TW201331299A - Conductive silicone composition and method for producing the same - Google Patents

Abstract

An addition-curable conductive silicone composition includes the components as following: (A) denoted by an average composition formula (1), which is organopolysiloxane including at least two alkenyls connected with one silicon atom in one molecule, Ra R/bSiO(4-a-b)/2 (1); (B), which is organic hydrogen polysiloxane including at least two hydrogen atoms connected with one silicon atom in one molecule; (C) silver powder or silver coated microsphere powder; (D) conductive microphere power (which does not include silver, copper or metal including silver or copper); and (E) an addition reaction catalyst; and (F) one or more than two selected from fatty acids, fatty acid derivatives and their metal salts. Cured material specially silicon rubber with high conductivity 1.0*10<SP>-2</SP> Ω*cm is formed from the conductive silicone composition, which can be used for coating, the shape maintenance is good, and the storage stability is good.

Description

Conductive fluorenone composition and method of producing the same

The present invention relates to a conductive fluorenone composition for imparting a conductive fluorenone cured product such as a conductive fluorenone rubber, and more particularly to a high electrical conductivity and capable of coating, and after coating (before hardening) An addition-curable conductive fluorenone composition excellent in shape retention and a method for producing the same.

Since the conductive fluorenone rubber composition is an fluorenone rubber which is excellent in conductivity after curing, it is used in the field of heat resistance which is required to exhibit the advantages of fluorenone. A conductive anthrone rubber composition is known in the art as an organic polyoxosiloxane having at least two alkenyl groups in one molecule and an organic hydrogen polyoxygen group having at least two halogen atoms bonded to one atom in one molecule. A composition of an addition-curable conductive fluorenone rubber composed of an alkane, a platinum-based catalyst, and a silver powder. The filler for imparting high conductivity is a silver coated powder, an electrolytic silver powder, an atomized silver powder, and a silver coating for cerium oxide or copper powder. Although the shape has various shapes such as a spherical shape, a flat shape, a dendritic shape, and an indefinite shape, a silver powder which can be highly filled with silver powder and which can be used as a high conductivity composition is often used.

However, when a metal powder such as silver powder or copper powder or a filler after silver plating is added to the addition-curable fluorenone rubber composition, the platinum group catalyst acts to deteriorate the hardenability, or The problem of hardening gradually disappears as time passes.

In addition, the highly conductive anthrone rubber composition is mainly used between the conductors. Although it is electrically connected, in order to form a high-filled silver powder, a low-viscosity fluorenone rubber composition that can be applied is used. Therefore, if the coating or screen printing by the dispenser is performed, the problem of shape collapse may occur. .

The previous literature series on these are as follows.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 61-266462

[Patent Document 2] Japanese Patent Laid-Open No. Hei 3-170081

[Patent Document 3] Japanese Patent Laid-Open No. Hei 5-230373

[Patent Document 4] JP-A-7-133432

[Patent Document 5] Japanese Patent Laid-Open No. Hei 7-150048

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-336273

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2002-212426

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2004-27087

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2004-176165

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2005-162827

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2006-328302

[Patent Document 12] Japanese Patent Laid-Open Publication No. 2008-303233

The present invention has been made in view of the above circumstances, and an object thereof is to provide a highly conductive fluorenone composition which can be applied and which is excellent in shape retention and storage stability after coating, and a method for producing the same.

The present inventors have found that in order to achieve the above object, it has been found that the high conductivity and the shape retention are both established, so that the platinum catalyst is inactivated by the highly filled silver powder. It is effective to further suppress the addition of a composition having excellent stability, and to further add a conductive fine powder and a fatty acid or a fatty acid derivative and/or a metal salt thereof, and thus the present invention has been completed.

