JP2014141636A - Conductive composition, structure and junction device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition having extremely small variation of a resistance even when coated on a transparent electrode substrate and exposed to a high temperature high moisture condition, and to provide a structure using the composition and a junction device.SOLUTION: There is provided a structure obtained by coating a transparent electrode substrate with a liquid conductive composition containing (A) a saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bound to a silicon atom and at least one crosslinkable silicon group capable of being crosslinked by forming a siloxane bond and (B) a conductive filler.

Description

  The present invention relates to a conductive composition, a structure using the conductive composition, and a bonding device.

  Conventionally, an anisotropic conductive film is used for connection between an electrode and a connection target in an organic EL display device or the like (for example, Patent Document 1). However, in the case of connection using an anisotropic conductive film, there is a problem that damage to the substrate is inevitable because thermocompression bonding is required.

  Therefore, a connection method using a room temperature curing type conductive adhesive has been desired. For example, the conductive adhesive described in Examples 1 to 11 and 14 to 22 of Patent Document 2 is used, and the conductive material is applied to the transparent electrode substrate. When the adhesive is applied in a bead shape and exposed to high temperature and high humidity conditions for a long time, the resistance at the interface between the electrode and the conductive adhesive increases, and the resistance between the two beads varies significantly. It turns out that the problem of doing.

JP 2009-87951 A WO2012 / 085588 JP 2002-298654 A JP 2013-100592 A

  The present invention provides a conductive composition having a very small change in resistance value even when it is applied to a transparent electrode substrate and exposed to high temperature and high humidity conditions, a structure using the composition, and a bonding device. With the goal.

  In order to solve the above problems, the structure of the present invention is a structure obtained by applying a liquid conductive composition to a transparent electrode substrate, and the liquid conductive composition is bonded to (A) silicon atoms. A saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group and having at least one crosslinkable silicon group that can be crosslinked by forming a siloxane bond, and (B) a conductive filler. Features.

  The bonding device of the present invention is a bonding device formed by bonding a transparent electrode substrate and a member to be bonded using a liquid conductive composition, wherein the liquid conductive composition is (A) a hydroxyl group bonded to a silicon atom. Or a saturated hydrocarbon polymer having a hydrolyzable group and having at least one crosslinkable silicon group that can be crosslinked by forming a siloxane bond, and (B) a conductive filler. To do.

  The conductive composition of the present invention is a conductive composition used in the structure of the present invention, and (A) has a hydroxyl group or hydrolyzable group bonded to a silicon atom, thereby forming a siloxane bond. A region containing 5 to 7 mm from the left and right ends of an ITO substrate having a width of 45 mm and a length of 45 mm, comprising a saturated hydrocarbon polymer having at least one crosslinkable silicon group capable of crosslinking, and (B) a conductive filler. The conductive composition was applied in the form of a bead with a width of 2 mm and a height of 1.2 mm to form two beads, which were then placed under conditions of 23 ° C. and 50% RH for 2 days, and then at 50 ° C. The structure obtained by heating for 12 hours and then heating at 80 ° C. for 1 hour was initially (cooled for 3 hours at 23 ° C. and 50% RH) and stored (the structure was 85 ° C. and 85% RH). After 100 hours storage at 23 ° C 50% RH condition Wherein the 3-hour cooling) the two after storage at the time of measuring the resistance value between the bead / initial rate of change of the resistance value is not more than 80% to 200% after.

  The conductive composition of the present invention has (C) a (meth) acrylic group having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having at least one crosslinkable silicon group that can be crosslinked by forming a siloxane bond. It is preferable to further contain an acid ester polymer.

  According to the present invention, there is an enormous effect that the variation in resistance value is extremely small even when applied to a transparent electrode substrate and exposed to high temperature and high humidity conditions. In addition, the conductive composition of the present invention can be cured at room temperature and moisture, and can prevent damage to the substrate.

2 is a schematic explanatory diagram of a test specimen produced in Example 1. FIG.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The conductive composition of the present invention comprises (A) a saturated hydrocarbon group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one crosslinkable silicon group that can be crosslinked by forming a siloxane bond. A polymer and (B) a conductive filler are contained.

  As a typical example of the crosslinkable silicon group having a hydroxyl group or hydrolyzable group bonded to a silicon atom in the (A) saturated hydrocarbon polymer and capable of crosslinking by forming a siloxane bond, the following formula (1) ).

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹ ₃ SiO— (R ¹ is the same as above), and when two or more R ¹ are present, they may be the same or different, and X is a hydroxyl group or a hydrolyzable group. Represents a group, and when two or more X are present, they may be the same or different, a represents 0, 1, 2 or 3, b represents 0, 1 or 2; In the following n formulas (2), b need not be the same, and n represents an integer of 0 to 19, provided that a + (sum of b) ≧ 1.

  The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.

The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms. A crosslinkable silicon group represented by the following formula (3) (wherein R ¹ , X, and a are the same as described above) is preferable from the viewpoint of easy availability.

Specific examples of R ¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a small number of carbon atoms have high reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.
In the case of the crosslinkable silicon group represented by the formula (3), a is preferably 2 or more in consideration of curability. Usually, when a is 3, the curing rate is higher than when a is 2.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups such as a trimethoxysilyl group and a triethoxysilyl group, dialkoxy such as —Si (OR ² ) ₃ , a methyldimethoxysilyl group, and a methyldiethoxysilyl group. And a silyl group, —SiR ² ₁ (OR ² ) ₂ . Here, R ² is an alkyl group, preferably an alkyl group having 10 or less carbon atoms, and more preferably a methyl group or an ethyl group. When two or more R ² are present, they may be the same or different. Among these, the methyldimethoxysilyl group has mild reactivity and is also used as a crosslinkable silicon group in industrially produced saturated hydrocarbon polymers. A trimethoxysilyl group having high reactivity is known as a crosslinkable silicon group, and may be used as a crosslinkable silicon group in the saturated hydrocarbon polymer of the present invention.

