KR101795127B1 - Curable electroconductive adhesive composition, electromagnetic shielding film, electroconductive adhesive film, adhesion method, and circuit board - Google Patents

Abstract

The present invention provides a curable conductive adhesive composition capable of controlling the resin flow and securing the filling property. The present invention relates to a polyurethane resin (A) having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group, an epoxy resin (B) having two or more epoxy groups per molecule , At least one additive (C) selected from the group consisting of a cross-linking agent, a polymerization initiator and a tin-based metal catalyst, and an electrically conductive filler (D). The present invention also relates to a resin composition comprising a polyurethane resin (A ') having a carboxyl group, an epoxy resin (B) having at least two epoxy groups per molecule, and at least one selected from the group consisting of isocyanate compounds, block isocyanate compounds and oxazoline compounds , An additive (C ') of a conductive filler (D), and an electrically conductive filler (D).

Description

FIELD OF THE INVENTION The present invention relates to a curable conductive adhesive composition, an electromagnetic wave shield film, a conductive adhesive film, a bonding method, and a circuit board,

TECHNICAL FIELD The present invention relates to a curable conductive adhesive composition, an electromagnetic wave shield film, a conductive adhesive film, a bonding method, and a circuit board.

Conductive adhesives are often used for the flexible substrate (Patent Documents 1 to 3).

These conductive adhesives can be used for adhesion when the electromagnetic shielding film is connected to a conductor circuit of a flexible substrate or for bonding when a reinforcing plate is connected to a conductor circuit of a flexible substrate in order to impart electromagnetic shielding performance to the metal reinforcing plate .

However, in recent years, from the viewpoint of improving the required properties, improvement of the physical properties of the conductive adhesive composition has been demanded. For example, when the conductor circuit is formed by high-density mounting, the flexible substrate may have irregularities. When an electromagnetic wave shielding film or a reinforcing plate is adhered to such an uneven shape, it is important that the resin flows properly in the hot pressing step for adhering.

Conventional conductive adhesives used when connecting an electromagnetic wave shielding film or a reinforcing plate have difficulty in controlling the resin flow because a resin having good fluidity is used for securing fluidity. On the other hand, in the case of using a resin having a high molecular weight for controlling the resin flow, the embeddability with respect to the openings and rigid flex steps for connection to the ground circuit portion of the flexible substrate is impaired.

Patent Document 4 describes a curable polyurethane polyurea adhesive composition containing a polyurethane polyurea resin, two kinds of epoxy resins and an electrically conductive filler. However, there is no description about the use of such an adhesive composition for bonding a reinforcing plate and a circuit board, and the above-described problems can not be sufficiently solved.

Patent Document 5 describes that an adhesive composition containing a polyurethane polyurea resin and an epoxy resin is used for bonding a reinforcing plate and a flexible substrate. However, it is not described that the adhesive composition is made conductive and the electromagnetic wave shielding performance is maintained in the reinforcing plate.

Japanese Patent Application Laid-Open No. 2007-189091 Japanese Patent Application Laid-Open No. 2009-218443 Japanese Laid-Open Patent Publication No. 2005-317946 Japanese Patent Application Laid-Open No. 2010-143981 International Publication No. 2007/032463

In view of the above, it is an object of the present invention to provide a curable conductive adhesive composition capable of controlling the resin flow and securing the filling property.

The present invention relates to a polyurethane resin (A) having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group, an epoxy resin (B) having two or more epoxy groups per molecule , At least one additive (C) selected from the group consisting of a crosslinking agent, a polymerization initiator and a tin-based metal catalyst, and a conductive filler (D).

The present invention also relates to a polyurethane resin composition comprising a polyurethane resin (A ') having a carboxyl group, an epoxy resin (B) having at least two epoxy groups per molecule, and an isocyanate compound, a block isocyanate compound and an oxazoline compound , One additive (C '), and the conductive filler (D).

It is preferable that at least one of the polyurethane resin (A) and the polyurethane resin (A ') has an acid value of 3 to 100 mgKOH / g. It is preferable that at least one of the polyurethane resin (A) and the polyurethane resin (A ') has a weight average molecular weight of 1,000 to 1,000,000.

The epoxy resin (B) is preferably composed of at least one of an epoxy resin (B1) having an epoxy equivalent of 800 to 10,000 and an epoxy resin (B2) having an epoxy equivalent of 90 to 300.

In this case, it is preferable that the epoxy resin (B1) is a bisphenol type epoxy resin and the epoxy resin (B2) is a novolak type epoxy resin.

The conductive filler (D) is preferably at least one selected from the group consisting of silver powder, silver-coated copper powder and copper powder.

The conductive filler (D) preferably has an average particle diameter of 3 to 50 mu m.

The present invention is also an electromagnetic wave shielding film characterized by laminating a conductive adhesive layer and a protective layer using the above-mentioned curable conductive adhesive composition. The present invention is also an electromagnetic wave shielding film characterized by laminating a conductive adhesive layer, a metal layer and a protective layer using the above-mentioned curable conductive adhesive composition.

