composition for a conductive member of the present invention on one side or both sides of various sheet-like substrates. The pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet for conductive members is “pressure-sensitive” and therefore has tack at about room temperature. When applying the pressure-sensitive adhesive composition for conductive members, an appropriate liquid medium, for example, an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, isopropyl alcohol, other hydrocarbon solvents, or water is further added. The viscosity can be adjusted, and the pressure-sensitive adhesive composition for conductive members can be heated to lower the viscosity. However, care should be taken because addition of a large amount of water, alcohol or the like may cause reaction inhibition between the urethane urea resin (A) and the curing agent (B).

  Sheet-like substrates include cellophane, various plastic sheets, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plates, metal plates, wood, optical films such as polarizing plates, etc. Can be mentioned. Various base materials can be used alone or in a multi-layered state in which a plurality of base materials are laminated. Furthermore, the surface of which has been subjected to a peeling treatment or an antistatic treatment can also be used.

  Various plastic sheets are also called various plastic films, such as polyvinyl alcohol film, triacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, polyolefin resin film such as ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate. , Polyester resin film such as polyethylene naphthalate, Polycarbonate resin film, Polynorbornene resin film, Polyarylate resin film, Acrylic resin film, Polyphenylene sulfide resin film, Polystyrene resin film, Vinyl Resin film, polyamide resin film, polyimide resin film, epoxy resin, cycloolefin Films such emissions resins.

  When the pressure-sensitive adhesive composition for a conductive member is applied to the sheet-like base material by an appropriate method according to a conventional method, and then the pressure-sensitive adhesive composition for the conductive member contains a liquid medium such as an organic solvent or water In the case where the liquid medium is removed or the pressure sensitive adhesive composition for conductive members does not contain a liquid medium to be volatilized, the adhesive layer in a molten state is cooled and solidified to form a sheet. An adhesive layer can be formed on the substrate. The thickness of the pressure sensitive adhesive layer is preferably 0.1 μm to 250 μm, and more preferably 20 μm to 200 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained. If the thickness exceeds 250 μm, characteristics such as adhesive strength are often not improved further.

  The method for applying the pressure-sensitive adhesive composition for a conductive member of the present invention to a sheet-like substrate is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, Various coating methods such as a comma coater, a knife coater, a reverse coater, and a spin coater can be used. There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although it depends on the cured form of the adhesive composition, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

  The laminate of the present invention is formed from the pressure-sensitive adhesive composition for a conductive member of the present invention on a transparent optical member such as PET film or glass, or a transparent conductive film such as ITO, or a conductive member such as a metal circuit. The pressure-sensitive adhesive layer is laminated. Particularly effective from the viewpoint of corrosion resistance, when a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition for a conductive member is laminated on a transparent conductive film such as ITO or a conductive member such as a metal circuit. is there. On the other surface of the pressure-sensitive adhesive layer, a sheet-like base material subjected to a release treatment can be laminated.

  The laminate of the present invention is, for example, (a) a pressure-sensitive adhesive composition for a conductive member is applied to a release-treated surface of a sheet-like base material that has been subjected to a release treatment, and dried, starting with PET film or glass. A transparent optical member or a sheet-like conductive member is laminated on the surface of the pressure-sensitive adhesive layer, [transfer coating], or (b) conductive to a transparent optical member or a sheet-like conductive member such as PET film or glass. It can be obtained by coating and drying the pressure-sensitive adhesive composition for members and laminating the peel-treated surface of the peeled sheet-like substrate on the surface of the pressure-sensitive adhesive layer or [direct coating]. it can.

  For example, the pressure-sensitive adhesive is peeled off from the laminate having the structure of “peeled sheet / pressure-sensitive adhesive layer / transparent optical member” and the peel-treated sheet-like substrate covering the surface of the pressure-sensitive adhesive layer. By attaching the layer to a sheet-like conductive member (a transparent conductive film such as ITO or a conductive member such as 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. Further, the surface of the pressure-sensitive adhesive layer is covered from a laminate having a structure of “peeled sheet / pressure-sensitive adhesive layer / sheet-like conductive member (transparent conductive film such as ITO or conductive member such as a metal circuit)”. A sheet for a touch panel having a configuration of “transparent optical member / pressure-sensitive adhesive layer / conductive member” is obtained by peeling off the peeled sheet-like base material and sticking the pressure-sensitive adhesive layer to the transparent optical member. Can be obtained.

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

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.

  The weight average molecular weight (Mw) of each resin obtained in Synthesis Examples 4 to 25 was determined according to the following method.

<Measurement of weight average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

[Synthesis of amino compounds]
Synthesis example 1
A 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 25.0 parts of isophoronediamine (IPDA) and 25.0 parts of toluene. 19.1 parts of 4-hydroxybutyl acrylate and 18.8 parts of butyl acrylate were 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. Further, ethyl acetate was added to adjust the solid content to 50% to obtain a compound (1) solution.

