JP2015124321A - Conductive adhesive composition, conductive adhesive sheet, and manufacturing method of the conductive adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive adhesive composition having excellent conductivity in spite of blending of a relatively small amount of a conductive material, a conductive adhesive sheet using such the conductive adhesive composition, and an efficient manufacturing method of the conductive adhesive sheet.SOLUTION: There are provided a conductive adhesive composition containing at least a (meth)acrylic acid ester copolymer as a (A) component, a urethane polymer as a (B) component, and a tackifier resin as a (C) component, and a manufacturing method of a conductive adhesive sheet which uses such the conductive adhesive composition. In the conductive adhesive composition, with respect to 100 pts.wt. of the (meth)acrylic acid ester copolymer as the (A) component, an amount of blending of the urethane polymer as the (B) component is a value within the range of 80 to 800 pts.wt. and an amount of blending of the tackifier resin as the (C) component is a value within the range of 80 to 800 pts.wt., and a conductive material as a (D) component is contained.

Description

  The present invention relates to a conductive pressure-sensitive adhesive composition, a conductive pressure-sensitive adhesive sheet, and a method for producing a conductive pressure-sensitive adhesive sheet. In particular, even when the amount of the conductive material is small, a conductive pressure-sensitive adhesive composition capable of obtaining good conductivity and pressure-sensitive adhesive properties, and a conductive pressure-sensitive adhesive using such a conductive pressure-sensitive adhesive composition The present invention relates to a sheet and a method for producing a conductive pressure-sensitive adhesive sheet.

Conventionally, a conductive pressure-sensitive adhesive composition and a conductive pressure-sensitive adhesive sheet using the conductive pressure-sensitive adhesive composition are frequently used in order to avoid the influence of static electricity in the manufacturing process and packaging process of semiconductors and precision electronic devices.
That is, the conductive pressure-sensitive adhesive composition or the like exerts a predetermined conductivity by mixing a predetermined amount of a conductive material in the electrically insulating pressure-sensitive adhesive composition, thereby making it possible to produce a product in a manufacturing process or a packaging process. This prevents damage and failure of semiconductors and precision electronic equipment caused by static electricity.

Then, the antistatic adhesive tape excellent in antistatic property, an adhesive characteristic, etc. which uses such a conductive adhesive composition is proposed (for example, patent document 1).
More specifically, as shown in FIG. 6, a conductive material 104 a such as carbon nanofiber is provided in one or both surfaces of the base material 103 treated with the back surface treatment material 102 in an acrylic adhesive or the like. A conductive pressure-sensitive adhesive layer 104 formed from a conductive pressure-sensitive adhesive composition dispersed; an electrically insulating pressure-sensitive adhesive layer 105 that does not contain a conductive material and has a predetermined thickness (0.5 to 10 μm); An antistatic pressure-sensitive adhesive tape 101 is sequentially laminated.

In addition, a pressure-sensitive adhesive sheet has been proposed that has an antistatic ability and can exhibit high adhesive strength even when the pressure-sensitive adhesive layer is thinned (for example, Patent Document 2).
More specifically, it is an adhesive sheet having an adhesive layer containing an acrylic copolymer, a urethane resin, and carbon nanotubes on at least one side of a substrate, and the content of carbon nanotubes is an acrylic copolymer. And the adhesive sheet which is 0.01-0.9 mass part is disclosed with respect to 100 mass parts of total amounts of urethane resin.

In addition, as a pressure-sensitive adhesive sheet used when assembling an electronic device or an electrical device, although not a conductive pressure-sensitive adhesive composition, etc., a heat-resistant pressure-sensitive adhesive composition containing a predetermined terminal silyl group polymer as a main ingredient is used. An adhesive sheet is proposed (for example, Patent Document 3).
More specifically, 100 parts by mass of a terminal silyl group polymer having a urethane bond and / or a urea bond in the main chain or side chain and containing a hydrolyzable silyl group at the terminal, and 10 to 150 parts by mass of a tackifier resin , A pressure-sensitive adhesive precursor in which 0.001 to 10 parts by mass of a fluorine compound selected from the group consisting of boron trifluoride and / or a complex thereof, a fluorinating agent and an alkali metal salt of a fluorine-based inorganic acid are uniformly mixed Is applied to the surface of a tape base material or a sheet base material, and then the terminal silyl group polymer is cured, whereby the pressure sensitive adhesive precursor is used as a pressure sensitive adhesive layer. .

JP 2008-55710 A (Claims and specification) JP 2013-189562 A (claims, specification) WO2010 / 038715 (Claims and specification)

However, the antistatic pressure-sensitive adhesive tape described in Patent Document 1 includes a conductive pressure-sensitive adhesive layer made of a conductive pressure-sensitive adhesive composition and an electric insulating pressure-sensitive adhesive layer made of an electric insulating pressure-sensitive adhesive composition on a substrate. Are required to be sequentially stacked from below, and the structure becomes complicated. For this reason, there are problems that the number of manufacturing steps is increased and the manufacturing cost is increased.
In forming a conductive pressure-sensitive adhesive layer made of a conductive pressure-sensitive adhesive composition, a considerable amount of conductive material (carbon-based fibrous conductive filler) is used (for example, 9%) with respect to 100 parts by weight of the acrylic pressure-sensitive adhesive. Despite the addition of (part by weight), there was a problem that the volume resistivity value of the obtained conductive adhesive layer was high.
In addition, since it is necessary to further laminate a pressure-sensitive adhesive layer made of an electrically insulating pressure-sensitive adhesive composition on the surface of the conductive pressure-sensitive adhesive layer, the surface resistivity of the obtained antistatic pressure-sensitive adhesive tape is also considerably high. There was a problem of high values, for example, in the range of about 9 × 10 ^{9 to} 7 × 10 ¹⁰ Ω / □.

  In addition, since the pressure-sensitive adhesive sheet described in Patent Document 2 is a thin film with a thickness of the pressure-sensitive adhesive layer of 10 μm or less, the pressure-sensitive adhesive sheet is limited to a specific application and the amount of carbon nanotubes is small. There was a problem that the surface resistivity was still high.

On the other hand, the pressure-sensitive adhesive sheet described in Patent Document 3 must contain a predetermined amount of a fluorine compound such as boron trifluoride or a fluorinating agent as a curing catalyst for increasing the reactivity of the terminal silyl group in the terminal silyl group polymer. However, there are problems that the manufacturing cost becomes high, the reaction control becomes difficult, and the handling property becomes difficult depending on the kind of the curing catalyst.
In addition, there is no concept of blending a predetermined acrylic copolymer and tackifying resin with the terminal silyl group polymer, let alone blending a conductive material to obtain a conductive adhesive composition. There was no concept.

In view of the circumstances as described above, the present inventors have made extensive efforts to blend a urethane polymer and a tackifying resin into a (meth) acrylic acid ester copolymer, and to add a predetermined amount of a conductive material. It has been found that, by blending, good conductivity and adhesive properties can be exhibited, and the present invention has been completed.
That is, the object of the present invention is to provide a conductive pressure-sensitive adhesive composition capable of obtaining good conductivity and adhesive properties even when the amount of the conductive material is relatively large, as well as a relatively small amount, It is providing the efficient manufacturing method of the electroconductive adhesive sheet and electroconductive adhesive sheet which use such an electroconductive adhesive composition.

  According to the present invention, a conductive adhesive comprising at least a (meth) acrylic acid ester copolymer as the component (A), a urethane polymer as the component (B), and a tackifying resin as the component (C). It is an agent composition, Comprising: With respect to 100 weight part of (meth) acrylic acid ester copolymers as (A) component, the compounding quantity of the urethane polymer as (B) component exists in the range of 80-800 weight part. And (C) the amount of the tackifying resin as component (C) is in the range of 80 to 800 parts by weight, and (D) component contains a conductive material. An agent composition is provided to solve the above-mentioned problems.

That is, if it is the electroconductive adhesive composition of this invention, the urethane polymer as (B) component and the tackifier resin as (C) component are mix | blended with respect to the acrylic copolymer which is (A) component. At the same time, by blending a conductive material as the component (D), good conductivity and adhesive properties can be exhibited.
Moreover, even if the blending amount of the conductive material as the component (D) is relatively small, good conductivity can be obtained, so that the adhesive property is further improved and the production of the conductive adhesive composition Costs are reduced, which is economically advantageous and handling is improved.
In addition, by blending the (A) component (meth) acrylic acid ester copolymer, the (B) component urethane polymer, and the (C) component tackifying resin in a predetermined blending amount, The balance between the adhesive force and the cohesive force in the conductive pressure-sensitive adhesive composition can be made better, and the volume resistivity of the conductive pressure-sensitive adhesive composition can be adjusted to a value within a suitable range.

Moreover, in comprising the electroconductive adhesive composition of this invention, the compounding quantity of the electroconductive material as (D) component with respect to 100 weight part of (meth) acrylic acid ester copolymers as (A) component. Is preferably set to a value within the range of 0.01 to 100 parts by weight.
By comprising in this way, the balance among the electroconductivity in an electroconductive adhesive composition, adhesive force, and cohesion force can be made more favorable.

Moreover, in composing the conductive pressure-sensitive adhesive composition of the present invention, as a monomer component when copolymerizing the (meth) acrylic acid ester copolymer as the component (A), a carboxyl group-containing vinyl monomer is included. The amount of the carboxyl group-containing vinyl monomer is preferably set to a value in the range of 0.1 to 40% by weight with respect to 100% by weight of all monomer components.
By comprising in this way, not only the polymerization of the (meth) acrylic acid ester copolymer as the component (A) can be facilitated, but also the adhesiveness of the conductive adhesive composition can be stably improved. .

Moreover, in composing the conductive pressure-sensitive adhesive composition of the present invention, as a monomer component when copolymerizing the (meth) acrylic acid ester copolymer as the component (A), a nitrogen-containing vinyl monomer is included. The blending amount of the nitrogen-containing vinyl monomer is preferably set to a value within the range of 0.1 to 40% by weight with respect to 100% by weight of all monomer components.
By comprising in this way, not only the polymerization of the (meth) acrylic acid ester copolymer as the component (A) can be facilitated, but also the adhesiveness of the conductive adhesive composition can be stably improved. .