That is, the present invention provides an addition-curable conductive fluorenone composition comprising: (A) one of the molecules represented by the following average composition formula (1) having at least two bonds bonded to a ruthenium atom. Alkenyl organopolyoxane: 100 parts by mass, R _a R' _b SiO _(4-ab)/2 (1) (wherein R is an alkenyl group, and R' is a non-aliphatic unsaturated bond a substituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a and b satisfying 0<a≦2, 0<b<3, 0<a+b≦3) (B) at least 2 in one molecule An organic hydrogen polyoxyalkylene bonded to a hydrogen atom of a halogen atom: a hydrogen atom bonded to a halogen atom in the component (B) is 0.5 with respect to a total alkene bonded to an alkenyl group in the component (A). ~5.0 times the molar amount, (C) silver powder or silver-plated fine powder particles: 100 to 1,500 parts by mass, (D) conductive fine powder (in which the screen removes silver, copper and metals containing the same) : 0.5 to 30 parts by mass, (E) addition reaction catalyst: amount of catalyst, and (F) fatty acid or fatty acid derivative and/or metal salt thereof: 0.1 to 20 parts by mass.

The conductive anthrone composition of the present invention is given 1.0 × 10 ^-2 Ω. A cured product having a high electrical conductivity of not more than cm, particularly when an oxime rubber is formed, and has good coatability and good stability in storage stability.

The conductive fluorenone composition of the present invention contains: (A) an organopolyoxane having at least two alkenyl groups bonded to a ruthenium atom in a molecule represented by the following average composition formula (1): 100 mass Parts, R _a R' _b SiO _{(4-ab) / 2} (1) (wherein R is an alkenyl group, and R' is an unsubstituted or substituted carbon number of 1 to 10 having no aliphatic unsaturated bond. a valence hydrocarbon group, a, b is a number satisfying 0 < a ≦ 2, 0 < b < 3, 0 < a + b ≦ 3) (B) an organic molecule having at least two hydrogen atoms bonded to a ruthenium atom in one molecule Hydrogen polyoxyalkylene: The hydrogen atom bonded to the ruthenium atom in the component (B) is 0.5 to 5.0 times the molar amount relative to the total ruthenium atom-bonded alkenyl group in the component (A), (C) Silver powder or silver-plated fine powder particles: 100 to 1,500 parts by mass, (D) conductive fine powder (in which, screen silver, copper, and metals containing the same): 0.5 to 30 parts by mass, (E) plus The reaction catalyst: the amount of the catalyst, and (F) a fatty acid or a fatty acid derivative and/or a metal salt thereof: 0.1 to 20 parts by mass.

(A) Alkenyl-containing organopolyoxane

The alkenyl group-containing organopolyoxane of the component (A) is represented by the following average composition formula (1), and contains at least two alkenyl groups bonded to a ruthenium atom in one molecule.

R _a R' _b SiO _{(4-ab) / 2} (1) (wherein R is an alkenyl group, and R' is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms which does not have an aliphatic unsaturated bond. , a, b are the numbers satisfying 0<a≦2, 0<b<3, 0<a+b≦3).

The alkenyl group-containing organopolyoxane of the component (A) is a main component (matrix polymer) of the composition, and contains at least two or more (generally 2 to 50) molecules per molecule, preferably 2 to 20, more preferably 2 to 10 or so, bonded to an alkenyl group of a halogen atom. Organic polyoxane of component (A) The alkenyl group R may, for example, be a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group or a heptenyl group, and particularly preferably a vinyl group. The bonding position of the alkenyl group of the component (A) is, for example, a molecular chain terminal and/or a molecular chain side chain.

In the organopolyoxane of the component (A), the organic group R' which is bonded to the ruthenium atom other than the alkenyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group. An alkyl group such as phenyl, tolyl, xylyl or naphthyl; an aralkyl group such as benzyl or phenethyl; chloromethyl, 3-chloropropyl, 3,3,3- A halogenated alkyl group such as a trifluoropropyl group or the like is preferably a methyl group or a phenyl group.

The molecular structure of the component (A) may be, for example, a linear chain, a linear chain having a partial branch, a cyclic chain, a branched chain, a three-dimensional network, or the like, but a substantially main chain is a diorganosiloxane. The alkane unit (D unit) is repeatedly formed, and the two ends of the molecular chain are linear diorganopolyoxyalkylene blocked by a triorganophosphonyl group, a linear diorganopolyoxyalkylene and a branched chain. Or a mixture of three-dimensional networked organopolyoxane is preferred.