Synthesis example 2
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 40.0 parts of isophoronediamine (IPDA) and 40.0 parts of toluene. 67.8 parts of 4-hydroxybutyl acrylate was added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 2 hours, and 67.8 parts of toluene was added. Further, ethyl acetate was added to adjust the solid content to 50% to obtain a compound (2) solution.

Synthesis example 3
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 30.0 parts of isophoronediamine (IPDA) and 30.0 parts of toluene. 18.4 parts of 2-hydroxyethyl acrylate and 17.6 parts of ethyl acrylate were 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. Further, ethyl acetate was added to adjust the solid content to 50% to obtain a compound (3) solution.

[Synthesis of urethane urea resin]
Synthesis example 4
In a 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 790 parts Sanix PP-2000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries Ltd.), 110 parts isophorone diisocyanate, toluene 225 parts, dioctyltin dilaurate 0.075 part was charged as a catalyst, the temperature was gradually raised to 100 ° C., and the 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 compound (1) solution was added dropwise over 1 hour, and further aged for 1 hour. After confirming 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, and NCO characteristic absorption (2,270 cm- ¹ ) of IR chart disappeared. It was confirmed that the reaction was completed. The urethane urea resin (A-1) had a weight average molecular weight Mw of 115,000.

[Synthesis of urethane urea resin]
Synthesis Examples 5 to 21
According to the formulation shown in Table 1, urethane urea resins (A-2) to (A-18) were obtained in the same manner as in Synthesis Example 4.

The abbreviations in Table 1 are as follows.
PP600: SANNICS PP-600 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 587)
PP1000: Sannix PP-1000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 1020)
PP2000: Sanniks PP-2000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 1996)
PP3000: Sannix PP-3000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 3032)
PP4000: Sannix PP-4000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 4007)
PE-62: Newpol PE-62 (Propylene glycol and ethylene glycol copolymer, manufactured by Sanyo Chemical Industries, 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: Dioctyltin dilaurate DBTDL: Dibutyltin dilaurate IPDA: Isophoronediamine AMP: 2-amino-2-methyl-propanol

[Synthesis of urethane resin]
Synthesis Example 22
Polyester polyol P-1010 (bifunctional polyester polyol, manufactured by Kuraray Co., Ltd.) 68 parts, polyether polyol G-3000B (3) in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel Functional polyol (manufactured by Asahi Denka Co., Ltd.) 265 parts, 125 parts toluene, 0.03 part iron 2-ethylhexanoate and 0.04 part lead naphthenate as a catalyst, 24 parts of methylene diisocyanate (manufactured by Sumitomo Bayer Co., Ltd.) was added dropwise over 1 hour and reacted at 90 ° C. for 3 hours. It was confirmed that the NCO characteristic absorption (2,270 cm ⁻¹ ) on the IR chart had disappeared, and the reaction was completed. 115 parts of toluene was added to obtain a urethane resin (A-19). The urethane resin (A-19) had a weight average molecular weight Mw of 50,000.

[Synthesis of acrylic resin]
Synthesis Example 23
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 98.5 parts of butyl acrylate, 1.5 parts of acrylic acid, and 150 parts of ethyl acetate, and 70 ° C. under nitrogen substitution. And 0.15 part of azobisisobutyronitrile was added to initiate polymerization. 0.13 parts of azobisisobutyronitrile was added from 3 hours after the start of polymerization to 5 hours after every other hour, and polymerization was further performed for 2 hours. Thereafter, 150 parts of ethyl acetate was added to terminate the polymerization, and an acrylic resin (A-20) was obtained. The weight average molecular weight of this acrylic resin (A-20) was 790,000.

[Synthesis of acrylic resin]
Synthesis Example 24
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 97.7 parts of butyl acrylate, 1.5 parts of 2-hydroxyethyl acrylate, and 150 parts of ethyl acetate, under nitrogen replacement. The mixture was heated to 70 ° C. and 0.15 part of azobisisobutyronitrile was added to initiate polymerization. 0.13 parts of azobisisobutyronitrile was added from 3 hours after the start of polymerization to 5 hours after every other 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
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 89.9 parts of butyl acrylate, 10.0 parts of acrylic acid, 0.1 part of 4-hydroxybutyl acrylate, 63 ethyl acetate And 100 parts of acetone were charged, heated to 65 ° C. under nitrogen substitution, and 0.03 part of azobisisobutyronitrile was added to initiate polymerization. Six hours after the start of polymerization, 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, and an acrylic resin (A-22) was obtained. The weight average molecular weight of this acrylic resin (A-22) was 910,000.