Moreover, when comprising the electroconductive adhesive composition of this invention, it is preferable to make the weight average molecular weight of the urethane polymer which is (B) component into the value within the range of 15,000-200,000.
By comprising in this way, the balance among the softness | flexibility, adhesive force, and cohesion force in an electroconductive adhesive composition can be made more favorable.

  In constituting the conductive pressure-sensitive adhesive composition of the present invention, the urethane polymer as the component (B) has a polyoxyalkylene structure in the main chain and is bonded to a part of the main chain or a side chain. And a terminal silyl group polymer having a hydrolyzable silyl group represented by the following general formula (1) at both ends of the main chain.

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.)

By comprising in this way, since the terminal silyl group polymer which is (B) component has the hydrolyzable silyl group represented by General formula (1) in the both ends of a principal chain, (B) components mutually The crosslink density is adjusted to a suitable range, and the balance between the adhesive force and the cohesive force in the conductive adhesive composition can be made better.
Moreover, since the reactivity of a hydrolyzable silyl group improves with the (meth) acrylic acid ester copolymer as (A) component, the adhesiveness of an electroconductive adhesive composition can be improved stably. .
In addition, since the terminal silyl group polymer as the component (B) has a polyoxyalkylene structure in the main chain, it is possible to impart moderate flexibility to the obtained conductive pressure-sensitive adhesive composition.

Moreover, when comprising the electroconductive adhesive composition of this invention, it is preferable that tackifying resin as (C) component is a terpene phenol-type resin.
By comprising in this way, the glass transition point of the electroconductive adhesive composition obtained is adjusted to an appropriate range, and a favorable adhesive characteristic can be obtained.

Moreover, when comprising the electroconductive adhesive composition of this invention, it is preferable that the electroconductive material as (D) component is a carbon nanotube.
With this configuration, even when the amount of the conductive material is smaller, good conductivity can be obtained, mixing and dispersion are facilitated, and it is economically advantageous.

In constituting the conductive pressure-sensitive adhesive composition of the present invention, the volume resistivity of the conductive pressure-sensitive adhesive composition is preferably set to a value less than 1 × 10 ⁵ Ω · cm.
By comprising in this way, suitable electroconductivity can be provided to an adhesive sheet provided with an electroconductive adhesive composition.

Another aspect of the present invention is a conductive pressure-sensitive adhesive sheet provided with a conductive pressure-sensitive adhesive layer comprising the above-mentioned conductive pressure-sensitive adhesive composition on both sides or one side of a substrate.
By comprising in this way, the adhesive sheet excellent in electroconductivity and adhesiveness can be obtained.

Moreover, when comprising the electroconductive adhesive sheet of this invention, it is preferable to make the surface resistivity of an electroconductive adhesive layer into the value of less than 1 * 10 < ⁶ > ohm / square.
By comprising in this way, the adhesive sheet excellent in electroconductivity and adhesiveness can be obtained.

Still another embodiment of the present invention is a method for producing a conductive pressure-sensitive adhesive sheet comprising a conductive pressure-sensitive adhesive layer made of a cross-linked conductive pressure-sensitive adhesive composition on both sides or one side of a substrate, which comprises the following steps: It is a manufacturing method of the conductive adhesive sheet characterized by including (1)-(3).
(1) A conductive pressure-sensitive adhesive composition comprising at least a (meth) acrylic acid ester copolymer as the component (A), a urethane polymer as the component (B), and a tackifier resin as the component (C). And, with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the (A) component, the blending amount of the urethane polymer as the (B) component is a value within the range of 80 to 800 parts by weight, (C) The amount of the tackifying resin as the component is set to a value within the range of 80 to 800 parts by weight, and as the component (D), an uncrosslinked conductive pressure-sensitive adhesive composition containing a conductive material is prepared. Step (2) Step of laminating the uncrosslinked conductive adhesive composition on both sides or one side of the substrate (3) Curing reaction of the uncrosslinked conductive adhesive composition to crosslink the conductive adhesive composition With a conductive adhesive layer Step of the conductive adhesive sheet

  By carrying out like this, in the conductive pressure-sensitive adhesive composition used for the conductive pressure-sensitive adhesive sheet of the present invention, the urethane polymer as the component (B) and the acrylic copolymer as the component (A) and (C) While blending a tackifier resin as a component and blending a conductive material as a component (D), efficiently produce a pressure-sensitive adhesive sheet having excellent conductivity and adhesive properties. Can do.

FIGS. 1A to 1B are reaction formulas for explaining a synthesis method and a crosslinking reaction of a predetermined terminal silyl group polymer, respectively. 2 (a) to 2 (b) are FT-IR spectra of tackifying resins (non-hydrogenated terpene phenol resin and fully hydrogenated terpene phenol resin), respectively. FIG. 3 is a diagram provided for explaining the relationship between the blending amount of the conductive material and the surface resistivity. 4 (a) to 4 (c) are diagrams provided to explain each aspect of the conductive adhesive sheet. Drawing 5 (a)-(d) is a figure offered in order to explain the manufacturing method and use mode of a conductive adhesive sheet, respectively. FIG. 6 is a diagram for explaining a conventional antistatic pressure-sensitive adhesive sheet.

[First Embodiment]
The first embodiment of the present invention comprises at least a (meth) acrylic acid ester copolymer as the component (A), a urethane polymer as the component (B), and a tackifier resin as the component (C). 80 to 800 parts by weight of the urethane polymer as the component (B) with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A) Characterized in that the blending amount of the tackifying resin as the component (C) is a value within the range of 80 to 800 parts by weight and the conductive material is contained as the component (D). The conductive pressure-sensitive adhesive composition.

  Hereinafter, the conductive adhesive composition according to the first embodiment of the present invention will be specifically described with reference to the drawings as appropriate.

1. (A) component: (meth) acrylic acid ester copolymer (1) type Moreover, the (meth) acrylic acid ester copolymer as (A) component mainly has a structural unit derived from (meth) acrylic acid alkyl ester. The kind of the (meth) acrylic acid alkyl ester contained as a component monomer is not particularly limited, and conventionally known ones can be appropriately used.
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate and (meth) acrylic acid One kind alone or a combination of two or more kinds such as stearyl can be mentioned.
Moreover, since the (meth) acrylic acid alkyl ester is a main component constituting the (meth) acrylic acid ester polymer which is the (A) component, it is usually 60% of all monomer components constituting the (A) component. The value is preferably at least% by weight, more preferably within the range of 70 to 99% by weight, and even more preferably within the range of 75 to 95% by weight.

  Moreover, it is preferable that the (meth) acrylic ester polymer which is (A) component contains a carboxyl group-containing vinyl monomer, a nitrogen-containing vinyl monomer, etc. as a monomer component at the time of superposing | polymerizing.

  More specifically, examples of the carboxyl group-containing vinyl monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic acid monomethyl ester, citraconic acid monomethyl ester, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, One kind of succinic acid mono (2-acryloyloxyethyl), one kind of succinic acid mono (2-methacryloyloxyethyl), or a combination of two or more kinds may be mentioned.

Further, the amount of the carboxyl group-containing vinyl monomer used when copolymerizing the (meth) acrylic acid ester copolymer is a value within the range of 0.1 to 40% by weight with respect to 100% by weight of all monomer components. It is preferable to do.
The reason for this is that not only the polymerization of the (meth) acrylic acid ester copolymer is facilitated by controlling the amount of the carboxyl group-containing vinyl monomer used, but also the (meth) acrylic acid ester copolymer is used. This is because the pressure-sensitive adhesive properties of the pressure-sensitive adhesive composition can be stably improved.
Therefore, the amount of the carboxyl group-containing vinyl monomer used when copolymerizing the (meth) acrylic acid ester copolymer is set to a value within the range of 1 to 30% by weight with respect to 100% by weight of all monomer components. Is more preferable, and a value in the range of 3 to 15% by weight is even more preferable.

The nitrogen-containing vinyl monomer is not particularly limited as long as it is a vinyl compound having a nitrogen atom in the molecule. For example, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine , N-vinyl piperazine, N-vinyl pyrazine, N-vinyl pyrrole, N-vinyl oxazole, N-vinyl morpholine, N-vinyl caprolactam, N-vinyl pyrrolidone, N-vinyl imidazole, etc. Acryloyl morpholine, dimethyl (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc. (Meth) acrylamide derivatives; (meth) acrylic acid monomethyl (meth) acrylic acid monomethylaminoethyl, (meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl, etc. Examples thereof include (meth) acrylic acid ester containing an amino group such as alkylaminoalkyl; N-vinylacetamide; N-vinylformamide alone or in combination of two or more.
The (meth) acrylamide derivative refers to a compound having a structure in which (meth) acrylic acid and an arbitrary secondary or lower amine are bonded with an amide bond.

Among the compounds described above, a vinyl compound having an amide structure in the molecule is preferable because the adhesiveness of the conductive adhesive composition can be improved more effectively.
Examples of the vinyl compound having such an amide structure include N-vinylpyrrolidone, N-vinylcaprolactam, any (meth) acrylamide derivative, N-vinylacetamide, N-vinylformamide and the like.
Of vinyl compounds having an amide structure in the molecule, it is more preferable to use a (meth) acrylamide derivative in view of ease of polymerization.
Among these, it is particularly preferable to use at least one selected from the group consisting of acryloylmorpholine, dimethylacrylamide, and N-isopropylacrylamide.

Further, the amount of the nitrogen-containing vinyl monomer used when copolymerizing the (meth) acrylic acid ester copolymer is set to a value within the range of 0.1 to 40% by weight with respect to 100% by weight of all monomer components. It is preferable.
The reason for this is that not only the polymerization of the (meth) acrylic acid ester copolymer is facilitated by controlling the amount of the nitrogen-containing vinyl monomer used, but the use of the nitrogen-containing vinyl monomer makes the (meth) acrylic Outgas derived from the acid ester copolymer is less likely to occur, and when the adherend is a metal, corrosion of the adherend can be suppressed, so that it is difficult to cause problems even when used inside an electronic device. Because.
Therefore, the amount of the nitrogen-containing vinyl monomer used when copolymerizing the (meth) acrylic acid ester copolymer is set to a value within the range of 1 to 30% by weight with respect to 100% by weight of all monomer components. More preferably, the value is more preferably in the range of 3 to 15% by weight.