In this case, the resinous (branched, three-dimensional network) organopolyoxane contains an alkenyl group and an SiO _4/2 unit (Q unit) and/or R"SiO _3/2 (T unit) (R). The organopolyoxane of "R or R') is not particularly limited, but may be exemplified by a SiO _4/2 unit (Q unit) and an RR' ₂ SiO _1/2 unit or an R' ₃ SiO _1/2 unit. a resinous organopolyoxane composed of M units having an M/Q molar ratio of 0.6 to 1.2, or a resinous organopolyoxane composed of a T unit and an M unit and/or a D unit. Wait.

The amount of resinous organic polyoxane, the coating properties of the composition From the viewpoint of the filling property of the silver powder, the preferred blending ratio of the linear organopolyoxane to the resinous organopolyoxane is preferably 70:30 to 100:0 by mass ratio, which is particularly preferable. It is an amount of 80:20~100:0.

a is 0 < a ≦ 2, preferably 0.001 ≦ a ≦ 1; b is 0 < b < 3, preferably 0.5 ≦ b ≦ 2.5; a + b is 0 < a + b ≦ 3, preferably satisfied The number of 0.5≦a+b≦2.7.

The viscosity of the component (A) at 23 ° C is good, and the physical properties of the obtained fluorenone composition are good, and the processing workability and coating property of the composition are good, and it is 100 to 5,000 mPa. The range of s is better, especially 100~1,000mPa. Those within the range of s are preferred. When a resinous organopolysiloxane is used in combination with a linear organopolysiloxane, the resinous organopolysiloxane is dissolved in a linear organopolyoxane, and thus mixed to have a viscosity in a uniform state. Further, in the present invention, the viscosity can be measured by a rotary viscometer.

The organopolyoxyalkylene of the above component (A) may, for example, be a dimethyloxy group at the end of the molecular chain. Methyl vinyl alkane copolymer, molecular chain two-terminal trimethyl methoxy group blocking methyl vinyl polyoxyalkylene, molecular chain two-terminal trimethyl methoxy group blocking dimethyl oxane. Methyl vinyl siloxane. Methylphenyl fluorene copolymer, molecular chain two-terminal dimethylvinyl methoxy group blocking dimethyl polyoxyalkylene, molecular chain two terminal dimethyl vinyl methoxy group blocking methyl vinyl fluorene Oxygenane, the two ends of the molecular chain dimethyl vinyl methoxy group block dimethyl oxa oxide. Methyl vinyl alkane copolymer, molecular chain two-terminal dimethyl vinyl methoxy group block dimethyl oxa oxide. Methyl vinyl siloxane. a methylphenyl siloxane copolymer, a trivinyl methoxy group at the two ends of the molecular chain, which blocks dimethyl polyoxane, a siloxane unit represented by the formula: R ¹ ₃ SiO _0.5 and a formula: R ¹ ₂ R ² SiO _0.5 represents a oxoxane unit and a formula: an organooxane copolymer represented by R ¹ ₂ SiO and an organooxane copolymer represented by a siloxane unit represented by the formula: SiO ₂ , An organic compound composed of a oxoxane unit represented by the formula: R ¹ ₃ SiO _0.5 and a oxoxane unit represented by the formula: R ¹ ₂ R ² SiO _0.5 and a decane unit represented by the formula: SiO ₂ a siloxane copolymer, a fluoran oxide unit represented by the formula: R ¹ ₂ R ² SiO _0.5 and a oxoxane unit represented by the formula: R ¹ ₂ SiO and an oxygen represented by the formula: SiO ₂ An organooxane copolymer composed of an alkane unit, a siloxane unit represented by the formula: R ¹ R ² SiO, and a siloxane unit represented by the formula: R ¹ SiO _1.5 or a formula: R ² SiO A mixture of two or more kinds of an organic oxirane copolymer composed of a siloxane unit represented by _1.5 and an organic polysiloxane.