  One type of crosslinkable silicon group may be used, or two or more types may be used in combination. The crosslinkable silicon group can be present in the main chain, the side chain, or both. It is preferable that a crosslinkable silicon group is present at the end of the molecular chain in view of excellent cured product properties such as tensile properties of the cured product.

  At least one, preferably 1.1 to 5, crosslinkable silicon groups may be present in one molecule of the component (A) polymer. When the number of crosslinkable silicon groups contained in the molecule is less than one, the curability is insufficient, and when the number is too large, the network structure becomes too dense, and good mechanical properties are not exhibited.

  The crosslinkable silicon group may be present at the terminal of the saturated hydrocarbon polymer molecular chain, may be present inside, or may be present in both. In particular, when a crosslinkable silicon group is present at the end of the molecular chain, the amount of the effective network chain of the saturated hydrocarbon polymer component contained in the finally formed cured product increases, so that the strength and elongation are high. This is preferable from the viewpoint of easily obtaining a rubber-like cured product. Further, these saturated hydrocarbon polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

The polymer that forms the skeleton of the saturated hydrocarbon polymer having a crosslinkable silicon group used in the present invention,
(1) polymerizing an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like as a main monomer;
(2) Homogeneous polymerization of diene compounds such as butadiene and isoprene, or copolymerization of the olefin compounds and diene compounds,
However, it is easy to introduce a functional group at the terminal, to easily control the molecular weight, and to increase the number of terminal functional groups, so that an isobutylene polymer or a hydrogenated polybutadiene system can be obtained. A polymer is preferred.
In addition, the saturated hydrocarbon polymer referred to in this specification is a concept that means a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring.

  In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, and the monomer units copolymerizable with isobutylene are preferably 50% (weight%, in the isobutylene polymer). The same shall apply hereinafter), more preferably 30% or less, particularly preferably 10% or less.

  Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. Specific examples of such copolymer components include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, Vinyl cyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, dimethyl styrene, monochlorostyrene, dichlorostyrene, β-vinene, indene, vinyl trichlorosilane, vinyl methyl dichlorosilane, vinyl dimethyl chlorosilane, vinyl dimethyl methoxy Silane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3, -tetramethyldisiloxane, trivinylmethylsilane, tetrabi Nylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane and the like.

  When vinyl silanes or allyl silanes are used as monomers copolymerizable with isobutylene, the silicon content increases, the number of groups that can act as silane coupling agents increases, and the adhesiveness of the resulting composition improves. To do.

  The hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers also contain other monomer units in addition to the main monomer unit, as in the case of the isobutylene-based polymer. You may let them.

  In addition, the saturated hydrocarbon polymer used in the present invention contains a small amount of monomer units such that a double bond remains after polymerization, such as a butadiene compound such as butadiene and isoprene, to the extent that the object of the present invention is achieved. Preferably, it may be contained in a range of 10% or less, further 5% or less, and particularly 1% or less.

  The number average molecular weight of the saturated hydrocarbon polymer, preferably an isobutylene polymer or a hydrogenated polybutadiene polymer, is preferably about 500 to 80,000, more preferably about 1000 to 50,000. In particular, a liquid material having a fluidity of about 2,000 to 30,000 to a fluid material is preferable from the viewpoint of easy handling. The saturated hydrocarbon polymer (A) may be used alone or in combination of two or more. In the present specification, the number average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

  Among the isobutylene polymers having a crosslinkable silicon group, an inbutylene polymer having a crosslinkable silicon group at the molecular chain terminal is a polymerization method called an inifer method (initiator and chain transfer agent called an inifer are combined. It can be produced using a terminal functional type, preferably an all terminal functional type isobutylene polymer obtained by a cationic polymerization method using a specific compound. Such production methods are described, for example, in JP-A-63-006041, JP-A-63-006003, JP-A-63-254149, JP-A-01-038407, and the like.

  An isobutylene polymer having a crosslinkable silicon group in the molecular chain is produced by adding a vinylsilane or allylsilane having a crosslinkable silicon group to a monomer mainly composed of isobutylene and copolymerizing the monomers.

  Furthermore, in the polymerization for producing an isobutylene polymer having a crosslinkable silicon group at the molecular chain end, a terminal is obtained by copolymerizing vinylsilanes or allylsilanes having a crosslinkable silicon group in addition to the main component isobutylene monomer. By introducing a crosslinkable silicon group into an isobutylene polymer having a crosslinkable silicon group at the terminal and inside the molecular chain is produced.

  Specific examples of vinylsilanes and allylsilanes having a crosslinkable silicon group include, for example, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, Examples include allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

In the hydrogenated polybutadiene polymer, for example, the hydroxyl group of the terminal hydroxy hydrogenated polybutadiene polymer is first converted into an oxymetal group such as -ONa or -OK, and then the following formula (4):
^{_{CH 2 = CH-R 3 -Y}} ··· (4)
(In the formula, Y is a halogen atom such as a chlorine atom or an iodine atom, R ³ is —R ⁴ —, —R ⁴ —OCO—, or —R ⁴ —CO— (R ⁴ is a divalent having 1 to 20 carbon atoms. of a hydrocarbon group, preferably an alkylene group examples, a cycloalkylene group, an arylene group, a divalent organic group represented by aralkylene group), -CH 2 _-,

A hydrogenated polybutadiene-based polymer having a terminal olefin group is reacted with an organic halogen compound represented by (R ″ is a divalent group selected from hydrocarbon groups having 1 to 10 carbon atoms). Hereinafter, it is also referred to as a terminal olefin hydrogenated polybutadiene polymer).