On the other hand, monomers other than the above may be included as other structural units. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy (meth) acrylate Hydroxy group-containing vinyl monomers such as butyl and 4-hydroxybutyl (meth) acrylate, vinyl esters such as vinyl acetate and vinyl propionate, olefins such as ethylene, propylene and isobutylene, halogenation such as vinyl chloride and vinylidene chloride olefins, styrene, an aromatic vinyl monomer such as methyl styrene vinyl toluene, butadiene, isoprene, diene monomer of chloroprene include nitrile monomers such as (meth) acrylonitrile.

(2) Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of the (meth) acrylic acid ester copolymer which is (A) component into the value within the range of 1,000-3,000,000.
This is because when the weight average molecular weight of the (meth) acrylic acid ester copolymer is less than 1,000, the adhesive properties of the adhesive composition may be significantly deteriorated.
On the other hand, when the weight average molecular weight of the (meth) acrylic acid ester copolymer exceeds 3,000,000, the compatibility with the urethane polymer as the component (B) is remarkably lowered, or the polymerization time is excessively long. This is because it may be easily decomposed into a low molecular weight substance.
Therefore, the weight average molecular weight of the (meth) acrylic acid ester copolymer which is the component (A) is more preferably in the range of 5,000 to 2,000,000, and 10,000 to 1,500. More preferably, the value is within the range of 1,000.

(3) Compounding quantity Moreover, the compounding quantity of the (meth) acrylic acid ester copolymer which is (A) component is the value within the range of 7 to 37 weight% with respect to the whole quantity of an electroconductive adhesive composition. It is preferable that
The reason for this is that a conductive pressure-sensitive adhesive composition having an excellent balance between adhesive strength and conductivity can be obtained by setting the blending amount of the (meth) acrylic acid ester copolymer to a value within this range. This is because it can.
That is, when the blending amount of the (meth) acrylic acid ester copolymer becomes a value outside the range, the conductivity in the conductive pressure-sensitive adhesive composition may be remarkably lowered.
Therefore, it is more preferable to set the blending amount of the (meth) acrylic acid ester copolymer as the component (A) to a value within the range of 8 to 35% by weight with respect to the total amount of the conductive adhesive composition. Preferably, the value is in the range of 9 to 33% by weight.

2. (B) Component: Urethane polymer (1) Type 1
Moreover, the kind of urethane polymer is not particularly limited, and any urethane polymer can be used as long as it is obtained by reacting a polyol and a polyisocyanate.
More specifically, examples of the low molecular weight polyol include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol and hexamethylene glycol, trivalent alcohols such as trimethylolpropane and glycerin, or pentaerythritol. And tetravalent alcohols.
Moreover, as a high molecular polyol, polyether polyol obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran or the like, or the above-mentioned dihydric alcohol, 1,4-butanediol, 1,6-hexanediol Examples include polyester polyols, acrylic polyols, carbonate polyols, epoxy polyols, caprolactone polyols, and the like, which are polycondensates of alcohols such as adipic acid, azelaic acid, and sebacic acid.
Examples of the acrylic polyol include a homopolymer or copolymer of a monomer having a hydroxyl group, and a copolymer of a monomer having a hydroxyl group and an acrylic monomer. Examples of the epoxy polyol include amine-modified epoxy resins.
These polyols may be used alone or in combination of two or more.

Examples of the polyisocyanate include aromatic, aliphatic, and alicyclic polyisocyanates.
Here, as the aromatic polyisocyanate, for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-tri Examples thereof include phenylmethane triisocyanate, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.
Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodecamethylene. Examples thereof include diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane Etc.
Examples of the polyisocyanate include isocyanurate type, burette type, and allophanate type.

  In the present invention, the use amount of the polyol component and the polyisocyanate component for forming the urethane polymer is such that the NCO / OH (molar ratio) is a value in the range of 1.1 to 3.0. It is preferable that

(2) Type 2
In addition, the urethane polymer as the component (B) has a urethane bond and / or a urea bond in the main chain or side chain, or one of them, and is hydrolyzable represented by the following general formula (1) at both ends of the main chain. A terminal silyl group polymer having a silyl group is preferred.

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.)

This is because the component (B) has a bifunctional hydrolyzable terminal silyl group represented by the general formula (1) if the urethane polymer as the component (B) is a terminal silyl group polymer described above. This is because a three-dimensional network structure can be effectively formed by hydrolytic dehydration condensation between each other.
Therefore, excellent adhesive force can be exhibited by a combination with a predetermined tackifying resin, and good adhesiveness can be exhibited when used in a conductive adhesive sheet.
Moreover, if it is such (B) component, since it has the bifunctional hydrolyzable terminal silyl group represented by General formula (1), the gel fraction in the electroconductive adhesive composition after bridge | crosslinking is predetermined. By adjusting to the range, excellent cohesive force can be exhibited.
Therefore, even when the conductive pressure-sensitive adhesive composition is applied to a conductive pressure-sensitive adhesive sheet and processed into a roll shape, the conductive pressure-sensitive adhesive composition oozes out from the side surface over time. Can be suppressed.
Therefore, by using a terminal silyl group polymer as the component (B), a conductive pressure-sensitive adhesive composition having an excellent balance between adhesive force and cohesive force can be obtained.
In general formula (1), the alkyl group represented by R has 1 to 20 carbon atoms, more preferably 1 to 12 because of good hydrolytic dehydration condensation reactivity. More preferably, it is ~ 3.
Further, in the general formula (1), when X ¹ or X ² is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 12 because of good hydrolytic dehydration condensation reactivity, It is more preferable that it is 1-3.

The terminal silyl group polymer is composed of a predetermined end portion and a predetermined skeleton portion.
A specific method for synthesizing the terminal silyl group polymer will be described in the third embodiment.

  First, specific structures of the terminal portion of the predetermined terminal silyl group polymer shown in FIG. 1A are shown in the following general formulas (2) to (8) (terminal portions -A to G).

(In the general formula (2), R ² and R ³ are alkyl groups having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and R, X ¹ and X ² are the same as in the case of the general formula (1). The same applies to the following general formulas (3) to (8).)

(In General Formula (8), X ³ is an alkylene group, and X ⁴ represents an organic group having 1 to 20 carbon atoms.)

  That is, when the terminal silyl group polymer has such a terminal portion, the adhesion to the adherend can be further strengthened.

Further, the skeleton of the main chain or side chain (not shown) of the predetermined terminal silyl group polymer shown in FIG. 1A is preferably polyoxyalkylene.
The reason for this is that if it is polyoxyalkylene, an appropriate flexibility can be imparted to the resulting conductive pressure-sensitive adhesive composition, and the adhesion to the adherend can be further improved.
Specific examples of such polyoxyalkylene include polyoxypropylene and polyoxyethylene.

Further, the terminal silyl group polymer as the component (B) does not have the hydrolyzable silyl group represented by the general formula (1) in the side chain as shown in FIG. Only a terminal silyl group polymer having a hydrolyzable silyl group represented by the general formula (1) is preferable.
The reason for this is that the cross-linking density between the components (B) is adjusted to a suitable range with such a silyl group polymer at both terminals, and the balance between the cohesive force and cohesive force in the conductive adhesive composition after cross-linking is adjusted. This is because it can be made easier.

In addition, as the component (B ′), the polymer further contains a single-terminal silyl group polymer having a hydrolyzable silyl group represented by the general formula (1) only at one end of the main chain, It is preferable to set the value within the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.
The reason for this is that the cross-linking density between the components (B) is adjusted to a more suitable range by mixing the one-end silyl group polymer within a predetermined range with respect to the both-end silyl group polymer, and the conductivity after crosslinking is increased. This is because it is possible to further easily adjust the balance between the adhesive force and the cohesive force in the adhesive composition.
That is, if the blending amount of the one-terminal silyl group polymer is less than 0.1 part by weight, the effect of addition may not be sufficiently obtained. On the other hand, when the blending amount of the one-terminal silyl group polymer exceeds 30 parts by weight, the crosslinking density between the components (B) may be excessively lowered, making it difficult to obtain a predetermined gel fraction. Because there is.
Therefore, the blending amount of the one-terminal silyl group polymer is more preferably set to a value within the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of both terminal silyl group polymers, and the range of 1 to 5 parts by weight. More preferably, the value is within the range.
However, since it has been confirmed that a conductive pressure-sensitive adhesive composition excellent in adhesive strength can be obtained even when only a both-end silyl group polymer is used, if not particularly required, a single-end silyl group It is also preferable from the viewpoint of simplifying the production process to use only the silyl group polymer at both terminals without mixing the polymers.

(3) Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of the urethane polymer which is (B) component into the value within the range of 15,000-200,000.
The reason for this is that when the weight average molecular weight of the urethane polymer is less than 15,000, the molecular structure becomes dense and sufficient adhesive strength cannot be obtained, and the viscosity becomes too low, and the sheet is processed by solution coating. This is because the sex may become worse.
On the other hand, when the weight average molecular weight of the urethane polymer exceeds 200,000, the processability due to an increase in viscosity becomes noticeable, the crosslink density decreases excessively, and the balance between adhesive force and cohesive force is adjusted. This is because it may be difficult to do.
Therefore, the weight average molecular weight of the urethane polymer as the component (B) is more preferably set to a value within a range of 20,000 to 150,000, and a value within a range of 30,000 to 100,000. Further preferred.
In addition, the weight average molecular weight of the urethane polymer which is (B) component can be measured using well-known molecular weight measuring apparatuses, such as a gel permeation chromatography (GPC).
In addition, when the component (B ′) described above is blended, the weight average molecular weight of the component (B ′) can be the same as that of the component (B).