Here, R ¹ in the above formula is a monovalent hydrocarbon group other than the alkenyl group, and examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; An aryl group such as a tolyl group, a xylyl group or a naphthyl group; an aralkyl group such as a benzyl group or a phenethyl group; a halogenated alkane such as a chloromethyl group, a 3-chloropropyl group or a 3,3,3-trifluoropropyl group; Base. Further, in the above formula, R ² is an alkenyl group, and examples thereof include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group.

(B) organic hydrogen polyoxyalkylene oxide

The organohydrogen polyoxane (B) used in the composition of the present invention is At least two (usually 2 to 300), preferably three or more (for example, about 3 to 150), more preferably from about 3 to 100, bonded to a hydrogen atom of a halogen atom in one molecule (ie, Any of the resin materials of a linear, branched, cyclic, or three-dimensional network structure, which may be a SiH group. The organic hydrogen polyoxyalkylene system described above is, for example, an organic hydrogen polyoxyalkylene represented by the following average composition formula (2).

H _c R ³ _d SiO _(4-cd)/2 (2) (wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group or alkoxy group independently containing no aliphatic unsaturated bond, c and d systems The number of 0 < c < 2, 0.8 ≦ d ≦ 2 and 0.8 < c + d ≦ 3 is preferably 0.05 ≦ c ≦ 1, 1.5 ≦ d ≦ 2 and 1.8 ≦ c + d ≦ 2.7. The number of atoms (or degree of polymerization) in one molecule is 2 to 100, especially 3 to 50.

Here, the unsubstituted or substituted monovalent hydrocarbon group of R ³ which does not contain an aliphatic unsaturated bond in the above formula may be, for example, the same as those exemplified as R' described above, and other methoxy group and ethoxy group. The alkoxy group or the substituted monovalent hydrocarbon group may, for example, be a monovalent hydrocarbon group containing an epoxy group, and the representative ones have a carbon number of 1 to 10, particularly a carbon number of 1 to 7, preferably A. a lower alkyl group having a carbon number of 1 to 3, a 3,3,3-trifluoropropyl group or an alkoxy group having 1 to 4 carbon atoms. In this case, the monovalent hydrocarbon group containing an epoxy group may be one of the above-mentioned unsubstituted one-valent hydrocarbon groups, and in particular, one or more hydrogen atoms of the alkyl group may be substituted with a glycidyl group or a glycidoxy group. R ^{3 is} particularly preferably a methyl group, a methoxy group, an ethoxy group or a monovalent hydrocarbon group containing an epoxy group.

Examples of the above-mentioned organic hydrogen polyoxyalkylene oxides include 1,1,3,3-tetramethyldioxane, 1,3,5,7-tetramethyltetracyclodecane, and 1,3. 5,7,8-pentamethylpentacyclononane, methylhydrocyclopolyoxyalkylene, methylhydroquinone. a methoxy alkane oligomer such as a dimethyl methoxy olefin cyclic copolymer or a dimethyl hydrazine oxide; a trimethyl methoxy group at the two ends of the molecular chain to block methyl hydrogen polyoxyl The alkane and the end of the molecular chain trimethyl methoxy group block the dimethyl oxane. The methylhydroquinone copolymer, the sterol group at both ends of the molecular chain blocks the methyl hydrogen polyoxyalkylene, and the sterol group at both ends of the molecular chain blocks the dimethyloxane. Methyl hydroquinone copolymer, dimethyl hydrazine oxy group at the two ends of the molecular chain, dimethyl polyoxyalkylene, dimethyl hydrazine at the two ends of the molecular chain, methyl hydrogen polyoxyalkylene, molecular The two ends of the chain, dimethylhydroquinone, block the dimethyloxane. a methylhydroquinone copolymer or the like; composed of R ³ ₂ (H)SiO _1/2 units and SiO _4/2 units, and optionally containing R ³ ₃ SiO _1/2 units, R ³ ₂ SiO _{2 / Other than the two} units, the R ³ (H) SiO _2/2 unit, the (H) SiO _3/2 unit or the R ³ SiO _3/2 unit fluorenone resin (however, the R ³ system is the same as described above), etc. These may be listed as a part or all of a methyl group in a compound, which may be substituted with another alkyl group such as an ethyl group or a propyl group, and the like. (In the formula, R ³ is the same as described above, and s and t are each an integer of 0 or 1 or more).