The method for converting the terminal hydroxyl group of the terminal hydroxy-hydrogenated polybutadiene polymer to an oxymetal group includes alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ; caustic alkalis such as caustic soda and caustic potash. And the like.

  In the above method, a terminal olefin hydrogenated polybutadiene polymer having almost the same molecular weight as that of the terminal hydroxy hydrogenated polybutadiene polymer used as a starting material is obtained. Before reacting the organic halogen compound (4), a polyvalent organic halogen compound containing two or more halogen atoms in one molecule, such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, and the like; When reacted, the molecular weight can be increased. After that, when reacted with the organic halogen compound represented by the formula (4), a hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal is obtained. be able to.

  Specific examples of the organic halogen compound represented by the formula (4) include, for example, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether. , Allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene, and the like, but are not limited thereto. Of these, allyl chloride is preferred because it is inexpensive and easily reacts.

The introduction of the crosslinkable silicon group into the terminal olefin-hydrogenated polybutadiene polymer is conducted, for example, in the same manner as in the case of an isobutylene polymer having a crosslinkable silicon group at the molecular chain terminal, with hydrogen being added to the group represented by the formula (1) It is produced by subjecting an atom-bonded hydrosilane compound, preferably a compound represented by the following formula (wherein R ¹ , X and a are the same as above) to an addition reaction using a platinum-based catalyst.

  Specific examples of the hydrosilane compound in which a hydrogen atom is bonded to the group represented by the formula (1) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxy Alkoxysilanes such as silane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoxy) Mate) ketoximate silanes such as methyl silane, but are not limited thereto. Of these, halogenated silanes and alkoxysilanes are particularly preferable.

  As the conductive filler (B), known fillers having conductive performance can be widely used, and there is no particular limitation. For example, silver powder, copper powder, nickel powder, aluminum powder, silver plating powder thereof, and silver coat Metal powders such as glass, silver-coated silica, and silver-coated plastics; zinc oxide, titanium oxide, ITO, ATO and the like can be mentioned, and silver powder is preferred.

  The shape of the conductive filler (B) is not particularly limited, and various shapes such as flakes and granules can be used, but the combined use of flakes and granules is preferable. In the present invention, the flake shape includes a shape called a flat shape, a flake shape, or a scale shape, and is a shape obtained by crushing a solid shape such as a spherical shape or a lump shape in one direction. In addition, granular means all shapes that are not flaked, for example, agglomerated powder in the shape of a bunch of grapes, spherical shape, approximately spherical shape, lump shape, dendritic shape, spike shape, and these A mixture of powders having the shape of The dendritic shape is a shape in which a plurality of cocoon-like and / or scaly pieces are bonded to each other, and examples of the resinous conductive filler include those described in Patent Document 3 and Patent Document 4. . Also, it is sold as ACAX-2, ACAX-3, or ACBY-3 by Mitsui Kinzoku Co., Ltd.

  The 50% average particle size of the conductive filler (B) is preferably 0.5 to 30 μm.

  In the present invention, the blending ratio of the conductive filler (B) is not particularly limited, but is preferably 50% by mass or more and 85% by mass or less of the total content (solid content conversion) not including the solvent of the conductive composition.

The conductive composition of the present invention has (C) a (meth) acrylic group having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having at least one crosslinkable silicon group that can be crosslinked by forming a siloxane bond. It is preferable to further contain an acid ester polymer.
The crosslinkable silicon group contained in the (C) (meth) acrylic acid ester polymer is the same group as the crosslinkable silicon group contained in the saturated hydrocarbon polymer (A).

  As in the case of the saturated hydrocarbon polymer (A), at least one crosslinkable silicon group is present in one molecule of the (meth) acrylic acid ester polymer, preferably 1.1 to 5, and (meth) The acrylate polymer may be present at the end of the molecular chain, may be present inside, or may be present at both, but is preferably present at the end of the molecular chain. Moreover, these (meth) acrylic acid ester-type polymers (C) which have a crosslinkable silicon group may be used independently, and may be used together 2 or more types.

The polymer which forms the skeleton of the (meth) acrylic acid ester polymer (C) used in the present invention is a (meth) acrylic acid ester monomer which is used if necessary with a (meth) acrylic acid ester monomer unit. It is preferable that the content of the (meth) acrylic acid ester monomer unit is 50% or more, and more preferably 70% or more. When the ratio of the (meth) acrylic acid ester monomer unit is less than 50%, the glass transition temperature (Tg) decreases, and the heat resistance and the elastic modulus tend to decrease.
The (meth) acrylic acid ester monomer unit has the following formula (5) (wherein R ⁴ is a monovalent substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and R ⁵ is a hydrogen atom or methyl. Represents a group).