(4) Compounding quantity Moreover, the compounding quantity of the urethane polymer which is (B) component is in the range of 80-800 weight part with respect to 100 weight part of (meth) acrylic acid ester copolymer which is (A) component. It is set as the value of.
The reason for this is that when the blending amount of the urethane polymer is less than 80 parts by weight, the conductivity in the conductive pressure-sensitive adhesive composition may be significantly lowered.
On the other hand, when the compounding amount of the urethane polymer exceeds 800 parts by weight, the adhesive property in the conductive adhesive composition may be remarkably deteriorated.
Therefore, the blending amount of the urethane polymer as the component (B) is set to a value within the range of 85 to 600 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A). Is more preferable, and a value in the range of 90 to 500 parts by weight is even more preferable.

3. Component (C): Tackifier resin (1) type The type of tackifier resin as component (C) is not particularly limited, and rosin resins such as polymerized rosin, polymerized rosin ester, rosin derivative, Polyterpene resin, aromatic modified terpene resin and hydride thereof, terpene phenol resin, coumarone indene resin, aliphatic petroleum resin, aromatic petroleum resin and hydride thereof, aliphatic / aromatic copolymer petroleum resin, One kind of a partially hydrogenated terpene phenol resin, styrene or a low molecular weight coalescence of a substituted styrene, or a combination of two or more kinds may be mentioned.
The reason for this is that if these tackifying resins are used, the conductive adhesive composition exhibits excellent adhesive strength and cohesive strength without inhibiting the interaction with the urethane polymer as the component (B). It is because it can do.

More specifically, the tackifier resin is preferably a terpene phenol resin, and more preferably a fully hydrogenated terpene phenol resin or a partially hydrogenated terpene phenol resin.
This is because the glass transition point of the urethane polymer as the component (B) can be easily adjusted by including the terpene phenol resin.
Further, if it is a fully hydrogenated terpene phenol resin or a partially hydrogenated terpene phenol resin, it becomes even easier to adjust the maximum value of the loss tangent in the conductive adhesive composition, that is, the glass transition point relatively high, And even if it is a case where the cohesion force in a conductive adhesive composition is a comparatively high value, it is because favorable electroconductivity can be obtained.

Here, the fully hydrogenated terpene phenol resin is a tackifying resin obtained by substantially completely hydrogenating a terpene phenol resin, and the partially hydrogenated terpene phenol resin is a terpene phenol resin. It is a tackifier resin obtained by partially hydrogenating.
The terpene phenol resin has a terpene-derived double bond and a phenol-derived aromatic ring double bond.
Therefore, the fully hydrogenated terpene phenol resin means a tackifying resin in which both the terpene moiety and the phenol moiety are completely or almost hydrogenated, and the partially hydrogenated terpene phenol resin is This means a terpene phenolic resin in which the degree of hydrogenation is not complete and partial.

In addition, it can be judged using the FT-IR spectrum obtained by a Fourier-transform infrared spectrophotometer (FT-IR) whether it corresponds to a fully hydrogenated terpene phenol-type resin.
Here, it demonstrates more concretely using the FT-IR spectrum of the fully hydrogenated terpene phenol-type resin shown in FIG.2 (b).
That is, when the height of the peak at about 2960 cm ⁻¹ derived from the carbon-hydrogen bond stretching vibration of the methyl group is defined as 100, 1625-1575 cm ⁻ derived from the aromatic carbon-carbon double bond stretching vibration of the phenol moiety. ^If the peak height of ¹ is less than 20%, the phenolic moiety is completely or almost hydrogenated.
On the other hand, when the peak height derived from the phenol moiety is 20% or more, it is a non-hydrogenated terpene phenol resin in which the phenol moiety and the terpene moiety are hardly hydrogenated as shown in FIG. to decide.
The hydrogenation method and reaction mode are not particularly limited, and examples of the completely hydrogenated terpene phenol resin include NH, manufactured by Yasuhara Chemical Co., Ltd., and the like.

(2) Compounding quantity Moreover, the compounding quantity of tackifying resin which is (C) component is the range of 80-800 weight part with respect to 100 weight part of (meth) acrylic acid ester copolymer which is (A) component. It is characterized by the value within.
This is because by setting the blending amount of the tackifying resin to a value within such a range, it is possible to obtain a conductive pressure-sensitive adhesive composition having an excellent balance between adhesive force and cohesive force.
That is, when the amount of the tackifying resin is less than 80 parts by weight, it may be difficult to obtain sufficient adhesive strength in the conductive adhesive composition.
On the other hand, when the compounding amount of the tackifying resin exceeds 800 parts by weight, the cohesive force of the conductive adhesive composition is decreased, and the conductive adhesive is gradually deteriorated when processed into a roll form. This is because the agent composition may ooze out.
Therefore, the blending amount of the predetermined tackifying resin as the component (C) is a value within the range of 85 to 600 parts by weight with respect to 100 parts by weight of the (meth) acrylate copolymer as the component (A). It is more preferable that the value be within the range of 90 to 500 parts by weight.

4). Component (D): Conductive material (1) Type The type of the conductive material as component (D) is not particularly limited, but for example, a single type of metal particles, ceramic particles, carbon-based particles or the like A combination of two or more types can be mentioned.
More specifically, examples of the metal particles include one kind of gold, silver, copper, nickel, tungsten, aluminum, stainless steel, and solder, or a combination of two or more kinds.
Examples of the ceramic particles include indium oxide, tin oxide, zinc oxide, indium tin oxide (ITO), indium zinc oxide (IZO), antimony tin oxide (ATO) and the like alone or in combination of two or more.
Furthermore, examples of the carbon-based particles include one kind or a combination of two or more kinds of carbon, carbon nanotube, fullerene, and the like.
In particular, if the conductive material is a carbon nanotube, a smaller amount, for example, a blending amount in the range of 0.5 to 2% by weight with respect to the total amount of the conductive adhesive composition. A good surface resistivity of less than 1 × 10 ⁶ Ω / □ is obtained, and not only mixing and dispersion are facilitated, but also economically advantageous.
Moreover, if a conductive material is a carbon nanotube, the diameter (fiber diameter) becomes like this. Preferably it is 1-1000 nm, More preferably, it is 3-500 nm, More preferably, it is 5-100 nm.
The length (fiber length) of the carbon nanotube is preferably 10 nm to 200 μm, more preferably 50 nm to 100 μm, and still more preferably 100 nm to 50 μm.
The aspect ratio of the carbon nanotube is preferably 10 to 10,000, more preferably 50 to 5000, and still more preferably 100 to 2000.
The average diameter, average length, and aspect ratio of the above carbon nanotubes were randomly extracted using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, product name “S-4700”). It is a value measured by observing 10 pieces.

(2) Compounding quantity Moreover, the compounding quantity of the electroconductive material which is (D) component is 0.01-100 weight part with respect to 100 weight part of (A) component (meth) acrylic acid ester copolymers. It is preferable to set the value within the range.
The reason for this is that the conductive pressure-sensitive adhesive composition has an excellent balance between electrical conductivity (surface resistivity and volume resistivity) and adhesive strength by setting the blending amount of the conductive material within the range. This is because things can be obtained.
That is, when the amount of the conductive material is less than 0.01 parts by weight, it may be difficult to obtain sufficient conductivity in the conductive adhesive composition.
On the other hand, if the amount of the conductive material exceeds 100 parts by weight, the adhesiveness of the conductive adhesive composition may be significantly reduced.
Therefore, the blending amount of the conductive material as the component (D) is a value within the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the (meth) acrylate copolymer as the component (A). More preferably, the value is more preferably in the range of 0.5 to 20 parts by weight.

Here, with reference to FIG. 3, the relationship between the blending amount (% by weight) of the conductive material as the component (D) and the surface resistivity (Ω / □) will be described.
That is, the horizontal axis in FIG. 3 shows the blending amount (% by weight) of the conductive material (carbon nanotube) with respect to the total amount of the conductive adhesive composition, and the vertical axis in FIG. The surface resistivity (Ω / □) obtained when the adhesive composition is made into a sheet is shown.
And the characteristic curve A in this FIG. 3 respond | corresponds to the electroconductive adhesive composition which consists of (A)-(F) component of this invention. Moreover, the characteristic curve B in FIG. 3 does not contain the (meth) acrylic acid ester copolymer which is the component (A), and corresponds to the conductive adhesive composition comprising the components (B) to (F). ing. Further, the characteristic curve C in FIG. 3 corresponds to the conductive pressure-sensitive adhesive composition comprising the components (A) and (C) to (F) without blending the urethane polymer as the component (B).

Therefore, judging from the characteristic curve A, according to the conductive adhesive composition comprising the components (A) to (F) of the present invention, the blending amount of the conductive material as the component (D) is 0.125% by weight. Even when the amount is extremely small, a moderately low surface resistivity of about 1 × 10 ¹¹ Ω / □ is obtained. When the amount of the conductive material is 0.25% by weight, the surface resistivity is rapidly increased. Is reduced to a value of about 1 × 10 ⁷ Ω / □. Furthermore, when the blending amount of the conductive material is 0.5% by weight, the surface resistivity is further lowered to about 1 × 10 ⁵ Ω / □, and then the blending amount of the conductive material is 0.5% by weight. Exceedingly, in the range of at least 2% by weight, an extremely low uniform surface resistivity of about 1 × 10 ⁴ Ω / □ can be obtained regardless of the blending amount of the conductive material.
Judging from the characteristic curve B, the conductive pressure-sensitive adhesive composition comprising the components (B) to (F) that does not contain the (A) component (meth) acrylate copolymer is also included in the present invention. It can be said that the surface resistivity having the same tendency as that of the conductive adhesive composition can be obtained.
On the other hand, judging from the characteristic curve C, in the case of the conductive adhesive composition comprising the components (A) and (C) to (F) without blending the urethane polymer as the component (B), blending of the conductive material Even if the amount is 0.5% by weight, it is a value of about 1 × 10 ¹⁰ Ω / □, and then the surface resistivity gradually changes and decreases as the amount of the conductive material is increased. Even if the blending amount of the conductive material exceeds 1.5% by weight, the value is about 1 × 10 ⁶ Ω / □.
Therefore, according to the conductive pressure-sensitive adhesive composition comprising the components (A) to (F) of the present invention, even if the blending amount of the conductive material is extremely low, it can exhibit low conductivity as such, It is understood that if the blending amount of the conductive material exceeds a certain level, a very low uniform surface resistivity can be obtained over a wide blending amount.