Examples 1-23
A curing agent and a silane coupling agent are blended according to Table 2 with respect to 100 parts of the solid content of the resins (A-1) to (A-16) obtained in Synthesis Examples 4 to 19, and pressure sensitive adhesives for conductive members. A composition was obtained. In the present specification, Examples 6, 7, 10, 15, 16, 22, and 23 are reference examples.

Comparative Examples 1-9
A curing agent, a metal deactivator, and a silane coupling agent are added to 100 parts of the solid content of the resins (A-1) and (A-17) to (A-22) obtained in Synthesis Examples 4 and 20 to 25. The pressure sensitive adhesive composition for conductive members was obtained by blending according to Table 3.

  The pressure-sensitive adhesive composition is applied onto a release-treated polyester film (hereinafter referred to as “release film”) so that the thickness after drying is 50 μm, and dried at 100 ° C. for 2 minutes. An adhesive layer was formed. 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 the condition of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the adhesive layer was advanced to obtain a pressure-sensitive adhesive sheet for a conductive member.

<Evaluation method of adhesive strength>
The pressure-sensitive adhesive sheet is cut to a width of 25 mm, the release film is peeled off, and the exposed pressure-sensitive adhesive layer is applied to a PET film having a thickness of 100 μm, a polycarbonate (PC) plate, a glass plate, and an ITO transparent conductive film. After adhering at 50 ° C.-50% RH and roll pressure bonding according to JIS Z 0237, a pressure of 0.5 MPa was applied in a 50 ° C. atmosphere for 15 minutes to obtain a test piece. After 24 hours of pressure bonding, the pressure-sensitive adhesive sheet was peeled off from each adherend with a peel tester in an atmosphere of 23 ° C.-50% RH at 180 ° peel and a pulling speed of 300 mm / min, and the adhesive strength was measured. .
The evaluation criteria are as follows.

6: “Adhesive strength is 35 N / 25 mm or more.”
5: “Adhesive strength is less than 35 N / 25 mm, 25 N / 25 mm or more.”
4: “Adhesive strength is less than 25 N / 25 mm, 15 N / 25 mm or more.”
3: “Adhesive strength is less than 15 N / 25 mm and 5 N / 25 mm or more.”
2: “Adhesive strength is less than 5 N / 25 mm and 1 N / 25 mm or more.”
1: “Adhesive strength is less than 1 N / 25 mm.”

<Evaluation method for heat and moisture resistance>
As an evaluation of heat resistance and moist heat resistance, the pressure-sensitive adhesive sheet was cut into a width of 100 mm and a length of 100 mm, the release film was peeled off, and bonded and fixed to a glass plate. A test piece having a layer structure of PET film / pressure-sensitive adhesive layer / glass plate was produced by applying pressure and holding for 20 minutes. The floating peeling and foaming after standing for 500 hours at 80 ° C. relative humidity 0% (heat resistance) or 60 ° C. relative humidity 95% (heat and heat resistance) were visually observed. The heat resistance and moist heat resistance were evaluated based on the following three-stage evaluation criteria.
○: “No floating peeling or foaming is observed, and there is no problem in practical use.”
Δ: “Slightly floating peeling / foaming is observed, but there is no practical problem”
×: “There is floating peeling and foaming on the whole surface, which is impractical.”

<Evaluation method for resistance to foaming peeling>
As an evaluation of foaming peel resistance, the pressure-sensitive adhesive sheet was cut into a width of 100 mm and a length of 100 mm, the release film was peeled off, and bonded and fixed to a polycarbonate (PC) plate. A test piece having a layer structure of PET film / pressure-sensitive adhesive layer / PC board was produced by applying a pressure of 0.5 MPa and holding for 20 minutes. The test piece was subjected to heat treatment (heat resistance test) in an oven at 80 ° C. for 24 hours. After this heat resistance test, the adhesion interface of the sample piece (the interface between the pressure-sensitive adhesive layer and the PC plate) was visually observed, and “bubbles” and “floating” were not observed at all. The case where “bubbles” and “float” were slightly recognized was judged as “Δ”, and the case where “bubbles” and “float” were remarkably recognized was judged as “x”.

<Corrosive evaluation method>
For the evaluation of corrosiveness, the pressure-sensitive adhesive sheet cut to a width of 40 mm and a length of 100 mm on an ITO transparent conductive film of a PET film (width 40 mm, length 160 mm) having an ITO transparent conductive film with a thickness of 5 μm was used. The test piece having a layer structure of PET film / pressure-sensitive adhesive layer / ITO film held for 20 minutes under a pressure of 0.5 MPa in an atmosphere of 50 ° C. A touch panel sheet) was prepared. Electrodes were connected to both ends of this test piece, and the initial electrical resistance value was measured [manufactured by Mitsubishi Chemical Corporation, Laresta-GP MCP-T600]. Furthermore, after leaving the test piece to stand at 85 ° C. and a relative humidity of 90% for 500 hours, the electrical resistance value after aging was measured as described above. The rate of change in electrical resistance (electrical resistance value after aging / initial electrical resistance value) is less than 1.2 when it is “◯”, when it is 1.2 or more and less than 1.5, “△”, when 1.5 or more The thing of "x" was made. Further, the corrosivity of the metal circuit using the conductive paste containing Ag powder filler instead of the ITO transparent conductive film was evaluated in the same manner.