Specific examples of the monovalent C1-C30 substituted or unsubstituted hydrocarbon group which is R ⁴ in the formula (5) include, for example, a methyl group, an ethyl group, an n-butyl group, an isobutyl group, 1 -Ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylbenzyl group, 1-ethylbutyl group, 2-ethylbutyl group, isooctyl group, 3,5,5-trimethylhexyl group, 2-ethylhexyl Group, decyl group, dodecyl group, tridecyl group, hexadecyl group, stearyl group, allyl group and other branched or unbranched alkyl groups having 1 to 30 carbon atoms, alkylene groups, and benzyl groups having 1 to 30 carbon atoms Examples thereof include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms such as substituted alkyl groups, phenyl groups, and chlorophenyl groups.

  Among these, an alkyl group is preferable because it is easily available, and an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-butyl group, and an isobutyl group is particularly preferable.

  Specific examples of the monomer copolymerizable with the (meth) acrylic acid ester monomer used if necessary include acrylic acid-based monomers such as acrylic acid and methacrylic acid; di (meth) Such as ethylene glycol acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate Polyfunctional (meth) acrylic acid ester monomers; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and methylenebisacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate, Jie Monomers containing amino groups such as ruaminoethyl methacrylate and aminoethyl vinyl ether; other γ-acryloyloxypropyltriethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, maleic anhydride, acrylonitrile, methacrylonitrile, iminol Copolymerizable with monomers such as methacrylate, diallyl phthalate, styrene, α-methylstyrene, vinyl pyridine, alkyl vinyl ether, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, ethylene, propylene, isobutylene, and isobutylene. Examples thereof include olefins having 4 to 12 carbon atoms, conjugated dienes, vinyl ethers, vinyl silanes, allyl silanes and the like already described.

  The method for producing the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is disclosed in JP-A-60-31556, 61-34067, 57-36109, 57-55954, Although disclosed in JP-A-61-225205, etc., among these polymers, a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group at the molecular chain terminal should be produced, for example, by the following method. Can do.

That is,
(I) (meth) acrylic acid ester monomer contained if a monomer having copolymerizability with a (meth) acrylic acid ester monomer is required using a radical polymerization initiator containing a crosslinkable silicon group Polymerize the body,
(Ii) polymerizing the (meth) acrylic acid ester monomer of (i) using a radical polymerization chain transfer agent containing a crosslinkable silicon group;
(Iii) The (meth) acrylic acid ester monomer of (i) is polymerized in combination with the radical polymerization initiator and radical polymerization chain transfer agent used in (i) and (ii).
(Iv) Using a radical polymerization initiator and / or a radical polymerization chain transfer agent containing a functional group (hereinafter referred to as Z) such as a carboxyl group, a hydroxyl group, a halogen atom, an amino group, and an epoxy group ( By polymerizing a meth) acrylic acid ester monomer, a polymer having a Z group at the polymer molecule end is produced, or a polymer is produced by further reacting the Z group with a polyfunctional compound such as triisocyanate. An isocyanate group, a carboxyl group, a hydroxyl group, a halogen atom, an amino group, an epoxy that can react with the Z group or the Z ′ group by producing a polymer having a functional group (hereinafter referred to as Z ′ group) at the molecular end A silicon compound having a functional group such as a group, a mercapto group or an acrylic group and having a crosslinkable silicon group is reacted with a Z group or a Z ′ group at the end of the polymer. .

  Specific examples of the radical polymerization initiator having a crosslinkable silicon group include azo radicals such as compounds represented by the following formulas (I) to (III) disclosed in JP-A-60-31558, for example. Examples thereof include polymerization initiators and peroxide radical polymerization initiators such as compounds represented by the following formulas (IV) and (V).

Examples of the radical polymerization chain transfer agent having a crosslinkable silicon group include (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SH, [(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ S—] ₂ , [(CH ₃ O) ₃ SiC ₆ H ₄ S—] ₂ , compounds represented by the following formula (VI), and the like.

  In addition, (meth) acrylic acid ester-based polymers having a crosslinkable silicon group in the molecular chain are vinylsilanes and allylsilanes having a crosslinkable silicon group in monomers mainly composed of (meth) acrylate monomer units. It is produced by adding a copolymer or the like and copolymerizing it.

  Further, the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group at the molecular chain terminal and inside is further crosslinked when the (meth) acrylic acid polymer having a crosslinkable silicon group at the molecular terminal is produced. It is manufactured by adding vinyl silanes or allyl silanes having a functional silicon group and copolymerizing them.

  Specific examples of vinyl silanes and allyl silanes having a crosslinkable silicon group include those similar to those used in the production of the above-mentioned isobutylene polymer having a crosslinkable silicon group in the molecular chain. It is done.

  JP 2001-040037 A, JP 2003-048923 A and JP 2003-048924 A have a crosslinkable silicon group (meth) obtained by using a mercaptan having a crosslinkable silicon group and a metallocene compound. Acrylic acid alkyl ester polymers are described. Moreover, the synthesis example of Unexamined-Japanese-Patent No. 2005-026881 describes the (meth) acrylic-acid alkylester type polymer which has a crosslinkable silicon group by high temperature continuous polymerization. Such a polymer can be used as the component (C) of the present invention.

  Further, as disclosed in JP 2000-086999 A, a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group, in which a crosslinkable silicon group is introduced at a high rate at the molecular chain terminal. Coalescence is also known. Since such a polymer is produced by living radical polymerization, a crosslinkable silicon group can be introduced into the molecular chain terminal at a high rate. Such a polymer can be used as the component (C) of the present invention.

  In the present invention, a (meth) acrylic acid alkyl ester polymer as described above can be used. Among these, a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group obtained by using a mercaptan having a crosslinkable silicon group and a metallocene compound is preferable.