5-1. Component (E1): Crosslinking Agent (1) Type As the crosslinking agent for the urethane polymer of component (B), for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent Agents, amine crosslinking agents, amino crosslinking agents and the like, and isocyanate crosslinking agents are more preferable.
Examples of the isocyanate-based crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2 , 4'-diphenylmethane diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 2,4'-methylenebis ( Cyclohexyl isocyanate) and polyisocyanate compounds such as lysine isocyanate.
The polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.

(2) Compounding quantity Moreover, when mix | blending the crosslinking agent which is (E1) component, the compounding quantity is in the range of 0.1-30 weight part with respect to 100 weight part of urethane polymers of (B) component. The value is preferably set to a value within the range of 0.5 to 10 parts by weight.

5-2. (E2) Component: Curing Catalyst (1) Type When the component (B) is a terminal silyl group polymer, the curing catalyst as the component (E) for reacting the hydrolyzable silyl group is Although it is unnecessary, it is also preferable to mix it in a small amount.
That is, when the (meth) acrylic acid ester copolymer as the component (A) has a polymerization region derived from a carboxyl group-containing monomer, or when a silane coupling agent described later has an amino group. Since the reaction of the hydrolyzable silyl group can be remarkably improved by them, it is preferable that the curing catalyst as the component (E) is unnecessary or the blending amount thereof is reduced as much as possible.
However, when the (meth) acrylic acid ester copolymer as the component (A) does not have a polymerization region derived from a carboxyl group-containing monomer, the reactivity of the hydrolyzable silyl group is increased, and the crosslinking density When it is desired to considerably increase the ratio, it is preferable to blend a relatively small amount of the curing catalyst as the component (E).

Here, the curing catalyst is preferably at least one selected from the group consisting of an aluminum catalyst, a titanium catalyst, a zirconium catalyst, and a boron trifluoride catalyst.
The reason for this is that if these curing catalysts are used, it becomes easy to control the crosslinking density between the terminal silyl group polymers as the component (B), and the adhesive force and cohesive force in the conductive adhesive composition after crosslinking are This is because the balance between them can be further improved. In addition, aluminum-based catalysts, titanium-based catalysts, and zirconium-based catalysts are non-halogen-based and have higher safety.

More specifically, the aluminum catalyst is preferably an aluminum alkoxide, an aluminum chelate, or aluminum (III) chloride.
The titanium-based catalyst is preferably titanium alkoxide, titanium chelate, or titanium (IV) chloride.
Further, as the zirconium-based catalyst, zirconium alkoxide, zirconium chelate, and zirconium (IV) chloride are preferable.
Furthermore, as the boron trifluoride-based catalyst, an amine complex or an alcohol complex of boron trifluoride is preferable.

(2) Blending amount When blending the curing catalyst which is the component (E), the blending amount is more than 0 and 0.1% by weight with respect to the total amount of the components (A) to (C). The following values are preferable.
The reason for this is that when the amount of the curing catalyst exceeds 0.1% by weight, the catalytic action becomes excessive, and the conductive adhesive composition is cured before being applied to the substrate or mixed uniformly. This is because it may be difficult to perform, or the manufacturing cost may increase.
Therefore, the blending amount of the curing catalyst which is the component (E) is more preferably set to a value of 0 to 0.05% by weight with respect to the total amount of the components (A) to (C). More preferably, it is more than 0 and 0.01% by weight or less.

6). (F) Component: Silane Coupling Agent (1) Type It is also preferable that the conductive adhesive composition contains a silane coupling agent as the (F) component.
The reason for this is that by adding a predetermined amount of the silane coupling agent, the adhesive force and moisture resistance of the conductive adhesive composition can be improved, and the crosslinking reaction of the urethane polymer, particularly the terminal silyl group polymer, can be improved. It is because the effect to promote can be exhibited.
And in order to exhibit the effect as a crosslinking adjuvant effectively, it is more preferable to use the silane coupling agent which has an amino group among various silane coupling agents.
This is because the silane coupling agent having such an amino group controls the reactivity of the terminal silyl group polymer and stably exhibits the function as a crosslinking aid.
Therefore, by blending a predetermined amount of the amino group-containing silane coupling agent, not only can the adhesive strength and moisture resistance of the conductive pressure-sensitive adhesive composition be improved, but also the cohesive strength of the conductive pressure-sensitive adhesive composition is more suitable. Can be adjusted within a wide range.
Therefore, as a suitable silane coupling agent having an amino group, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc. The combination of is mentioned.

(2) Blending amount In blending the silane coupling agent as the component (F), 0.01 to 10 weights with respect to 100 parts by weight of the (meth) acrylate copolymer as the component (A). The value is preferably within the range of parts.
This is because, within such a range, a relatively inexpensive conductive adhesive composition can be provided, and the adhesive strength and moisture resistance of the conductive adhesive composition can be stably improved. is there.
On the other hand, when a silane coupling agent is blended as a crosslinking aid, the silane coupling agent (a silane coupling agent having an amino group) is 1 mol or more per 1 mol of the curing catalyst of the component (E). It is preferable to do.
The reason for this is that by blending the silane coupling agent as a crosslinking aid in such a range, the effect of the predetermined terminal silyl group polymer as a crosslinking aid is effectively exhibited, and the cohesive strength of the conductive adhesive composition. This is because can be adjusted to a more suitable range.
Accordingly, the blending amount of the silane coupling agent as the crosslinking aid is more preferably set to a value within the range of 1 to 30 mol with respect to 1 mol of the curing catalyst of the component (E), and the range of 2 to 10 mol. More preferably, the value is within the range.

7). Various additives In addition to the above-described components, the conductive adhesive composition includes, for example, an anti-aging agent, a dehydrating agent such as a vinyl silane compound and calcium oxide, a filler, a thermally conductive material, a plasticizer, and anhydrous silica. , Thixotropic agents such as amide wax, diluents such as isoparaffin, aluminum hydroxide, halogen flame retardant, phosphorus flame retardant, flame retardant such as silicone flame retardant, functional oligomer such as silicone alkoxy oligomer, acrylic oligomer, It is also preferable to add and mix a pigment, titanate coupling agent, aluminum coupling agent, drying oil and the like.
Moreover, when adding these additives, although it depends also on the kind of additive, it is preferable to mix | blend to such an extent that the effect of this invention is not impaired, and the compounding quantity is (A) component (meta). The value is preferably in the range of 0.01 to 100 parts by weight, preferably in the range of 0.01 to 70 parts by weight, with respect to 100 parts by weight of the acrylate copolymer. A value within the range of 0.01 to 40 parts by weight is particularly preferable.

8). Gel fraction Moreover, when comprising a conductive adhesive composition, it is preferable to make the gel fraction of an adhesive layer into the value within the range of 30 to 70%.
The reason for this is that by setting the gel fraction of the pressure-sensitive adhesive layer to a value within this range, excellent cohesive force can be exhibited, and when processed into a roll shape, the conductive pressure-sensitive adhesive immerses from the side surface over time. It is because it can suppress that it protrudes.
That is, when the gel fraction of the pressure-sensitive adhesive layer is less than 30%, the cohesive force becomes excessively small, and the conductive pressure-sensitive adhesive may ooze out from the side surface over time when the roll is formed. Because.
On the other hand, if the gel fraction of the pressure-sensitive adhesive layer becomes excessively high, sufficient adhesive strength may not be obtained.
Therefore, the gel fraction of the pressure-sensitive adhesive layer in the conductive pressure-sensitive adhesive composition is more preferably set to a value within the range of 35 to 65%, and further preferably set to a value within the range of 40 to 60%.
The “gel fraction of the pressure-sensitive adhesive layer” means that after applying a conductive pressure-sensitive adhesive composition to a substrate, seasoning for 14 days in a 23 ° C., 50% RH environment, It is measured by a dipping method using a conductive adhesive as a measurement sample.
In addition, about the detailed measuring method of a gel fraction, it describes concretely in an Example.

9. Volume resistivity Moreover, it is preferable to make the volume resistivity of the electroconductive adhesive composition measured based on JIS-K7194 into the value of less than 1 * 10 < ⁵ > ohm * cm.
The reason for this is that when the volume resistance value of the conductive pressure-sensitive adhesive composition is a value within such a range, it is possible to impart conductivity suitable for a conductive pressure-sensitive adhesive sheet.
Therefore, the volume resistance value of the conductive pressure-sensitive adhesive composition is more preferably set to a value less than 1 × 10 ⁴ Ω · cm, and further preferably set to a value less than 2 × 10 ³ Ω · cm.
In addition, about the detailed measuring method of volume resistivity, it describes concretely in an Example.

[Second Embodiment]
The second embodiment is a conductive pressure-sensitive adhesive sheet comprising a conductive pressure-sensitive adhesive layer comprising the conductive pressure-sensitive adhesive composition of the first embodiment described above on both sides or one side of a substrate. .

(1) Aspect More specifically, various aspects can be adopted as a conductive pressure-sensitive adhesive sheet. For example, as shown in FIG. 4A, a conductive pressure-sensitive adhesive layer comprising the conductive pressure-sensitive adhesive composition of the present invention. 12 is preferably formed on one side of the substrate 10 to form a single-sided type conductive adhesive sheet 50.
If it is the aspect of such an electroconductive adhesive sheet 50, it can process into an electroconductive adhesive tape or the surface protection adhesive sheet for antistatic, etc., and can apply it to various uses.
Moreover, as shown in FIG.4 (b), the electroconductive adhesive layer 12 (12a, 12b) which consists of an electroconductive adhesive composition of this invention is formed in both surfaces of the base material 10, and double-sided type electroconductivity is formed. It is also preferable to adopt an embodiment of the pressure-sensitive adhesive sheet 52.
If it is the aspect of such an electroconductive adhesive sheet 52, it can apply suitably for uses, such as conveyance tapes, etc. of an electronic component adhesive material for temporarily fixing an electronic component etc. or an electronic component.
Furthermore, as shown in FIG. 4 (c), a conductive pressure-sensitive adhesive layer 12 made of the conductive pressure-sensitive adhesive composition of the present invention is formed on one surface of the base material 10, and the other surface has Other pressure-sensitive adhesive layers (including adhesive compositions) different from the invention, such as acrylic pressure-sensitive adhesives, styrene-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, epoxy-based adhesives and the like (adhesives) It is preferable that the conductive pressure-sensitive adhesive sheet 54 formed of 18 is also referred to as a conductive double-sided pressure-sensitive adhesive sheet with a different pressure-sensitive adhesive layer.
If it is the aspect of such an electroconductive adhesive sheet 54, it can apply suitably for uses, such as a fixing member for fixing an electronic component to a board | substrate.