Further, when the adhesion is important, a part or all of the component (B) is used as the one having the alkoxy group and/or the epoxy group in the molecule as represented by the following formulas (3) and (4). It is better. In particular, an organic hydrogen polyoxyalkylene having an alkoxy group and an epoxy group-containing molecule in the molecule as represented by the formula (4) is effective for improving the adhesion.

The organohydrogenpolyoxane used in the composition of the present invention can be obtained by a conventional method, for example, by the general formula: R ³ SiHCl ₂ and R ³ ₂ SiHCl (wherein the R ³ system) At least one of the chlorodecane selected in the same manner as described above is (co)hydrolyzed, or the chlorodecane is of the general formula: R ³ ₃ SiCl and R ³ ₂ SiCl ₂ (wherein the R ³ system is the same as the above) The at least one selected chlorodecane selected from the group is co-hydrolyzed and condensed. Further, the organic hydrogen polyoxyalkylene may be obtained by equilibrating a polyoxyalkylene obtained by performing the above (co)hydrolysis condensation.

The amount of the component (B) is an alkenyl group bonded to the total ruthenium atom in the component (A), and the hydrogen atom bonded to the ruthenium atom in the component (B) is 0.5 to 5.0 times the molar amount. The amount is better, and the better is 0.7 to 3.0 times the amount of Mo. In the case of less than 0.5 or more, there is a case where the crosslinked balance collapses and a cured product having sufficient strength cannot be obtained.

(C) Silver powder or silver-plated fine powder particles

In order to impart conductivity to the cured product of the anthrone composition, in the present invention, the conductive filler is a fine powder particle in which silver powder or silver plating is used. Specific examples of the silver powder include reduced silver powder, electrolytic silver powder, and atomized silver powder. The shape of the component (C) is not particularly limited as long as it has various shapes such as a spherical shape, a flat shape, a dendritic shape, and an indefinite shape. However, in order to highly fill the silver powder used to form the highly conductive composition, it is preferable to use a flat silver powder. Further, the silver-plated fine powder particles are not particularly limited as long as the substrate to be plated is cerium oxide or copper. In order to coat the surface with silver, it is preferred to use a spherical substrate. The average particle diameter of the component (C) is not particularly limited, but is preferably 0.1 to 15 μm. The average particle diameter can be obtained as the cumulative mass average value D ₅₀ in the particle size distribution measuring device by the laser light diffraction method.

The silver powder contains a rust preventive agent or a lubricant for preventing aggregation depending on the manufacturing process. If these acts on the platinum group catalyst of the addition reaction catalyst, there is a case where the hardening is delayed or incompletely hardened. Therefore, the silver powder or the silver plating filler is preferably washed with a large amount of water or an organic solvent of acetone or methyl ethyl ketone and then dried.

The amount of the component (C) to be added is 100 to 1,500 parts by mass, more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the component (A). When the component (C) is less than 100 parts by mass, the electrical conductivity of the cured product is lowered, and if it is more than 1,500 parts by mass, the treatment of the composition becomes difficult.

(D) Conductive fine powder (in which the screen removes silver, copper, and metals containing the same)

The component (D) is used to improve the shakeability while maintaining the conductivity of the composition and to improve the shape retention. The powder to which the conductivity is imparted is, for example, carbon black or conductive Chinese white (zinc oxide). However, in the present invention which is a composition having high conductivity, it is preferred to use carbon black.