The number average molecular weight of the (meth) acrylic acid ester polymer (C) is 500 to 100,000.
Are preferable from the viewpoint of easy handling and the like, and more preferably 1,000 to 75,000.

  The blending ratio of the (C) (meth) acrylic acid ester polymer is not particularly limited, but is 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing saturated hydrocarbon polymer. Is preferred.

  The conductive composition of the present invention may be used in combination with another organic polymer having a crosslinkable silicon group, for example, a crosslinkable silicon group-containing polyoxyarlequin polymer.

  In the conductive composition of the present invention, a curing catalyst, a filler, a plasticizer, an adhesion-imparting agent, a stabilizer, a physical property modifier, a thixotropic agent, a dehydrating agent (as needed to adjust viscosity and physical properties) Storage stability improvers), tackifiers, flame retardants, radical polymerization initiators and the like may be blended, or other compatible polymers may be blended.

  Examples of the curing catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dioctyltin dilaurate, dioctyltin Maleate, dioctyltin diacetate, dioctyltin dineodecanate (dioctyltin diversate), dioctyltin oxide, tetravalent tin compounds such as reaction product of dibutyltin oxide and phthalate, tin dioctylate, tin dinaphthenate, tin distearate, Organotin compounds such as divalent tin compounds such as tin dinedecanoate (tinversic acid tin); aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopro Organoaluminum compounds such as xyaluminum ethyl acetoacetate; reaction product of bismuth salt such as bismuth-tris (2-ethylhexoate), bismuth-tris (neodecanoate) and organic carboxylic acid or organic amine, etc .; zirconium tetraacetyl Chelate compounds such as acetonate and titanium tetraacetylacetonate; organic lead compounds such as lead octylate; organic iron compounds such as iron naphthenate; organic vanadium compounds; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine , Diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethyleneamine Amines such as tylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) Compounds or salts thereof with carboxylic acid, etc .; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, N— Examples include known silanol composite catalysts such as silane coupling agents having an amino group such as (β-aminoethyl) aminopropylmethyldimethoxysilane. These catalysts may be used alone or in combination of two or more.

  These curing catalysts may be used alone or in combination of two or more. Of these curing catalysts, organometallic compounds or a combined system of organometallic compounds and an amine compound are preferred from the viewpoint of curability. Furthermore, dibutyltin maleate, a reaction product of dibutyltin oxide and a phthalate ester, dibutyltin diacetylacetonate, and dioctyltin dineodecanate are preferred because of their high curing speed. Moreover, a dioctyl tin compound is preferable from the viewpoint of environmental problems. The curing catalyst is preferably used in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymer of component (A).

  Plasticizers include phthalates such as diisodecyl phthalate, diundecyl phthalate, diisoundecyl phthalate, dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate; aliphatics such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, etc. Dibasic acid esters; Glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester; Aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; Epoxidized soybean oil, epoxidized linseed oil, epoxy benzyl stearate, etc. Epoxy plasticizers such as: polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; polyethers such as polypropylene glycol and derivatives thereof; ) Poly (meth) acrylate plasticizers such as alkyl acrylates; polystyrenes such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymers, polychloroprene, polyisoprene, polyisobutene, paraffinic carbonization Plasticizers such as hydrogen, naphthenic hydrocarbons, paraffin-naphthene mixed hydrocarbons and chlorinated paraffins can be used alone or in the form of a mixture of two or more.

In particular, from the viewpoint of weather resistance, polyether plasticizers such as polypropylene glycol and its derivatives that do not contain unsaturated bonds in the polymer main chain, poly (meth) acrylate plasticizers,
Polyisobutene, paraffin and the like are preferable. In particular, polyether plasticizers such as polypropylene glycol and derivatives thereof and poly (meth) acrylate plasticizers, which are polymer plasticizers, are preferable. When using a plasticizer, it is preferable to add 1-200 weight part with respect to 100 weight part of polymer of (A) component, Furthermore, 5-150 weight part is added.

  Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- Amino group-containing silanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; N -(1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, etc. Ketimine type silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriet Epoxy group-containing silanes such as xysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc. Mercapto group-containing silanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane; γ-chloropropyltri Chlorine atom-containing silanes such as methoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; methyldimethoxysilane, tri Tokishishiran, although hydro silanes such as methyl diethoxy silane can be specifically exemplified, but the invention is not limited thereto. Using modified amino group-containing silanes in which the amino group is modified by reacting the amino group-containing silanes with an epoxy group-containing compound, isocyanate group-containing compound, or (meth) acryloyl group-containing compound containing the silanes. Also good.

  If the adhesiveness-imparting agent is added too much, the modulus of the cured product will be high, and if it is too low, the adhesiveness will decrease. It is preferable to add, more preferably 0.5 to 10 parts by weight.

  Fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, carbonic acid Magnesium, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and chloride Examples thereof include fillers such as resin powders such as organic microballoons of vinylidene resin, PVC powder, and PMMA powders; fibrous fillers such as asbestos, glass fibers, and filaments.

  When using a filler, the usage-amount is 1-250 mass parts with respect to 100 mass parts of polymers of (A) component, Preferably it is 10-200 mass parts. These fillers may be used alone or in combination of two or more.

  As described in JP-A No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, sealed in a bag made of an airtight material, and left for an appropriate time. It is also possible to dehydrate and dry in advance. By using this low water content filler, storage stability can be improved particularly when a one-component composition is used.