It is preferable that the thickness of the conductive adhesive layer of the electromagnetic wave shielding film is 3 to 30 占 퐉.

The present invention is also a circuit board characterized in that it has a conductive adhesive layer formed by the above-described electromagnetic shielding film, and the conductive adhesive layer is connected to a ground circuit of a printed board.

The present invention is also a conductive adhesive film characterized by having an adhesive layer obtained using the above-mentioned curable conductive adhesive composition.

The thickness of the conductive adhesive film is preferably 15 to 100 mu m.

The present invention relates to a process (1) of temporarily adhering a conductive adhesive film to an adherend substrate (X) which is a reinforcing plate or a flexible substrate, and a process for producing a conductive adhesive film And a step (2) of overlapping the adhesive substrate (X) with the adhesive substrate (Y) which is a flexible substrate or a reinforcing plate and thermally pressing the adhesive substrate (X).

The present invention is also a circuit board characterized in that the conductive adhesive layer is formed by the above-mentioned conductive adhesive film, wherein the conductive adhesive layer is a circuit board having at least a portion where a flexible substrate, a conductive adhesive layer and a conductive reinforcing plate are laminated in this order .

The surface of the circuit board other than the reinforcing plate on the surface of the flexible substrate may be covered with an electromagnetic wave shielding film.

The curable conductive adhesive composition of the present invention has excellent performance by appropriately flowing at the time of bonding. As a result, excellent adhesion can be achieved even in a substrate having a concavo-convex shape. In addition, it also has an advantage of being able to secure embeddability.

1 is an example of a circuit board obtained by using the conductive adhesive of the present invention as an electromagnetic wave shielding layer.
2 is an example of a circuit board obtained by using the conductive adhesive of the present invention as an electromagnetic wave shielding layer.
3 is an example of a circuit board obtained by using the conductive adhesive of the present invention as a conductive adhesive film.
4 is a schematic diagram showing a method of measuring a 90 ° steel strength of the embodiment.
5 is an example of a test piece for measuring connection resistance in the embodiment.
6 is a schematic diagram showing a method of measuring the 180 ° strength of steel according to the embodiment.
7 is a schematic diagram showing a state of the resin flow of the embodiment.

Hereinafter, the present invention will be described in detail.

≪ First Embodiment >

The curable conductive adhesive composition of the present invention comprises a polyurethane resin (A) having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, a carbon-carbon unsaturated group bond and an alkoxysilyl group, and a polyurethane resin , At least one additive (C) selected from the group consisting of a crosslinking agent, a polymerization initiator and a tin-based metal catalyst, and an electrically conductive filler (D). Thus, the curing reaction by a plurality of kinds of curing reaction is carried out, and the resin flow has an appropriate flow performance capable of coping with adhesion to a surface having an irregular shape by the action of controlling the resin flow.

(Polyurethane resin (A))

As used herein, the term " polyurethane " means a generic term of polyurethane and polyurethane-urea. The " polyurethane " may be one obtained by reacting an amine component as required.

The polyurethane resin (A) used in the present embodiment has at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group as a reactive functional group. By having such a reactive functional group, it is possible to control the resin flow by the function of controlling the hot rolling temperature in the hot pressing step to be described later.

At least one functional group selected from the group consisting of a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group may be present in the side chain of the polyurethane resin, or may be present in the main chain or may be present as a terminal group.

The polyurethane resin (A) used in the present invention is obtained by reacting a polyol compound (1) containing a carboxyl group, a polyol (2), a short-chain diol compound (3), a polyamine compound (4) And then reacting the polyisocyanate compound (5).

More preferably, the polyurethane resin (A) is obtained by reacting a polyol compound (1) containing a carboxyl group, a polyol (2) and, if necessary, a short chain diol compound (3) and / or a diamine compound Containing group (excluding the carboxyl group of the polyol compound (1)) and the isocyanate group (5) in an equivalent ratio of 0.5 to 1.5.

As a method for introducing a reactive functional group other than a carboxyl group into the polyurethane resin (A) used in the present invention, it is preferable to use a monomer having a reactive functional group to be introduced in the above components (1) to (5) A method of conducting the reaction; A method of reacting a side chain or terminal reactor in a polyurethane resin obtained by using the above-mentioned components (1) to (5) with a compound having a functional group to be introduced.