(2) Substrate Here, as the substrate for forming the conductive adhesive layer made of the conductive adhesive composition, for example, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyimide, polyether Imide, polyether ketone, polyether ether ketone, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polynorbornene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl chloride, polyurethane acrylate, polyethersulfone A resin film made of a resin such as polyphenyl ether sulfone is preferred.
And although it does not restrict | limit especially as thickness of a base material, Usually, it is preferable to set it as the value within the range of 1-1000 micrometers, and it is more preferable to set it as the value within the range of 10-100 micrometers. .

(3) Thickness of the conductive pressure-sensitive adhesive layer The thickness of the conductive pressure-sensitive adhesive layer made of the conductive pressure-sensitive adhesive composition is usually preferably set to a value in the range of 1 to 100 μm, preferably 5 to 50 μm. It is more preferable to set the value within the range.
The reason for this is that if the thickness of the conductive adhesive layer is less than 1 μm, sufficient adhesive properties and the like may not be obtained. Conversely, if the thickness of the conductive adhesive layer exceeds 100 μm, the residual This is because there are cases where the amount of solvent increases and the adhesive properties and the like are likely to change.

(4) Surface resistivity (sheet resistance)
Moreover, it is preferable to make the surface resistivity of the electroconductive adhesive layer measured based on JIS-K7194 into the value below 1 * 10 < ⁶ > ohm / square.
This is because, if the surface resistivity of the conductive pressure-sensitive adhesive layer is a value within such a range, suitable conductivity and antistatic properties can be exhibited when used in an electronic device.
Therefore, it is more preferable to set the surface resistivity of the conductive adhesive layer and ⁵ × 10 5 Ω / □ values below, and even more preferably from 1 × 10 ⁵ Ω / □ values below.
In addition, about the detailed measuring method of surface resistivity, it describes concretely in an Example.

(5) Others The conductive adhesive sheet of the present invention is also preferably an embodiment in which a release substrate (release film) is bonded to the surface of the conductive adhesive layer.
As such a release substrate, for example, a release layer such as a silicone resin is applied to a polyester film such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate, or a polyolefin film such as polypropylene or polyethylene to provide a release layer. Can be mentioned.
Moreover, it is preferable to make the thickness of this peeling base material into the value within the range of 20-150 micrometers normally.
In addition, by providing a predetermined difference in the peeling force between the two peeling substrates, it is possible to prevent the conductive pressure-sensitive adhesive layer from partially following when the peeling substrate with the lower peeling force is peeled off. can do.

[Third Embodiment]
3rd Embodiment is a manufacturing method of the electroconductive adhesive sheet provided with the electroconductive adhesive layer which consists of a bridge | crosslinking electroconductive adhesive composition on both surfaces or one side of a base material, Comprising: The following process (1)- It is a manufacturing method of the electroconductive adhesive sheet characterized by including (3).
(1) A conductive pressure-sensitive adhesive composition comprising at least a (meth) acrylic acid ester copolymer as the component (A), a urethane polymer as the component (B), and a tackifier resin as the component (C). And, with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the (A) component, the blending amount of the urethane polymer as the (B) component is a value within the range of 80 to 800 parts by weight, (C) The amount of the tackifying resin as the component is set to a value within the range of 80 to 800 parts by weight, and as the component (D), an uncrosslinked conductive pressure-sensitive adhesive composition containing a conductive material is prepared. Step (2) Step of laminating the uncrosslinked conductive adhesive composition on both sides or one side of the substrate (3) Curing reaction of the uncrosslinked conductive adhesive composition to crosslink the conductive adhesive composition With a conductive adhesive layer Step of the conductive adhesive sheet

  Hereinafter, with regard to the method for manufacturing and affixing the pressure-sensitive adhesive sheet of the third embodiment, for example, as a method for manufacturing a pressure-sensitive adhesive sheet and a method for affixing a terminal silyl group polymer as the urethane polymer of component (B), FIG. This will be specifically described with reference to (a) to (d) and the like.

1. Step (1) (Preparation step of an uncrosslinked conductive adhesive composition)
Step (1) is a step of preparing a predetermined conductive pressure-sensitive adhesive composition containing the components (A) to (D).
Here, with reference to Fig.1 (a), the synthesis example of the terminal silyl group polymer as a urethane polymer which is (B) component is shown.
First, in FIG. 1A, a urethane prepolymer (diisocyanate compound) having an isocyanate group at the end of the main chain or side chain of the molecule represented by the formula (1) is prepared.
Next, in FIG. 1 (a), an active hydrogen group capable of reacting with an isocyanate group is present at one end of the molecule represented by formula (2), and the other end of the molecule is represented by general formula (1). A silylating agent having a hydrolyzable silyl group is prepared.
Next, after uniformly mixing the urethane prepolymer represented by the formula (1) and the silylating agent represented by the formula (2), for example, by heating and reacting under a nitrogen atmosphere at 80 ° C. for 1 hour, A terminal silyl group polymer represented by the formula (3) can be obtained.
As shown in FIG. 1B, the terminal silyl group polymer represented by the formula (3) passes through hydrolysis of the hydrolyzable silyl group represented by the general formula (1), and is further crosslinked by dehydration condensation. As the reaction proceeds, a three-dimensional network structure can be formed.

In synthesizing the terminal silyl group polymer represented by the formula (3), the silylating agent has an isocyanate group and a predetermined polymer skeleton, contrary to the case of FIG. The compound which has may have an active hydrogen group.
In addition, the active hydrogen in the urethane bond or urea bond introduced into the main chain or side chain of the predetermined terminal silyl group polymer may be substituted with an organic group as described in the first embodiment.
Therefore, allophanate bonds are also included in the category of urethane bonds, and burette bonds are also included in the category of urea bonds.

Next, the obtained (B) component terminal silyl group polymer is diluted with a diluting solvent, if desired, and then separately polymerized, and the (A) component (meth) acrylic acid ester copolymer. Add a fixed amount to make a uniform mixture.
Next, (C) component tackifying resin, (D) component conductive material, and (E) component curing catalyst, and (F) component silane with respect to the obtained mixed liquid After adding a predetermined amount of each of a coupling agent (crosslinking aid) and other additives, the mixture is stirred until uniform, and further a dilution solvent is further added as necessary to obtain a desired viscosity. By adding, a conductive adhesive composition solution can be obtained.

2. Step (2) (Lamination step of uncrosslinked conductive adhesive composition)
Step (2) is a step of forming a coating layer 12 ′ by laminating a conductive adhesive composition solution on the substrate 10 as shown in FIG. 5 (a).
Examples of the method for laminating the conductive adhesive composition solution include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. And after laminating | stacking an adhesive composition solution and forming coating layer 12 ', it is preferable to disperse | distribute a solvent and to make it dry.
At this time, the thickness of the coating layer 12 ′ is preferably set to a value within the range of 1 to 100 μm, and more preferably set to a value within the range of 5 to 50 μm.
This is because if the thickness of the coating layer 12 'is too thin, sufficient adhesive properties and the like may not be obtained. Conversely, if it is too thick, the residual solvent may cause a problem.
Moreover, as drying conditions, it is usually preferable to set it within a range of 10 to 10 minutes at 50 to 150 ° C.

3. Step (3) (Coating layer crosslinking step)
Step (3) is a step of heating the coating layer 12 ′ of the conductive pressure-sensitive adhesive composition to form a crosslinked conductive pressure-sensitive adhesive layer 12.
That is, as shown in FIG. 5 (b), heat treatment is performed in a state in which the peeling substrate 22 is laminated on the surface of the coating layer 12 ′ in a dried state on the substrate 10, thereby causing a crosslinking reaction, It is preferable that the conductive adhesive layer 12 is introduced with a three-dimensional network structure.
Alternatively, the conductive adhesive composition coating layer 12 ′ applied on the release substrate 22 is previously crosslinked by heat treatment to form the conductive adhesive layer 12, and then transferred to the substrate 10 by a transfer method. May be laminated.
Furthermore, it is also preferable that the coating layer 12 ′ formed on the base material 10 is heat-treated without causing the release base material 22 to be subjected to a crosslinking reaction to form the conductive pressure-sensitive adhesive layer 12.

In addition, bridge | crosslinking in coating layer 12 'of a conductive adhesive composition is performed through the drying process mentioned above and a seasoning process.
That is, as a condition of the seasoning process, the conductive adhesive composition coating layer 12 ′ and the base material 10 are not damaged, and the conductive adhesive composition coating layer 12 ′ is uniformly crosslinked. From the viewpoint, the heating temperature is preferably 20 to 50 ° C, more preferably 23 to 30 ° C.
Moreover, as humidity at the time of heating, it is preferable to set it as 30 to 75% RH, and it is more preferable to set it as 45 to 65% RH.

4). Process (4) (Attaching process)
In this step, the conductive adhesive sheet 50 finally obtained is bonded to the adherend 60.
For example, as shown in FIG. 5 (d), first, after peeling off the release film 22 laminated on the conductive adhesive layer 50 ′, the surface of the conductive adhesive layer 12 that appears is attached to the adherend 60. It is preferable to bond evenly by pressing at a predetermined pressure using a laminator, a pressing roll, or the like in a state of being opposed to each other.
In addition, since the electroconductive adhesive sheet 50 of this invention contains the urethane polymer as (B) component in the electroconductive adhesive composition which comprises the electroconductive adhesive layer 12, predetermined | prescribed flexibility is given. In addition, it has excellent affinity for an adherend, and can be attached so as to be moistened without entraining air or the like, so that it is possible to suppress a decrease in conductivity at the application interface.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, the range of this invention is not limited by these Examples etc. without a particular reason.