  When you want to obtain a hardened material with high strength by using these fillers, mainly fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment A filler selected from fine calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable and used in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the organic polymer (A) having a crosslinkable silicon group. Favorable results are obtained. In addition, when it is desired to obtain a cured product having low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the organic polymer (A) having a crosslinkable silicon group, preferable results are obtained. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. When calcium carbonate is used, it is desirable to use a combination of surface treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and an untreated surface can be used.

  Addition of an organic balloon or an inorganic balloon is preferable for improving the workability (crisis, etc.) of the composition. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less.

  In the present invention, it is preferable to add silica in order to prevent bleeding while ensuring flowability without increasing the viscosity. These silicas can be surface-treated, and may be used alone or in combination of two or more. From the viewpoint of preventing bleeding, it is preferable to use hydrophilic silica or hydrophobic silica hydrophobized with a specific surface treatment agent. The hydrophobic silica is at least one surface treatment selected from the group consisting of dimethyldichlorosilane, hexamethyldisilazane, (meth) acrylsilane, octylsilane (for example, trimethoxyoctylsilane), and aminosilane. Hydrophobic silica hydrophobized with an agent is preferred.

  You may mix | blend a solvent and a diluent in the range by which the objective of this invention is achieved for the improvement of workability | operativity, the fall of a viscosity, etc. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Examples of the diluent include normal paraffin, isoparaffin, and the like.

  A tackifier may be added to improve the wettability to the adherend and to increase the peel strength. Examples include petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin, phenolic resin copolymer thereof, and phenol / phenol novolac resin-based tackifier resin.

  Examples of other additives include sagging inhibitors such as hydrogenated castor oil, organic bentonite, and calcium stearate, colorants, antioxidants, ultraviolet absorbers, and light stabilizers. Furthermore, additives such as other resins such as epoxy resins, curing agents such as epoxy resin curing agents, physical property modifiers, storage stability improvers, lubricants, and foaming agents can be added as necessary. .

  The conductive composition of the present invention can be a one-component type or a two-component type as required, and can be suitably used particularly as a one-component type. The conductive composition of the present invention can be cured at room temperature by moisture in the atmosphere, and is suitably used as a room temperature moisture curable conductive composition, but if necessary, curing is accelerated by heating appropriately. You may let them.

  Since the conductive composition of the present invention is a liquid composition, it is excellent in workability. The conductive composition of the present invention preferably has a viscosity at 23 ° C. in the range of 100 to 800 Pa · s.

The conductive composition of the present invention is a conductive composition used for a structure formed by applying a liquid conductive composition to a transparent electrode substrate, has high conductivity, and has a volume resistivity of 10 × 10 ^−3. A low resistance value of less than Ω · cm can be achieved, and there is a tremendous effect that even when applied to a transparent electrode substrate and exposed to high-temperature and high-humidity conditions, the variation in resistance value is extremely small. Specifically, as shown in FIG. 1, the present invention is applied to a region of 5 mm to 7 mm from the left and right ends of the ITO substrate 10 having a width of 45 mm and a length of 45 mm (that is, two regions having a width of 2 mm and a length of 45 mm). Two conductive compositions 12 are applied in the form of a bead with a width of 2 mm and a height of 1.2 mm to form two beads 14, which are then placed under conditions of 23 ° C. and 50% RH for 2 days, and then at 50 ° C. The structure 20 obtained by leaving for 12 hours and further heating at 80 ° C. for 1 hour was initially (cooled at 23 ° C. and 50% RH for 3 hours) and stored (the structure was 85 ° C. and 85% After storage for 100 hours at RH and then cooled for 3 hours under conditions of 23 ° C. and 50% RH), when the resistance value is measured between the two beads 14, the change rate of the initial resistance value after storage is 80% or more It is 200% or less.

  The structure of the present invention is a structure formed by applying the liquid conductive composition of the present invention to a transparent electrode substrate. There is no restriction | limiting in particular as this transparent electrode substrate, A well-known transparent electrode substrate can be used widely, For example, the board | substrate containing an ITO electrode is preferable. Since the conductive composition of the present invention is adhered to the transparent electrode substrate, it also has an effect that it does not peel off.

  The joining device of this invention is a joining device formed by adhere | attaching a transparent electrode substrate and a to-be-joined member using the liquid conductive composition of this invention. There is no restriction | limiting in particular as this transparent electrode substrate, A well-known transparent electrode substrate can be used widely, For example, the board | substrate containing an ITO electrode is preferable. Although there is no restriction | limiting in particular as this to-be-joined member, For example, the board | substrate containing an electrode is preferable.

  As a joining device of this invention, organic EL, a solar cell panel, a touch panel, etc. are mentioned, for example.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Synthesis Example 1)
In a flask, 40 parts by mass of ethyl acetate as a solvent, 59 parts by mass of methyl methacrylate, 25 parts by mass of 2-ethylhexyl methacrylate, 22 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 0.1 part by mass of ruthenocene dichloride as a metal catalyst were added. The mixture was heated to 80 ° C. while introducing charged nitrogen gas. Next, 8 parts by mass of 3-mercaptopropyltrimethoxysilane was added to the flask and reacted at 80 ° C. for 6 hours. After cooling to room temperature, 20 parts by mass of a benzoquinone solution (95% THF solution) was added to terminate the polymerization. The solvent and unreacted substances are distilled off, the polystyrene-reduced mass average molecular weight is about 6000, Mw (mass average molecular weight) / Mn (number average molecular weight) is 1.6, and Tg is 61.2 ° C. An acrylate polymer C1 having a trimethoxysilyl group was obtained.