Specific examples of the carboxyl group-containing polyol compound (1) include dimethylolalkanoic acids such as dimethylolpropanoic acid and dimethylolbutanoic acid; Alkylene oxide low molar adduct of dimethylolalkanoic acid (number-average molecular weight less than 500 by terminal functional group quantitation); ? -Caprolactone adduct of dimethylolalkanoic acid (number-average molecular weight less than 500 determined by terminal functional group determination); Half esters derived from acid anhydrides of dimethylolalkanoic acid and glycerin; A compound obtained by free radical reaction of a monomer having a carboxyl group and an unsaturated bond, and a hydroxyl group of a dimethylol alkanoic acid, a monomer having an unsaturated bond, and the like. Among them, dimethylol propanoic acid and dimethylol alkanoic acid such as dimethylolbutanoic acid are preferred from the viewpoint of easiness of obtaining water, easiness of adjustment of acid value, and the like. The content of the polyol compound (1) in the polyurethane resin (A) is preferably in a range from the viewpoint of both improvement in heat resistance and durability and flexibility and adhesion due to crosslinking of the obtained polyurethane resin (A) with the epoxy resin (B) Respectively. More specifically, the content of the polyol compound (1) in the reaction component is preferably such that the acid value of the obtained polyurethane resin (A) is 3 to 100 mgKOH / g, more preferably 3 to 50 mgKOH / g By weight or more.

The polyol (2) is a component having two or more hydroxyl groups, and preferably has a number average molecular weight of 500 to 3,000. Further, the polyol (2) refers only to the polyol compound (1).

The polyol (2) is not particularly limited, and conventionally known polyols used for urethane synthesis can be used. Specific examples of the polyol (2) include a polyester polyol, a polyether polyol, a polycarbonate polyol and other polyols. Examples of the polyester polyol include aliphatic dicarboxylic acids (e.g., succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.) and / or aromatic dicarboxylic acids (e.g., Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, 1,4-bis hydroxymethylcyclohexane), and the like. Specific examples of such polyester polyols include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, polyneopentyl / hexyl adipate Diol, poly-3-methylpentane adipate diol, polybutylene isophthalate diol, polycaprolactone diol, and poly-3-methylvalerolactone diol.

Specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random / block copolymers thereof. Specific examples of the polycarbonate polyol include polytetramethylene carbonate diol, polypentamethylene carbonate diol, poly neopentyl carbonate diol, polyhexamethylene carbonate diol, poly (1,4-cyclohexanedimethylene carbonate) diol, and random / Block copolymers and the like.

Specific examples of other polyols include dimer diols, polybutadiene polyols and hydrogenated products thereof, polyisoprene polyols and hydrogenated products thereof, acrylic polyols, epoxy polyols, polyether ester polyols, siloxane modified polyols, α, ω-polymethyl methacrylate Diol,?,? - polybutyl methacrylate diol, and the like.

The number average molecular weight (M _n , determined by the terminal functional group amount) of the polyol (2) is not particularly limited, but is preferably 500 to 3,000. When the polyol (2) the number average molecular weight (M _n) is in excess of 3,000, tends to have reduced mechanical properties is more difficult to express the cohesive force of urethane bonds. In addition, the crystalline polyol having a number average molecular weight of more than 3,000 may cause whitening when it is formed into a film. The polyol (2) may be used singly or in combination of two or more.

It is also preferable to use a short-chain diol component (3) and / or a diamine component (4) as necessary as a reaction component for obtaining the polyurethane resin (A). This makes it easy to control the hardness, viscosity and the like of the polyurethane resin (A). Specific examples of the short chain diol component (3) include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, And its alkylene oxide adduct (having a number average molecular weight of less than 500 as determined by terminal functional groups); Alicyclic glycols such as 1,4-bis hydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol, and alkylene oxide adducts thereof (number average molecular weight less than 500, homology); Aromatic glycols such as xylene glycol and alkylene oxide adduct thereof (number average molecular weight less than 500, homology); Bisphenols such as bisphenol A, thiobisphenol, sulfone bisphenol and alkylene oxide adduct thereof (number average molecular weight less than 500, homology); Diallo alkyl, such as C ₁ ~ C ₁₈ alkyl diethanolamine and the like kanol amine.

Specific examples of the diamine compound (4) include short chain aliphatic diamine compounds such as methylene diamine, ethylenediamine, trimethylenediamine, hexamethylenediamine and octamethylenediamine; Phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis (phenylamine), 4,4'-diaminodiphenyl ether, Aromatic diamine compounds such as diaminodiphenylsulfone; And alicyclic diamine compounds such as cyclopentyldiamine, cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane and isophoronediamine. Further, hydrazines such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide can be used as the diamine compound (4). Examples of the long chain include long-chain alkylenediamines, polyoxyalkylene diamines, terminal amine polyamides, and siloxane-modified polyamines. These diamine compounds (4) can be used singly or in combination of two or more.

As the polyisocyanate compound (5), conventionally known polyisocyanates used in the production of polyurethane can be used. Specific examples of the polyisocyanate (5) include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl- Dienes such as 3-phenylenediisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylene bis (phenylene isocyanate) aromatic diisocyanates such as diisocyanate, trididine diisocyanate, xylenediisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzyl; Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate and 1,10-decamethylene diisocyanate; Alicyclic diisocyanates such as 1,4-cyclohexylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI and hydrogenated XDI; And polyurethane prepolymers obtained by reacting these diisocyanates with low molecular weight polyols or polyamines so that the terminals thereof become isocyanates. From the viewpoint of obtaining a polymer composition excellent in weatherability, aliphatic diisocyanate and alicyclic diisocyanate are preferable.