[Example 1]
1. Preparation of conductive adhesive composition (1) Preparation of acrylic ester copolymer In a stirred vessel purged with nitrogen, as a monomer component, 90 parts by weight of n-butyl acrylate (BA) and 10 parts by weight Acrylic acid (AAc), ethyl acetate as a solvent, and a polymerization initiator were respectively accommodated.
Subsequently, solution polymerization was performed while heating and stirring to obtain an acrylate copolymer having a weight average molecular weight of 700,000.
The obtained acrylic ester copolymer was dissolved in ethyl acetate as a solvent, and the solid content concentration was 33.6% by weight.

(2) Creation of uncrosslinked conductive pressure-sensitive adhesive composition Next, in a stirring vessel, in terms of solid content, with respect to 100 parts by weight of the acrylate copolymer, urethane polymer (manufactured by Yushi Co., Ltd., US-902A) 100 parts by weight and fully hydrogenated terpene phenol resin as a tackifier resin (softening point: 125 ° C., YShara Chemical Co., Ltd., YS Polyster NH, hereinafter simply referred to as “NH”) 125 parts by weight And 3.3 parts by weight of a conductive material (carbon nanotubes, average diameter: 10 nm, average length: 1.5 μm, aspect ratio: 150) and an isocyanate-based crosslinking agent (Nihon Polyurethane Industry Co., Ltd., Coronate L) 6.7 parts by weight were accommodated and stirred in the presence of a predetermined amount of ethyl acetate until uniform to obtain an uncrosslinked conductive adhesive composition.

2. Preparation of conductive pressure-sensitive adhesive sheet Next, the obtained uncrosslinked conductive pressure-sensitive adhesive composition was applied to one side of a 50 μm-thick polyester film (Lumirror PET50, manufactured by Toray Industries, Inc.) by a knife coater method. Then, it heat-dried on 100 degreeC and 1 minute conditions, and was set as the electroconductive adhesive sheet provided with the electroconductive adhesive layer of thickness 25 micrometers.

3. Seasoning of the conductive pressure-sensitive adhesive sheet Next, a conductive pressure-sensitive adhesive sheet comprising a conductive adhesive composition coating layer before the completion of crosslinking and a base material (polyester film) was placed in an environment of 23 ° C. and 50% RH, 14 The conductive pressure-sensitive adhesive composition was sufficiently cross-linked by being allowed to stand (seasoning) for days, and the conductive pressure-sensitive adhesive sheet of Example 1 was obtained.

4). Evaluation (1) Evaluation of adhesive strength The adhesive strength of the adhesive sheet was measured according to JIS Z0237: 2000. Specifically, a test piece having a width of 25 mm and a length of 200 mm was cut out from the obtained conductive pressure-sensitive adhesive sheet and bonded to an SUS304 plate (# 360 file processing) using a 2 kgf rubber roller, and then 23 ° C., 50 It was left for 24 hours in a standard environment of% RH.
Next, using a tensile tester (Orientec Co., Ltd., Tensilon), the test piece was peeled from the SUS304 plate (# 360 file processing) at a peeling speed of 300 mm / min and a peeling angle of 180 °. The measured peeling load was defined as the adhesive strength (N / 25 mm) of the conductive adhesive sheet. The obtained results are shown in Table 1.

(2) Surface resistivity and volume resistivity The surface resistivity and volume resistivity of the obtained conductive adhesive sheet were measured.
That is, a test piece having a width of 20 mm and a length of 40 mm was cut out from the obtained conductive adhesive sheet and allowed to stand for 24 hours in a standard environment of 23 ° C. and 50% RH.
Next, using a low resistivity meter (Loresta GP MCP-T610 type, manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the surface resistivity and volume resistivity of the test piece were measured three times in accordance with JIS-K7194. The average value was defined as the surface resistivity and volume resistivity of the conductive adhesive sheet.
However, for the test piece that was overranged by the low resistivity meter, using a high resistivity meter (manufactured by Mitsubishi Chemical Analytech, Hiresta UP MCP-HT450 type), in accordance with JIS K 6911, The surface resistivity and volume resistivity of the test piece were measured three times, and the average values were taken as the surface resistivity and volume resistivity of the conductive adhesive sheet. The obtained results are shown in Table 1.

(3) Evaluation of gel fraction The gel fraction of the adhesive layer in the obtained electroconductive adhesive sheet was measured.
That is, only the pressure-sensitive adhesive layer in the conductive pressure-sensitive adhesive sheet was immersed in ethyl acetate for 120 hours in an environment of 23 ° C. and 50% RH, then dried at 100 ° C. for 30 minutes, and the weight before and after immersion was measured. Was substituted into the following formula (10) to calculate the gel fraction. The obtained results are shown in Table 1.
Gel fraction (%) = (weight after immersion / weight before immersion) × 100 (10)

[Example 2]
In Example 2, the influence when the urethane polymer of the component (B) was changed to the following terminal silyl group polymer was examined.

1. Preparation of conductive adhesive composition (1) Preparation of silylating agent In a reaction vessel equipped with a stirrer, 206 parts by weight of N-aminoethyl-γ-aminopropylmethyldimethoxysilane, 172 parts by weight of methyl acrylate, Was heated and reacted at 80 ° C. for 10 hours with stirring in a nitrogen atmosphere to obtain a silylating agent.

(2) Preparation of urethane prepolymer In a reaction vessel equipped with a stirrer, 1000 parts by weight of polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd., PML S4015, weight average molecular weight 15,000) and 24.6 parts by weight of isophorone diisocyanate (NCO / OH ratio = 1.7) and 0.05 part by weight of dibutyltin dilaurate were added and heated under a nitrogen atmosphere with stirring at 85 ° C. for 7 hours to obtain a urethane prepolymer (diisocyanate). Compound) was obtained.

(3) Synthesis of terminal silyl group polymer In a reaction vessel equipped with a stirrer, 1000 parts by weight of the obtained urethane prepolymer and 42.1 parts by weight of the obtained silylating agent were accommodated, under a nitrogen atmosphere, While stirring, heat treatment was performed at 80 ° C. for 1 hour to obtain a terminal silyl group polymer.
At this time, the disappearance of isocyanate group absorption (2265 cm ⁻¹ ) was observed using a Fourier transform infrared spectrophotometer (FT-IR), thereby confirming the progress of the reaction.
The obtained terminal silyl group polymer is a both-end silyl group polymer having a terminal moiety represented by the following formula (9) at both ends of polyoxypropylene as a main chain and having a weight average molecular weight of 40,000. there were.
Further, by using N-aminoethyl-γ-aminopropylmethyldimethoxysilane as a raw material for the silylating agent, a bifunctional terminal silyl group was introduced into the obtained terminal silyl group polymer.

(4) Preparation of conductive pressure-sensitive adhesive composition Next, 450 parts by weight of terminal silyl group polymer and 100% by weight as a tackifier resin in terms of solid content in a stirring vessel with respect to 100 parts by weight of an acrylate copolymer. Contains 450 parts by weight of fully hydrogenated terpene phenol resin (NH) and 10 parts by weight of conductive material (carbon nanotubes, average diameter: 10 nm, average length: 1.5 μm), and presence of a predetermined amount of ethyl acetate Under stirring, the mixture was stirred until a uniform pressure-sensitive adhesive composition was obtained.
Next, a conductive pressure-sensitive adhesive sheet was prepared and evaluated in the same manner as in Example 1. The obtained results are shown in Table 1.

[Examples 3 to 4]
In Examples 3 to 4, when the conductive pressure-sensitive adhesive composition was prepared, component (B) with respect to 100 parts by weight of acrylic acid ester copolymer (weight average molecular weight: 700,000) as component (A) The blending amount of the terminal silyl group polymer as the urethane polymer is from 450 parts by weight to 200 parts by weight and 116.7 parts by weight, respectively, and the blending amount of the tackifying resin as the component (C) is from 450 parts by weight. A conductive adhesive sheet was prepared and evaluated in the same manner as in Example 2 except that the amount was changed to 200 parts by weight and 116.7 parts by weight, respectively.
However, about the compounding quantity of the electroconductive material which is (D) component, 5.0 weight part and 3.3 weight part with respect to 100 weight part of acrylic acid ester copolymers which are (A) component in conversion of solid content. Although it changed with the weight part, the compounding quantity with respect to the whole quantity (100 weight%) of each conductive adhesive composition was 1 weight%, and was the same value as Example 1. The obtained results are shown in Table 1.

[Examples 5 to 9]
In Examples 5 to 9, the type of the acrylic ester copolymer as the component (A) is changed to an ACMO acrylic ester copolymer, and the terminal silyl group polymer as a urethane polymer as the component (B), The influence of the compounding amount of the tackifier resin as component (C), the curing catalyst as component (E), and the silane coupling agent (crosslinking aid) as component (F) was examined.
The ACMO acrylic ester copolymer was obtained by solution polymerization as follows.
That is, after purging the inside of a reaction vessel equipped with a stirrer with nitrogen, as monomer components, 80 parts by weight of n-butyl acrylate (BA), 2 parts by weight of methyl acrylate (MA), and 16 parts by weight of acryloyl Morpholine (ACMO), 2 parts by weight of 2-hydroxyethyl acrylate (HEA), ethyl acetate as a solvent, and a polymerization initiator were accommodated.
Next, solution polymerization was performed while heating and stirring to obtain a polymer solution (solvent: ethyl acetate, solid content concentration: 35% by weight) containing an ACMO acrylate copolymer having a weight average molecular weight of 600,000.
And as shown in Table 1, while changing the kind of acrylic ester copolymer which is (A) component to ACMO type acrylic ester copolymer, the terminal silyl group as urethane polymer which is (B) component Example 1 except that the blending amounts of the polymer, the tackifier resin (C), the curing catalyst (E), and the silane coupling agent (crosslinking aid) (F) were changed. A conductive pressure-sensitive adhesive sheet was prepared and evaluated in the same manner as described above.
In addition, about the compounding quantity of the electroconductive material which is (D) component, with respect to 100 weight part of acrylic ester copolymers which are (A) component, 10.1 weight part, 5.0 weight part, 4. Although 0 parts by weight, 3.3 parts by weight, and 2.9 parts by weight, the blending amount with respect to the total amount (100% by weight) of the conductive adhesive composition is 1% by weight, which is the same value as in Example 1. It was. The obtained results are shown in Table 1.