(Synthesis Example 2)
A methanol solution of sodium methoxide (NaOMe) was added to polyoxypropylene diol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group to an allyl group. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added to react with trimethoxysilane, and the weight average molecular weight in terms of PPG (polypropylene glycol) is about 25,000, and 1.5 per molecule. Polyoxypropylene polymer X1 having a number of terminal trimethoxysilyl groups was obtained.

(Synthesis Example 3)
Add a methanol solution of sodium methoxide (NaOMe) to a polyoxypropylene diol having a molecular weight smaller than that of the polyoxypropylene diol used in Synthesis Example 2 and distill off the methanol. Converted to the base. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added and reacted with trimethoxysilane, so that the weight average molecular weight in terms of PPG is about 15000, and 1.5 terminal trioxyls per molecule. A polyoxypropylene polymer X2 having a methoxysilyl group was obtained.

Example 1
As shown in Table 1, as a saturated hydrocarbon polymer having a crosslinkable silicon group, methyldimethoxysilyl group-terminated polyisobutylene (containing 33% process oil) (manufactured by Kaneka Corporation, EPION EP505S), 150 parts by weight, crosslinked As a (meth) acrylic acid ester-based polymer having a functional silicon group, the polymer C1 having a crosslinkable silyl group obtained in Synthesis Example 1; 15 parts by weight, as a plasticizer, paraffin-based process oil (Idemitsu Kosan Co., Ltd. ), Diana Process Oil PS-32) 15 parts by weight, 4,4- (α, α-dimethylbenzyl) diphenylamine (Ouchi Shinsei Chemical Co., Ltd., NOCRACK CD) 3 parts by weight, hindered phenol oxidation 3 parts by weight of inhibitor (manufactured by ADEKA, Adeka Stub AO-60), hindered amine light stabilizer (manufactured by ADEKA, A 3 parts by weight of Dekastab LA-63P), 3 parts by weight of hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd., Aerosil R972) were stirred and degassed with a stirring mixer, and then heated and dehydrated at 100 ° C. for 1 hour. And it cooled to 50 degrees C or less.

Subsequently, 2 parts by mass of tetraethoxysilane (manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 28), 4 parts by weight of decyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-3103C) as a dehydrating agent, diluent As a paraffinic diluent (manufactured by JX Nippon Oil & Energy Corporation, trade name: Cactus normal paraffin N-11), followed by sill coat AgC-B (specific surface area 1.35 m ² / g, as a conductive filler, Tap density 4.6 g / cm ³ , 50% average particle size 4 μm, trade name, trade name of Fukuda Metal Foil Powder Co., Ltd., flaky silver powder) 540 parts by mass, sill coat AgC-G (specific surface area 2.5 m) ² / g, tap density 1.4 g / cm ³ , 360 parts by mass of Fukuda Metal Foil Powder Co., Ltd., trade name, granular silver powder), 3-aminopropyl as an adhesion promoter 6 parts by mass of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903), 3 parts by mass of dioctyltin-based curing catalyst (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan S-1) as a curing catalyst, A conductive composition was obtained by stirring and defoaming.

  The viscosity at 23 ° C. of the obtained conductive composition was measured using a BS type rotational viscometer (rotor No. 7 10 rpm). The results are shown in Table 2.

  Further, using the obtained conductive composition, as shown in FIG. 1, a region of 5 mm to 7 mm from the left and right edges of the ITO substrate having a width of 45 mm and a length of 45 mm (that is, a region having a width of 2 mm and a length of 45 mm). 2 places), the conductive composition was applied in the form of a bead with a width of 2 mm and a height of 1.2 mm. After forming the two beads, the mixture was placed at 23 ° C. and 50% RH for 2 days, then 50 A structure obtained by placing at 12 ° C. for 12 hours and further heating at 80 ° C. for 1 hour was obtained. The structure was initially (cooled at 23 ° C. and 50% RH for 3 hours) and stored (the structure was stored at 85 ° C. and 85% RH for 60 hours or 100 hours, and then 23 ° C. and 50%. After cooling for 3 hours under RH conditions), the resistance value between the beads of the two conductive compositions was measured using a two-terminal tester (Kyoritsu Electric Meter Co., Ltd., Digital Multimeter, KEW1052). The results are shown in Table 2.

Further, the obtained conductive composition was cured in an environment of 23 ° C. and 50% RH for 14 days, and then dried with an 80 ° C. dryer for 12 hours to prepare a cured product having a thickness of 500 μm. Using this cured product, a moisture permeability test was conducted according to JIS Z 0208 (moisture-proof packaging material) condition A (25 ° C., 90% condition). Test results, the case of ^{1~20g / m 2 · 24h ◎,} 21~40g / m 2 · If the 〇 of 24h, were as × when 41 or more ^{g /} m 2 · 24h.

  Moreover, after apply | coating the electrically conductive composition to bead shape similarly to an ITO board | substrate, it confirmed that the applied material was adhere | attached and it did not peel even if it pulled by hand. Furthermore, after apply | coating the electrically conductive composition to bead shape similarly to the ITO substrate, PET was bonded together and it pressed by hand. The evaluation of adhesiveness is “○” when the cured product of the conductive composition is agglomerated and broken when peeled off by hand, or “△” when there is a sense of resistance when peeling, “△”, The piece peeled off without resistance was designated as “x”. The results are shown in Table 2.