<Plasticizer resistance evaluation method>
For the evaluation of plasticizer resistance, the pressure-sensitive adhesive sheet was cut into a width of 100 mm and a length of 100 mm, the release film was peeled off, and bonded and fixed to a polycarbonate (PC) plate. A test piece having a layer structure of PET film / pressure-sensitive adhesive layer / PC board was produced by applying a pressure of 5 MPa and holding for 20 minutes. After this test piece was immersed in a plasticizer (oleic acid) and taken out, the test piece was left to stand for 24 hours at 85 ° C. and 90% relative humidity for 24 hours (adhesion interface between the pressure-sensitive adhesive layer and the PC plate). The interface was visually observed and evaluated based on the evaluation criteria of 5 (no floating or peeling was observed at all) to 1 (no significant lifting or peeling was observed).

<Processing evaluation method>
As an evaluation of workability, the pressure-sensitive adhesive sheet was cut into a width of 100 mm × a length of 100 mm and pressed at 40 ° C. and 60 kg / cm ² for 1 hour to show the state of protrusion of the adhesive layer as 5 (adhesive layer Evaluation was performed based on evaluation criteria of 1 to 1 (no protrusion of the adhesive layer was observed).

The abbreviations in Table 2 and Table 3 are as follows.
B-1: Hexamethylene diisocyanate trimethylolpropane adduct B-2: Hexamethylene diisocyanate isocyanurate B-3: Hexamethylene diisocyanate burette B-4: Xylylene diisocyanate trimethylolpropane adduct B-5: Tolylene diisocyanate Trimethylolpropane adduct B-6: Epoxy curing agent (Tetrad X, manufactured by Mitsubishi Gas Chemical Company, Inc.)
C-1: 3-glycidoxypropyltrimethoxysilane C-2: 3-isocyanatopropyltriethoxysilane C-3: IM-1000 (imidazole group-containing silane coupling agent, manufactured by Nikko Metal Co., Ltd.)
BTZM: Metal deactivator (manufactured by Kyodo Yakuhin Co., Ltd.)
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 conductive members of the present invention has high adhesive strength, heat resistance, moist heat resistance, plasticizer resistance, and workability. It was found to have excellent corrosion resistance against ITO transparent conductive films and metal circuits. On the other hand, in Comparative Examples 1 to 9 in Table 3, the physical properties of each were not balanced, and many of them caused problems particularly in corrosiveness.

Claims (9)

Urethane whose weight average molecular weight (Mw) obtained by reacting a polyamino compound (c) with a urethane prepolymer obtained by reacting a polyol (a) and a polyisocyanate (b) is 50,000 to 200,000. For 100 parts by weight of urea resin (A),
Curing agent (B) viewed 0.1-3 parts including,
The pressure sensitive adhesive composition for conductive members , wherein the amount of the polyamino compound (c) used is 0.5 to 5% by weight in 100% by weight of the urethane urea resin (A) .
A pressure-sensitive adhesive composition for conductive members. The pressure-sensitive adhesive composition for conductive members according to claim 1, wherein the amount of the polyisocyanate (b) used is 8 to 23% by weight in 100% by weight of the urethane urea resin (A).   The pressure-sensitive adhesive composition for conductive members according to claim 1 or 2, wherein the polyol (a) contains a polyol having a polypropylene glycol skeleton.   The curing agent (B) is at least one selected from hexamethylene diisocyanate trimethylolpropane adduct, hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate burette, and xylylene diisocyanate trimethylolpropane adduct. 3. The pressure-sensitive adhesive composition for conductive members according to any one of 3 above.   0.1 to 1.0 weight of silane coupling agent having 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, or imidazole group with respect to 100 parts by weight of urethane urea resin (A) The pressure-sensitive adhesive composition for conductive members according to claim 1, comprising parts.   A pressure-sensitive adhesive sheet for a conductive member formed by forming a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for a conductive member according to any one of claims 1 to 5 on one side or both sides of a sheet-like substrate.   The laminated body by which the pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition for conductive members in any one of Claims 1-5 is laminated | stacked on a conductive member.   The laminate according to claim 7, wherein the conductive member is a transparent conductive film or a metal circuit.   The sheet | seat for touchscreens which has the laminated body of Claim 7 or 8.