The polyisocyanate compound (5) may have a blocking group at the terminal. That is, an isocyanate terminal may be formed by reacting excess isocyanate group, and end-blocked by reacting the isocyanate terminal with the monofunctional compound.

These functional groups may be introduced by using at least any one of the compounds for introducing a hydroxyl group, the compounds for introducing an unsaturated bond, and the compounds for introducing an alkoxysilyl group during or after the reaction of the respective components described above.

Monoamines having a hydroxyl group and diamines can be used as a compound introducing a hydroxyl group, and monoamines can be obtained by introducing a hydroxyl group into the chain of the polyurethane resin by using diamine at the terminal of the polyurethane resin as a chain elongating agent have. A polyhydric alcohol containing two or more hydroxyl groups in a molecule can also introduce a hydroxyl group into the terminal of the polyurethane resin by reacting an excessive amount with respect to the prepolymer.

Examples of the monoamine having a hydroxyl group include monoethanolamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, N-hydroxyethylpiperazine and the like. As the diamine having a hydroxyl group, Ethanolamine, N-aminoethyl isopropanolamine, and the like. Examples of polyhydric alcohols include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,3-butanediol, N-methylene diethanolamine, triethanolamine, glycerin and trimethylolpropane.

When a hydroxyl group is introduced into the polyurethane resin, the hydroxyl value is preferably 3 to 300 mgKOH / g.

Monools and diols having an unsaturated bond can be used as a compound introducing an unsaturated bond. The monool can be used as a terminal of a polyurethane resin, the diol can be used as a chain extender, an unsaturated bond can be introduced into a chain of a polyurethane resin can do. Specific examples of the monool having an unsaturated bond include allyl alcohol, hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA) (hereinafter, also referred to as " (Meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, and their derivatives such as ethylene oxide, propylene oxide, Examples of the diol include glycerin monoallyl ether, glycerin mono (meth) acrylate, polybutadiene diol (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di , Dimer diol, and the like.

Further, after a carboxyl group-containing polyurethane resin is synthesized, glycidyl (meth) acrylate is added to the polyurethane resin, and the carboxyl group of the polyurethane resin is reacted with the epoxy group of glycidyl (meth) An unsaturated bond may be introduced into the side chain of the urethane resin.

When an unsaturated bond is introduced into the polyurethane resin, it is preferable that the unsaturated bond equivalent is 300 to 10,000 g / eq.

As the compound for introducing an alkoxysilyl group, monoamines having an alkoxysilyl group, diamines, or thiols can be used. Monoamines and thiols can be used at the ends of the polyurethane resin, diamines can be used as chain elongation agents, The alkoxysilyl group can be introduced into the chain of the polymer. Specific examples of the monoamine having an alkoxysilyl group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like. Examples of the diamine include N-2- (amino Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- Examples of the thiol having an alkoxysilyl group include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.

When an alkoxysilyl group is introduced into the polyurethane resin, the amount of the alkoxysilyl group introduced is preferably 0.01 to 10% by weight in terms of silicon atoms in the resin.

The polyol compound (1) having a carboxyl group is reacted with an active hydrogen group such as a polyol (2) and optionally a short chain diol compound (3) and, if necessary, a polyamine compound (4) , The equivalent ratio of the isocyanate group of the polyisocyanate compound (5) is preferably 0.5 to 1.5. Within the above range, a polyurethane resin (A) having high heat resistance and high mechanical strength can be obtained.

(Production method of polyurethane resin (A)) [

The polyurethane resin (A) can be produced by a conventionally known method for producing a polyurethane. Concretely, firstly, a polyol compound (1) containing a carboxyl group, a polyol (2), and a short-chain diol optionally used as a chain extender are reacted in the presence or absence of an organic solvent containing no active hydrogen in the molecule (For example, a prepolymer) by reacting a compound (3), a polyamine compound (4) to be used if necessary, a functional group-introduced component to be used as required, and a reaction component comprising a polyisocyanate (5) .

Generally, the reaction component may be a blend composition in which a prepolymer having a terminal isocyanate group is formed. The reaction may be carried out at 20 to 150 ° C, preferably 60 to 110 ° C, until the theoretical isocyanate percentage is reached by the one-shot method or the multistage method.

The obtained reaction product (prepolymer) may be subjected to chain elongation by reacting the diamine compound (4) so as to have a desired molecular weight, and at the same time, a compound having the above-mentioned functional group may be used to introduce a functional group to be a reaction point. The total active hydrogen-containing group (excluding the carboxyl group of the compound (1)) of the carboxyl group-containing polyol compound (1), polyol (2), short chain diol compound (3), and polyamine compound (4) It is preferable to react the isocyanate group (2) of the isocyanate compound (5) at an equivalent ratio of 0.5 to 1.5.