For carbon black, those generally used for conductive rubber compositions can be used, and examples thereof include acetylene carbon, conductive furnace black (CF), superconducting furnace black (SCF), special conductive furnace black (XCF), and conductive groove carbon. Black (CC), Heat treated furnace black or tank carbon black at a high temperature of about 1,500 to 3,000 °C. Among these, acetylene carbon is particularly suitable for use in the present invention because of its low impurity content and excellent conductivity in view of the developed two-dimensional structure.

The amount of the component (D) to be added is 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 3 to 20 parts by mass, per 100 parts by mass of the component (A). In the case where the amount added is less than 0.5 parts by mass, the effect of improving the shake denaturation is insufficient, and the shape retainability after coating of the composition is deteriorated, and in the case of more than 30 parts by mass, the viscosity is excessively increased. The workability of the composition is lowered.

(E) Addition reaction catalyst

The addition reaction catalyst (hydrazine hydrogenation reaction catalyst) used in the present invention is a hydrogen atom for promoting the bonding of an alkenyl group of the above-mentioned (A) component and a component (B) to a halogen atom (that is, As the catalyst for the addition reaction of the SiH group, a well-known catalyst such as a platinum group metal catalyst can be used as a catalyst for the hydrogenation reaction.

This platinum group metal-based catalyst system can be used as a ruthenium hydrogenation catalyst, and a platinum group metal catalyst such as platinum, rhodium or palladium can be used. For example, a platinum group metal monomer such as platinum black, rhodium or palladium; H ₂ PtCl ₄ . yH ₂ O, H ₂ PtCl ₆ . yH ₂ O, NaHPtCl ₆ . yH ₂ O, KHPtCl ₆ . yH ₂ O, Na ₂ PtCl ₆ . yH ₂ O, K ₂ PtCl ₄ . yH ₂ O, PtCl ₄ . yH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ . yH ₂ O (wherein, y is an integer of 0 to 6, preferably 0 or 6), such as platinum chloride, chloroplatinic acid, and chloroplatinate; alcohol-modified chloroplatinic acid (refer to U.S. Patent No. 3,220,972) The specification is a complex of chloroplatinic acid and an olefin (refer to the specification of U.S. Patent No. 3,159,601, the specification of the same as No. 3,159,662, the specification of the same as No. 3,775,452); the support of alumina, cerium oxide, carbon, etc. Platinum group metals such as platinum black, palladium, etc.; ruthenium-olefin complex; chlorohydrazine (triphenylphosphine) ruthenium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate A complex with a vinyl-containing alkane, particularly a vinyl-containing cyclic siloxane. Preferred among these, from the viewpoint of compatibility and chlorine impurities, chloroplatinic acid may be exemplified by fluorenone, and specific examples thereof include chloroplatinic acid via tetramethyl bis Platinum catalyst modified with vinyl dioxane.

The amount of the component (E) to be added is platinum atom and is 0.5 to 1,000 ppm, preferably 1 to 500 ppm, more preferably 5 to 200 ppm, based on the mass of the component (A).

(F) a fatty acid or a fatty acid derivative and/or a metal salt thereof

The fatty acid of the component (F) or the fatty acid derivative and/or its metal salt may be prepared by blending the addition curability of the composition, and may be used commercially.

The amount of the component (F) to be added is 0.1 to 20 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (A). If it is less than 0.1 part by mass, the effect of preserving stability improvement may become insufficient, and if it exceeds 20 mass parts, hardenability may deteriorate. Here, the preferred carbon number of the fatty acid or the fatty acid derivative and/or its metal salt is 8 or more, preferably 8~. 20.

Specific examples of the fatty acid can be exemplified by caprylic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, alginic acid, tetracosic acid, hexacylic acid, and thirty Acid, nutmeg oleic acid, oleic acid, linoleic acid, succulent acid, and the like.

Examples of the fatty acid derivative include fatty acid esters, esters of aliphatic alcohols, and the like. The aliphatic ester system may, for example, be a polyhydric alcohol ester such as a fatty acid such as a fatty acid such as a C ₁ to C ₅ lower alcohol ester, a sorbitol ester or a glycerin ester. The ester of an aliphatic alcohol can be exemplified by a fatty acid alcohol such as octanol, octanol, lauryl alcohol, myristyl alcohol or stearyl alcohol, or a dibasic acid such as a glutarate or a suberate. a ternary acid ester such as an ester or a citric acid ester.