[Comparative Example 1]
In Comparative Example 1, the blending amount of the (B) component urethane polymer was changed from 100 parts by weight to 33.3 parts by weight, and the blending amount of the (C) component tackifying resin was changed from 125 parts by weight to 33.2 parts by weight. Otherwise, a conductive adhesive sheet was prepared and evaluated in the same manner as in Example 1.
In addition, about the compounding quantity of the electroconductive material which is (D) component, although it was 1.7 weight part with respect to 100 weight part of acrylic ester copolymer which is (A) component, a conductive adhesive composition The blending amount with respect to the total amount (100% by weight) of the product was 1% by weight, which was the same value as in Example 1. The obtained results are shown in Table 1.

[Comparative Example 2]
In Comparative Example 2, only the conductive material as the component (D) is blended with the acrylic ester copolymer as the component (A), the urethane polymer as the component (B), and the adhesive as the component (C) A conductive pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the application resin, the curing catalyst (E) component, and the silane coupling agent (crosslinking aid) (F) component were not blended. And evaluated.
And about the compounding quantity of the electroconductive material which is (D) component, the ratio of 1 weight part with respect to 100 weight part of acrylate ester copolymers which are (A) component, ie, an electroconductive adhesive composition. The total amount (100% by weight) was 1% by weight. The obtained results are shown in Table 1.

[Comparative Example 3]
In Comparative Example 3, as shown in Table 1, with respect to the acrylate ester copolymer as the component (A), the terminal silyl group polymer as the component (B) and the tackifier resin as the component (C) A conductive pressure-sensitive adhesive sheet was prepared and evaluated in the same manner as in Example 1 except that 950 parts by weight of each was blended.
And about the compounding quantity of the electroconductive material which is (D) component, although it was 20 weight part with respect to 100 weight part of acrylic ester copolymer which is (A) component, of conductive adhesive composition The blending amount relative to the total amount (100% by weight) was 1% by weight, which was the same value as in Example 1. The obtained results are shown in Table 1.

[Comparative Example 4]
In Comparative Example 4, as shown in Table 1, the type of the acrylate ester copolymer as the component (A) is changed to ACMO, and the terminal silyl group polymer as the component (B) and the component (C) are used. 950 parts by weight of a certain tackifying resin, 0.95 parts by weight of the curing catalyst as component (E), and 11.4 of the silane coupling agent (crosslinking aid) as component (F) A conductive pressure-sensitive adhesive sheet was prepared and evaluated in the same manner as in Example 1 except that parts by weight were added.
And about the compounding quantity of the electroconductive material which is (D) component, although it was 20.1 weight part with respect to 100 weight part of acrylic ester copolymer which is (A) component, a conductive adhesive composition The blending amount with respect to the total amount (100% by weight) of the product was 1% by weight, which was the same value as in Example 1. The obtained results are shown in Table 1.

[Comparative Example 5]
In Comparative Example 5, as shown in Table 1, the type of the acrylate ester copolymer as the component (A) is changed to an ACMO system, and the terminal silyl group polymer as the component (B) and the component (C) are used. 75 parts by weight of a certain tackifying resin, 0.08 parts by weight of the curing catalyst as component (E), and 0.9 of the silane coupling agent (crosslinking aid) as component (F) A conductive pressure-sensitive adhesive sheet was prepared and evaluated in the same manner as in Example 1 except that parts by weight were added.
And about the compounding quantity of the electroconductive material which is (D) component, although it was 2.5 weight part with respect to 100 weight part of acrylic ester copolymer which is (A) component, a conductive adhesive composition The blending amount with respect to the total amount (100% by weight) of the product was 1% by weight, which was the same value as in Example 1. The obtained results are shown in Table 1.

From Table 1, the electroconductive adhesive sheet of Examples 1-9 had the outstanding electroconductivity and adhesive force.
On the other hand, Comparative Example 1 and Comparative Example 5 in which the blending amount of the urethane polymer of component (B) and the tackifying resin of component (C) were relatively small were insufficient in both conductivity and adhesive strength.
Further, Comparative Example 3 and Comparative Example 4 in which the blending amount of the urethane polymer as the component (B) and the tackifying resin as the component (C) were relatively large were able to obtain a certain level of adhesive strength, but the surface resistivity. Was insufficient.
Moreover, although the comparative example 2 which did not mix | blend the urethane polymer of (B) component and tackifying resin of (C) component was able to obtain a certain amount of adhesive force, the surface resistivity was inadequate.

As described above in detail, according to the conductive pressure-sensitive adhesive composition of the present invention and the conductive pressure-sensitive adhesive sheet using the same, the copolymer derived from the carboxyl group-containing vinyl monomer or the nitrogen-containing vinyl monomer with respect to the urethane polymer. By blending an acrylic copolymer having a part, a tackifier resin and a conductive material, even if the amount of the curing catalyst is small or no curing catalyst is blended, good adhesive strength While maintaining the above, excellent conductivity and the like can be obtained.
Therefore, the conductive adhesive composition of the present invention and the conductive adhesive sheet using the same are expected to be used in various applications such as home appliances, automobiles, and OA equipment.
More specifically, it is expected to be used for laminating resin plates inside electronic devices such as mobile phones and personal computers, and laminating optical recording media, magneto-optical recording media, liquid crystal displays, and touch panel members. Is done.

10: base material, 12, 12a, 12b: conductive adhesive layer, 12 ': coating layer, 18: other adhesive layer, 22: release member, 50: conductive adhesive sheet (single-sided type conductive adhesive sheet) ), 50 ': conductive adhesive sheet with release member (single-sided adhesive sheet), 52: conductive adhesive sheet (double-sided type conductive adhesive sheet), 54: adhesive sheet (conductive double-sided adhesive sheet with different adhesive layers) , 60: adherend, 101: antistatic adhesive tape, 102: backside treatment agent, 103: base material, 104a: conductive material, 104: conductive adhesive layer, 105: electrically insulating adhesive layer

Claims (12)

A conductive pressure-sensitive adhesive composition comprising at least a (meth) acrylic acid ester copolymer as the component (A), a urethane polymer as the component (B), and a tackifier resin as the component (C). ,
With respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), the blending amount of the urethane polymer as the component (B) is set to a value within the range of 80 to 800 parts by weight, C) The amount of the tackifying resin as a component is set to a value within the range of 80 to 800 parts by weight,
And the conductive adhesive composition characterized by containing a conductive material as (D) component.   With respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the (A) component, the blending amount of the conductive material as the (D) component is a value within the range of 0.01 to 100 parts by weight. The conductive pressure-sensitive adhesive composition according to claim 1.   As the monomer component for copolymerizing the (meth) acrylic acid ester copolymer as the component (A), a carboxyl group-containing vinyl monomer is included, and the blending amount of the carboxyl group-containing vinyl monomer is changed to the total monomer component 100. The conductive pressure-sensitive adhesive composition according to claim 1 or 2, wherein the conductive pressure-sensitive adhesive composition has a value within a range of 0.1 to 40% by weight with respect to weight%.   As a monomer component when copolymerizing the (meth) acrylic acid ester copolymer as the component (A), a nitrogen-containing vinyl monomer is included, and the blending amount of the nitrogen-containing vinyl monomer is 100% by weight of the total monomer components. The conductive pressure-sensitive adhesive composition according to claim 1, wherein the conductive pressure-sensitive adhesive composition has a value within a range of 0.1 to 40% by weight.   5. The conductive pressure-sensitive adhesive according to claim 1, wherein the urethane polymer as the component (B) has a weight average molecular weight in the range of 15,000 to 200,000. Composition. The urethane polymer as the component (B) has a polyoxyalkylene structure in the main chain, has a urethane bond and / or a urea bond in a part of the main chain or a side chain, and further has a main chain It is a terminal silyl group polymer which has a hydrolyzable silyl group represented by following General formula (1) at both ends of a chain | strand, The electroconductive adhesive as described in any one of Claims 1-5 characterized by the above-mentioned. Composition.

(In the general formula (1), X ¹ and X ² are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.)   The conductive pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the tackifying resin as the component (C) is a terpene phenol-based resin.   The conductive adhesive composition according to any one of claims 1 to 7, wherein the conductive material as the component (D) is a carbon nanotube. The conductive adhesive composition according to any one of claims 1 to 8, wherein the volume resistivity of the conductive adhesive composition is set to a value less than 1 x 10 ⁵ Ω · cm.   A conductive pressure-sensitive adhesive sheet comprising a conductive pressure-sensitive adhesive layer made of the conductive pressure-sensitive adhesive composition according to any one of claims 1 to 9 on both sides or one side of a substrate. 11. The conductive adhesive sheet according to claim 10, wherein the surface resistivity of the conductive adhesive layer is set to a value less than 1 × 10 ⁶ Ω / □. It is a manufacturing method of the electroconductive adhesive sheet provided with the electroconductive adhesive layer which consists of a bridge | crosslinked electroconductive adhesive composition on both surfaces or one side of a base material, Comprising: The following process (1)-(3) is included. A method for producing a conductive adhesive sheet.
(1) A conductive pressure-sensitive adhesive composition comprising at least a (meth) acrylic acid ester copolymer as the component (A), a urethane polymer as the component (B), and a tackifier resin as the component (C). The value of the urethane polymer as the component (B) is in the range of 80 to 800 parts by weight with respect to 100 parts by weight of the (meth) acrylate copolymer as the component (A). And the amount of the tackifying resin as the component (C) is set to a value within the range of 80 to 800 parts by weight, and the non-crosslinked conductive adhesive composition containing a conductive material as the component (D). Step (2) of preparing a product Step (3) Laminating the uncrosslinked conductive adhesive composition on both sides or one side of the substrate (3) Curing reaction of the uncrosslinked conductive adhesive composition, Is it a cross-linked conductive adhesive composition? Step to having a becomes conductive adhesive layer electrically conductive adhesive sheet