The weight average molecular weight (M _w) of the polyurethane resin (A) obtained as above is more than the properties such as 1,000 ~ 1,000,000 is preferable, and further 2,000 ~ 1,000,000 in that the flexibility of the polyurethane, the adhesion, heat resistance and coating performance It is preferable to use it effectively.

The properties such as the obtained polyurethane resin (A) The number average molecular weight (M _n) of 400 ~ 450,000 is preferable, and further 850 ~ 450,000 in that the flexibility of the polyurethane, the adhesion, heat resistance, and the coating performance in the manner described above It is preferable to use it more effectively.

Further, it is called "weight-average molecular weight (M _w)" and the "number average molecular weight (M _n)" in the present specification, in particular, not to mention one, the value in terms of polystyrene as measured by gel permeation chromatography (GPC) .

The higher the acid value of the polyurethane resin (A), the higher the crosslinking points and the higher the heat resistance. However, the polyurethane resin (A) having an excessively high acid value is too hard to lower the flexibility, or the carboxyl group may not react completely with the epoxy group and the like and the durability may be lowered. Therefore, the acid value of the polyurethane resin (A) is preferably 3 to 100 mgKOH / g, more preferably 3 to 50 mgKOH / g.

In the present invention, a catalyst may be used as needed in urethane synthesis. For example, salts and organic metal derivatives of metals with organic acids and inorganic acids such as dibutyltin laurate, dioctyltin laurate, stannous octoate, zinc octylate, tetra n-butyl titanate, Organic amines such as ethylamine, and diazabicycloundecene-based catalysts.

The polyurethane resin (A) may be synthesized without using a solvent, or may be synthesized using an organic solvent. As the organic solvent, an organic solvent inert to the isocyanate group or an organic solvent less active than the reaction component relative to the isocyanate group may be used. Specific examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Aromatic hydrocarbon solvents such as toluene, xylene, swazol (trade name, manufactured by Cosmo Sekiyu K.K.) and sorbesso (trade name, manufactured by Ekuson Kagaku Kogyo Co., Ltd.); aliphatic hydrocarbon solvents such as n-hexane; Alcohol solvents such as methanol, ethanol and isopropyl alcohol; Ether solvents such as dioxane and tetrahydrofuran; Ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate; Glycol ether ester type solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate and ethyl-3-ethoxypropionate; Amide solvents such as dimethylformamide and dimethylacetoamide; And lactam-based solvents such as N-methyl-2-pyrrolidone.

When the isocyanate group remains at the terminal of the polymer in the urethane synthesis, it is also preferable to perform the termination reaction of the isocyanate group. The termination reaction of the isocyanate group can be carried out using a compound having reactivity with an isocyanate group. Examples of such compounds include monofunctional compounds such as monoalcohol and monoamine; A compound having two kinds of functional groups having different reactivities with respect to isocyanate can be used. Specific examples of such compounds include monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol; Monoamines such as monoethylamine, n-propylamine, diethylamine, di-n-propylamine and di-n-butylamine; And alkanolamines such as monoethanolamine and diethanolamine. Of these, alkanolamine is preferred because reaction control is easy. In addition, the isocyanate group termination reaction may be performed using the above-mentioned functional group-containing component as a reaction point, and the functional group serving as a reaction point may be introduced to the terminal of the polyurethane molecule.

The effect of the present invention can be obtained by carrying out a crosslinking reaction with an isocyanate crosslinking agent, a block isocyanate crosslinking agent or the like in the polyurethane resin (A) having a hydroxyl group in addition to the carboxyl group.

The isocyanate crosslinking agent may be a buret type, an adduct type, a nourishing type, a prepolymer type and a block body thereof. The mass ratio of the hydroxyl group in the polyurethane resin (A) to the isocyanate crosslinking agent, the block isocyanate crosslinking agent or the like is preferably in the range of 0.5 to 200 parts by mass based on 100 parts by mass of the resin component of the polyurethane resin.

The polyurethane resin (A) having a further unsaturated bond in addition to the carboxyl group can undergo cross-linking reaction between unsaturated bonds by ultraviolet rays or electron beams in the presence or absence of various photopolymerization initiators. The crosslinking reaction may also be carried out by a thermal reaction in the presence of a known polymerization initiator such as peroxide or azo compound.

Further, the polyurethane resin (A) having a further unsaturated bond in addition to the carboxyl group can be subjected to a cross-linking reaction between the unsaturated bonds by using a peroxide as an initiator or oxygen in the presence of a catalyst by a heat treatment.