Examples of the fatty acid of the fatty acid metal salt include octanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, alginic acid, tetracosic acid, and hexacylic acid. And tridecanoic acid, nutmeg oleic acid, oleic acid, linoleic acid, ursolic acid, and the like; and the metal system may, for example, be lithium, calcium, magnesium, zinc or the like.

The component (F) is preferably a fatty acid, and stearic acid is preferred. Although the component (F) can be used alone, it is preferable to use the component (E) in advance to improve the preservation stability.

The composition of the present invention may be a two-liquid composition which is mixed with the general addition-curable fluorenone composition, and may be mixed before use. However, from the viewpoint of workability, It is preferred to be a one-liquid composition.

In the composition of the present invention, it can be used without impairing the object of the present invention. Further additives are added to the circumference. In particular, in order to improve the storage stability when the composition of the present invention is used in the one-liquid type, the hydrogenation reaction inhibitor can be formulated. The reaction inhibitor can be used, and examples thereof include an acetylene compound, a compound containing two or more alkenyl groups, a compound containing an alkynyl group, or a triallyl cyanurate or a modified product thereof. Among these, the use of a compound having an alkenyl group or an alkynyl group is preferred.

If the amount of the reaction inhibitor added is too small, the delayed effect of the hydrogenation reaction may not be obtained. If the amount is too large, the curing itself may be inhibited. Therefore, the component (A) to (F) is not affected. The total amount is 100 parts by mass, preferably in the range of 0.01 to 1.0 part by mass.

Further, a decane coupling agent may be formulated in order to improve adhesion.

In the method for producing the addition-curable conductive fluorenone composition of the present invention, for example, a component such as a planetary mixer, a kneader or a Shinagawa mixer is used to carry out the components (A) to (F) and others. A method of mixing arbitrary components, and the like. In this case, it is preferable to mix the components (E) and (F) in advance with other components, and it is preferable to improve the storage stability of the composition.

In the present invention, the viscosity and the coefficient of the shake of the composition are important factors in the shape stability after coating. The viscosity of the composition at 23 ° C when the rotational speed of the E-type viscosity is 10 rpm is 10 Pa. s above 500Pa. s below, especially 20~200Pa. s is better. When the viscosity is too low, there is a case where the film is applied by a dispenser or the like, or flows during heat curing, and the shape cannot be maintained. In addition, if the viscosity is too high, then There is a pattern in which a thread is generated when coating with a dispenser, or a pattern that cannot sufficiently follow the mask when screen printing is performed, and the pattern is defective. Further, the composition at 23 ° C has a viscosity at 10 rpm and a viscosity at 20 rpm (10 rpm / 20 rpm) (hereinafter, expressed by a rocking coefficient) of 1.5 or more, particularly preferably 2.0 to 5.0. If the coefficient of rocking is less than 1.5, the shape stability after coating may be insufficient. Therefore, when the shape stability after coating is important, the use of the rocking coefficient is 1.5 or more. It is better.

The curing conditions of the composition of the present invention are preferably 1 to 120 minutes at 100 to 150 ° C. At this time, the conductivity of the cured product is adjusted to be 1.0 × 10 ^-2 Ω by adjusting the amount of the components (C) and (D). The following is better than cm, especially 1.0 × 10 ^-2 ~ 1.0 × 10 ^-5 Ω. The cm is better.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 to 4, Comparative Examples 1 to 4]

Under the blending amounts shown in Tables 1 and 2, the components shown below were uniformly mixed by a THINKY (rotary/rotary mixer) (AWATORI) to prepare an anthrone composition. In the examples and the comparative examples, the viscosity was measured at 23 ° C by an E-type viscometer (RE80 manufactured by Toki Sangyo Co., Ltd.).