  The obtained conductive composition was stretched to a thickness of about 200 μm using a spacer, and cured for 7 days at 23 ° C. and 50% RH to prepare a cured product sheet, and the volume resistivity was measured. The volume resistivity was measured by a four-end needle method using Lorester MCP-T360 manufactured by Mitsubishi Chemical Corporation.

In Table 1, the compounding quantity of each compounding substance is shown by g. Polymer C1 is an acrylate polymer C1 having a trimethoxysilyl group obtained in Synthesis Example 1, and polymers X1 and X2 are polyoxypropylene systems having a trimethoxysilyl group obtained in Synthesis Examples 2 and 3. Polymers X1 and X2. Moreover, the compounding quantity of the polymer C1 is shown by solid content. * 1 to * 18 are as follows.
* 1) EP505S: methyldimethoxysilyl group-terminated polyisobutylene (containing 33% process oil) (manufactured by Kaneka Corp., EPION EP505S, number average molecular weight 20,000). * 2) SILCOAT AgC-B: specific surface area 1.35 m ² / g, tap density 4.6 g / cm ³ , 50% average particle size 4 μm, trade name, trade name of Fukuda Metal Foil Co., Ltd., Flakes Silver powder.
* 3) Silcote AgC-G: specific surface area 2.5 m ² / g, tap density 1.4 g / cm ³ , trade name of Fukuda Metal Foil Powder Industry Co., Ltd., granular silver powder.
* 4) Diana Process Oil PS-32: Paraffinic process oil, manufactured by Idemitsu Kosan Co., Ltd.
* 5) Aerosil R972: Hydrophobic fumed silica, manufactured by Nippon Aerosil Co., Ltd.
* 6) NOCRACK CD: 4,4- (α, α-dimethylbenzyl) diphenylamine (manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 7) AO-60: A hindered phenol antioxidant, manufactured by ADEKA Corporation, Adeka Stub AO-60.
* 8) LA-63P: Hindered amine light stabilizer, manufactured by ADEKA Corporation, Adeka Stub LA-63P.
* 9) N-11: Paraffin-based diluent, manufactured by JX Nippon Oil & Energy Corporation, trade name: Cactus normal paraffin N-11.
* 10) Ethyl silicate 28: Tetraethoxysilane, manufactured by Colcoat Co., Ltd.
: 11) KBM-3103C: Decyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
* 12) Silicone KBM-903: 3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
* 13) Neostan S-1: Dioctyl tin-based curing catalyst, manufactured by Nitto Kasei Co., Ltd.
* 14) U-830: Dioctyltin compound, trade name: Neostan U-830, manufactured by Nitto Kasei Co., Ltd.
* 15) ACAX-3: trade name made by Mitsui Mining & Smelting Co., Ltd. Silver-plated copper powder obtained by silver-plating dendritic copper powder at a weight ratio of 20%.
* 16) 1400YP (10%): Silver-plated copper powder obtained by silver plating at a weight ratio of 10% on 1400YP (copper powder) manufactured by Mitsui Mining & Smelting Co., Ltd.
* 17) SiO ₂ 5P-Ag30: Silver-plated silica made by Toyo Aluminum Co., Ltd., and silver-plated on spherical silica at a weight ratio of 30%. d ₅₀ (50% average particle size) = 5 μm.
* 18) Nickel flake HCA-1: manufactured by Novamet, flaky nickel powder, thickness of about 1 μm, width 15 to 20 μm.

(Examples 2 to 4, Comparative Examples 1 and 2)
A conductive composition was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. The viscosity and resistance values of the obtained conductive composition were measured in the same manner as in Example 1. The results are shown in Table 2. In addition, the structure obtained in Comparative Example 2 was in a resistance value measurement, and after being stored at 85 ° C. and 85% RH for 100 hours, the cured product was soft and the resistance value could not be measured.

  10: ITO substrate, 12: conductive composition, 14: bead, 20: structure.

Claims (4)

A structure obtained by applying a liquid conductive composition to a transparent electrode substrate, wherein the liquid conductive composition has (A) a hydroxyl group or hydrolyzable group bonded to a silicon atom, and forms a siloxane bond. A saturated hydrocarbon polymer having at least one crosslinkable silicon group that can be crosslinked, and (B) a conductive filler. A bonding device formed by bonding a transparent electrode substrate and a member to be bonded using a liquid conductive composition, wherein the liquid conductive composition has (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom. A bonding device comprising: a saturated hydrocarbon polymer having at least one crosslinkable silicon group that can be cross-linked by forming a siloxane bond; and (B) a conductive filler. A conductive composition used for the structure according to claim 1,
(A) a saturated hydrocarbon polymer having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having at least one crosslinkable silicon group that can be crosslinked by forming a siloxane bond; and (B) conductivity. Contains fillers,
Two conductive beads are applied in the form of a bead with a width of 2 mm and a height of 1.2 mm on a region of 5 mm to 7 mm from the left and right edges of an ITO substrate having a width of 45 mm and a length of 45 mm. After forming two beads 2 hours at 23 ° C. and 50% RH, followed by 12 hours at 50 ° C. and further heating at 80 ° C. for 1 hour. Measured resistance between the two beads after cooling for 3 hours under conditions) and storage (the structure was stored at 85 ° C. and 85% RH for 100 hours and then cooled at 23 ° C. and 50% RH for 3 hours) A conductive composition characterized in that the rate of change in resistance value after storage at the time of storage is 80% or more and 200% or less.   (C) It further contains a (meth) acrylic acid ester-based polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one crosslinkable silicon group that can be crosslinked by forming a siloxane bond. The electrically conductive composition according to claim 3.

Images