The polyurethane resin (A) having a further alkoxysilyl group in addition to the carboxyl group is hydrolyzed in the presence or absence of a catalyst, and the silanol groups are condensed with each other to form a siloxane bond. In addition, an isocyanate crosslinking agent, a block isocyanate crosslinking agent, or the like may be used in combination to react with such a crosslinking agent. As the polyisocyanate compound that can be used, those exemplified as the polyisocyanate compounds described above can be used.

These reactions are carried out at room temperature in a treatment at a lower temperature, for example, ultraviolet ray or electron beam crosslinking, as compared with the case where a reaction with an epoxy group and a carboxyl group requires a heat treatment at 130 to 180 ° C for 15 to 90 minutes, The reaction proceeds also in a treatment at a temperature of room temperature to 120 캜, whereby an adhesive layer excellent in workability can be obtained while maintaining adhesiveness and flexibility.

(Epoxy resin (B))

The curable conductive adhesive composition of the present invention also contains an epoxy resin (B).

The epoxy resin (B) to be used is not particularly limited, and any known epoxy resin having two or more epoxy groups per molecule can be used.

More specifically, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a spirocyclic epoxy resin, a naphthalene epoxy resin, a bisphenyl epoxy resin, a terpene epoxy resin , Glycidyl ether type epoxy resins such as tris (glycidyloxyphenyl) methane and tetrakis (glycidyloxyphenyl) ethane, glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, Novolak type epoxy resins such as tetrabromo bisphenol A type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin,? -Naphthol novolak type epoxy resin and brominated phenol novolak type epoxy resin can be used.

More preferably, two kinds of epoxy resins (B) are mixed and used. This is preferable in that balanced physical properties can be obtained. When two kinds of epoxy resins (B) are mixed, different epoxy equivalents of the same kind of epoxy resin (B) may be mixed and used, or other types of epoxy resin (B) may be used in combination.

(Epoxy resin (B1)) having an epoxy equivalent of 800 to 10,000 (epoxy resin (B1)) and an epoxy equivalent of 90 to 300 (epoxy resin (B2)) are used in combination as the two kinds of epoxy resins . In this case, the epoxy resin (B1) and the epoxy resin (B2) may be of the same kind or may have different chemical structures.

As the epoxy resin (B1), an epoxy equivalent of 800 to 10,000 is preferably used. This is preferable in that adhesion with a reinforcing plate or an adherend (Ni-SUS, SUS, gold-plated electrode, polyimide resin, etc.) is further improved. The lower limit of the epoxy equivalent is more preferably 1000, and still more preferably 1500. The upper limit of the epoxy equivalent is more preferably 5000, and still more preferably 3000. As the epoxy resin (B1), it is preferable to use a solid at room temperature. Solid at room temperature means a solid state at 25 ° C that has no fluidity in the absence of solvent.

Examples of commercially available epoxy resins that can be used as the epoxy resin (B1) include EPICLON 4050, 7050, HM-091, HM-101 (trade names, manufactured by DIC Corporation), jER1003F, 1004, 1004AF, 1004FS, 1005F, 1006FS, 1007, 1007FS, 1009, 1009F, 1010, 1055, 1256, 4250, 4275, 4004P, 4005P, 4007P and 4010P (trade names, manufactured by Mitsubishi Kagaku Kogyo K.K.).

The epoxy resin (B2) preferably has an epoxy equivalent of 90 to 300.

Thereby, an effect of increasing the heat resistance of the resin is obtained. The lower limit of the epoxy equivalent is more preferably 150, and still more preferably 170. The upper limit of the epoxy equivalent is more preferably 250, and still more preferably 230. As the epoxy resin (B2), it is preferable to use a solid at room temperature.

It is more preferable that the epoxy resin (B2) is a novolak type epoxy resin. The novolak-type epoxy resin has good compatibility with other epoxy resins, and the difference in reactivity between epoxy groups is small, even though the density of the epoxy resin is high. Therefore, the entire coating film can be made uniformly in high bridge density.

Examples of the novolak-type epoxy resin include, but are not limited to, cresol novolak type epoxy resins, phenol novolak type epoxy resins,? -Naphthol novolak type epoxy resins, and brominated phenol novolak type epoxy resins.

Examples of commercially available epoxy resins usable as the epoxy resin (B2) as described above include EPICLON N-660, N-665, N-670, N-673, N-680, N-695, N-655- EXP-S, N-662-EXP-S, N-665-EXP, N-665-EXP-S, N-672- N-680-75M, N-690-75M, N-740, N-770, N-775, N-740-80M, N-770-70M, N-865, N-865-80M YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN (trade names, manufactured by Mitsubishi Kagaku K. K.), YDPN-638, YDCN-700, YDCN- -700-7, YDCN-700-10, YDCN-704, YDCN-700-A (trade name, manufactured by Shinnitetsu Kagaku Kogyo Co., Ltd.).