(A) has a vinyl group bonded to a ruthenium atom in one molecule, and has a viscosity of 600 mPa. s methyl vinyl polyoxyalkylene

(B-1) viscosity at 23 ° C 5mPa. s, methyl hydrogen polyoxane having a hydrogen production of 350 ml/g

(B-2) SiH-containing compound represented by formula (4)

(C) Washing and drying the Fukuda Metal Foil Powder Industrial Co., Ltd. silver powder (AgC-237) with acetone

(D) Electrochemical Industry (Stock) DENKA BLACK HS-100

(E-1) Platinum catalyst having tetramethyldivinyldioxane derived from chloroplatinic acid as a ligand (platinum atomic weight: 1% by mass)

(E-2) mixing the above (E-1) with stearic acid at a mass ratio of 3/2

(F) stearic acid

(G) a fumed cerium oxide having a specific surface area of 200 m ² /g by the BET method and having a surface treated with hexamethyldioxane

(Reaction inhibitor) 1-ethynyl-1-cyclohexanol

The results of the electrical conductivity, viscosity, shaking coefficient, shape retention, and storage stability of the obtained fluorenone rubber composition are shown in Tables 1 and 2. Moreover, electrical conductivity, shape retention, and storage stability were performed by the method shown below.

[Measurement of conductivity]

In the mold of 1 mm thickness, the fluorenone rubber composition was subjected to in-furnace hardening at 150 ° C / 1 hour, thereby forming a conductive fluorenone rubber sheet.

Conductivity is measured using KEITHLEY 237 High Voltage Source Measure Unit

(constant current power)

KEITHLEY 2000 Multimeter (constant voltage) is used.

[shape retention]

For the shape retention, the composition was placed on a stainless steel (SUS) plate of 25 mm × 250 mm (thickness: 0.5 mm), and the fluidity of the composition at 150 ° C / 1 hour was determined by tilting at 30 degrees. : ◎ (no change at all), ○ (prone to no flow), △ (1 to 3 mm flow), × (more than 3 mm flow).

[save stability]

For the composition immediately after production and after storage at 5 ° C for 2 months, the hardness at 150 ° C / 1 hour was measured by a durometer type A durometer.

Claims (5)

An addition-curable conductive fluorenone composition comprising: (A) an organic polyfluorene having at least two alkenyl groups bonded to a ruthenium atom in a molecule represented by the following average composition formula (1) Oxytomane: 100 parts by mass, R _a R' _b SiO _{(4-ab) / 2} (1) (wherein R is an alkenyl group, and R' is an unsubstituted or substituted carbon number having no aliphatic unsaturated bond a monovalent hydrocarbon group of 1 to 10, a and b satisfying 0 < a ≦ 2, 0 < b < 3, and 0 < a + b ≦ 3) (B) at least 2 bonded to a ruthenium atom in one molecule Organic hydrogen polyoxyalkylene of a hydrogen atom: the hydrogen atom bonded to the halogen atom in the component (B) is 0.5 to 5.0 times the molar ratio with respect to the all-oxide atom-bonded alkenyl group in the component (A). Amount, (C) silver powder or silver-plated fine powder particles: 100 to 1,500 parts by mass, (D) conductive fine powder (wherein, silver, copper and metals containing the same): 0.5 to 30 parts by mass (E) Addition reaction catalyst: amount of catalyst, (F) fatty acid or fatty acid derivative and/or metal salt thereof: 0.1 to 20 parts by mass. The addition-curable conductive fluorenone composition according to the first aspect of the invention, wherein the component (D) is carbon black. The addition-curable conductive fluorenone composition according to the first or second aspect of the patent application, wherein the shake ratio at 23 ° C obtained by an E-type viscometer (viscosity at 10 rpm / viscosity at 20 rpm) It is 1.5 or more. The addition-curable conductive fluorenone composition according to the first aspect of the invention, wherein the conductivity of the cured product is 1.0×10 ^-2 Ω. Below cm. A method for producing a composition, which is prepared by mixing (E) a addition-curable conductive fluorenone composition according to any one of the first to fourth aspects of the invention. The component and the component (F) are mixed with other components.