When a novolak-type epoxy resin is used as the epoxy resin (B2), the epoxy resin (B1) may be a bisphenol-type epoxy resin which is solid at room temperature. This is because when the novolak type epoxy resin (B2) and the bisphenol type epoxy resin (B1) are used in combination, sufficient adhesion can be obtained.

The curable conductive adhesive composition of the present embodiment preferably contains the epoxy resin (B1) and the epoxy resin (B2) in a weight ratio of 85:15 to 99: 1. By providing the above ratio, it is possible to secure adhesion to a reinforcing plate or an adherend (Ni-SUS, SUS, gold-plated electrode, polyimide resin or the like) and to provide heat resistance capable of enduring the reflow process at component mounting . When the ratio of the epoxy resin (B1) is larger than 99: 1 in the above ratio, it is not preferable from the viewpoint that the reflow step at the time of component mounting may not be able to be endured. When the ratio is large, it is not preferable from the viewpoint of a decrease in adhesion to an adherend (Ni-SUS, SUS, gold-plated electrode, polyimide resin, etc.).

In the present specification, the epoxy equivalent is a value measured by potentiometric titration.

(Mixing ratio of the polyurethane resin (A) and the epoxy resin (B)

In the present embodiment, the mixing ratio of the polyurethane resin (A) and the epoxy resin (B) is preferably 70:30 to 30:70 by mass ratio of the polyurethane resin (A) and the epoxy resin (B). Within the above range, it is preferable that flexibility of the conductive adhesive film or the electromagnetic wave shielding film is imparted, film formability is imparted, and heat resistance is easily adjusted.

(Additive (C))

The curable conductive adhesive composition of the present embodiment can be obtained by adding the additive (C) (for example, a polymerization initiator, a crosslinking agent, a reaction catalyst, etc.) to the curable adhesive composition having further improved durability. In particular, the crosslinking reaction of the polyurethane resin (A) is preferably carried out using an additive (C) capable of reacting with a carboxyl group and a reactive functional group present in the molecule of the polyurethane resin (A). The additive (C) is intended to contribute to the reaction of the carboxyl group and the reactive functional groups present in the molecule of the polyurethane resin (A), but it may also contribute to the reaction of the epoxy resin (B) at the same time.

Examples of the polymerization initiator include organic peroxide-based polymerization initiators such as cumene hydroperoxide and t-butylperoxy-2-ethylhexanoate, aliphatic hydrocarbons such as 2,2'-azobisisobutylnitrile, 2,2'-azobis 4-dimethylvaleronitrile) and the like can be used. As the organic peroxide-based polymerization initiator of the marketed product, parumir H and pacmyr O (manufactured by Nichiyu Kagaku K.K.) were used. As the azo-based polymerization initiator of the marketed product, ABN-R and ABN-V (manufactured by Nippon Pine Chemical Co., Ltd.) .

As the crosslinking agent, conventionally known crosslinking agents such as an isocyanate compound, a block isocyanate compound, a carbodiimide compound, an oxazoline compound, a melamine, and a metal complex system crosslinking agent can be used. Of these crosslinking agents, isocyanate compounds, block isocyanate compounds, carbodiimide compounds and oxazoline compounds are preferred. Examples of commercially available isocyanate compounds that can be used as the crosslinking agent include dyrenate (available from Asahi Chemical Industry Co., Ltd.). Commercially available products of carbodiimide compounds include carbodiLite (manufactured by Nisshinbo Chemical Co., Ltd.). Examples of commercial products of the oxazoline compounds include Epocross (manufactured by Nippon Shokubai Co., Ltd.) and the like.

As the reaction catalyst of the alkoxysilyl group, tin-based metal catalysts such as monobutylstannic acid and stannous octylate can be used. Commercially available products include MBTO and stannot (manufactured by Epi-A Corporation).

These additives (C) are effective in improving heat resistance and durability in an appropriate amount. However, if the amount of the additive (C) to be used is too large, flexibility and weldability may be lowered. Therefore, the amount of the additive (C) to be used is preferably 0.1 to 200 parts by mass or less, more preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the resin component of the polyurethane resin (A).

Among the crosslinking agents of the additive (C), the isocyanate compound (including the block isocyanate compound) is a crosslinking agent generally used for the polyurethane resin, but the polyurethane resin (A) having a hydroxyl group in addition to the carboxyl group reacts with the hydroxyl group It becomes an effective crosslinking agent.

(Conductive filler (D))

The curable conductive adhesive composition of this embodiment contains a conductive filler (D). The conductive filler (D) is not particularly limited, and for example, a metal filler, a metal-coated resin filler, a carbon filler, and a mixture thereof can be used. Examples of the metal filler include copper powder, silver powder, nickel powder, silver coated copper powder, gold coated copper powder, silver coated nickel powder, and gold coated nickel powder, and these metal powders can be produced by an electrolytic method, an atomization method and a reduction method. In particular, it is preferable to use at least one conductive filler (D) selected from the group consisting of silver powder, silver-coated copper powder and copper powder. Moreover, in order to make it easy to obtain contact between the fillers, the average particle diameter of the conductive filler (D) is preferably 3 to 50 mu m. In addition, examples of the shape of the conductive filler (D) include a sphere, a flake, a resin, and a fiber.

The curable conductive adhesive composition may further contain additives such as a silane coupling agent, an antioxidant, a pigment, a dye, a tackifier resin, a plasticizer, an ultraviolet absorber, a defoaming agent, a leveling regulator, a filler and a flame retardant in a range that does not deteriorate solder reflow resistance Maybe.

(Anisotropic conductive adhesive layer, isotropic conductive adhesive layer)

The conductive adhesive layer of the present embodiment may be an anisotropic conductive adhesive layer or an isotropic conductive adhesive layer, and may be any of them depending on the purpose. For example, when used as a conductive adhesive film to be bonded to an electromagnetic wave shielding film or a reinforcing plate which does not have the metal layer described above, an isotropic conductive adhesive layer is preferable. In the case of an electromagnetic wave shielding film having a metal layer, an isotropic conductive adhesive layer may be used, but an anisotropic conductive adhesive layer is preferable.

They may be either an anisotropic conductive adhesive layer or an isotropic conductive adhesive layer depending on the amount of the conductive filler (D). In order to form the anisotropic conductive adhesive layer, it is preferable that the conductive filler is contained in the total solid content of the curable conductive adhesive composition in an amount of 5 wt% or more and less than 40 wt%. In order to form an isotropic conductive adhesive layer, it is preferable that the conductive filler (D) is 40 wt% or more and 90 wt% or less in the total solid content of the curable conductive adhesive composition.

(Electromagnetic wave shield film)

The curable conductive adhesive composition of the present invention may be used as a conductive adhesive layer in an electromagnetic wave shielding film. Such an electromagnetic wave shield film is also one of the present invention.

The electromagnetic wave shielding film of the present invention preferably has a conductive adhesive layer and a protective layer. The conductive adhesive layer is obtained from the curable conductive adhesive composition. The protective layer is not particularly limited and any known layer can be used. As the protective layer, a resin component (except for the conductive filler) used in the above-described conductive adhesive layer may be used.

The thickness of the conductive adhesive layer in the electromagnetic wave shielding film is preferably in the range of 3 to 30 mu m. If the thickness is less than 3 mu m, there is a fear that sufficient connection with the ground circuit is not obtained, and if it exceeds 30 mu m, it is not preferable because it can not meet the demand for thinning.

Next, specific forms of the method for producing an electromagnetic field film of the present invention will be described.

For example, a method of coating and drying a resin composition for a protective layer on one side of a peelable film to form a protective layer, coating and drying the curable conductive adhesive composition on the protective layer, and forming a conductive adhesive layer .

The electromagnetic wave shielding film in the laminated state of the conductive adhesive layer / protective layer / releasable film can be obtained by the manufacturing method as exemplified.

Examples of the method for providing the conductive adhesive layer and the protective layer include a known coating method such as a gravure coating method, a kiss coating method, a die coating method, a lip coating method, a comma coating method, a blade coating method, A coating method, a spray coating method, a bar coating method, a spin coating method, a dip coating method and the like.

The electromagnetic wave shielding film can be adhered to a substrate by a hot press. The conductive adhesive layer is softened by heating and flows into the ground portion from which the insulator layer is removed by pressurization. Thereby, it is electrically connected to the ground circuit.

A circuit board using such a conductive adhesive is shown in Fig. 1, the conductive adhesive layer 3 and the protective layer 1 are formed so as to be in contact with the ground portion 4. The conductive adhesive layer (3) of the present invention has favorable fluidity and therefore has good embeddability and enables good electrical connection at the ground portion (4).

(Electromagnetic wave shielding film having a metal layer)

The electromagnetic wave shielding film of the present invention may have a metal layer. By having a metal layer, more excellent electromagnetic wave shielding performance can be obtained.

Examples of the metal material for forming the metal layer include nickel, copper, silver, tin, gold, palladium, aluminum, chromium, titanium, zinc and alloys containing any two or more of these materials. The metal material and the thickness of the metal layer may be suitably selected in accordance with the required electromagnetic shielding effect and the repeated flexural and sliding resistance. However, the thickness of the metal layer may be about 0.1 탆 to 8 탆. Examples of the method of forming the metal layer include an electrolytic plating method, an electroless plating method, a spattering method, an electron beam evaporation method, a vacuum evaporation method, a CVD method, and a metal organic method. The metal layer may be a metal foil.

The electromagnetic wave shielding film having such a metal layer can be produced by the same method as the above-described electromagnetic wave shielding film, and is preferably composed of a conductive adhesive layer / metal layer / protective layer / peelable film.

A circuit board using an electromagnetic wave shielding film having a metal layer is shown in Fig. 2, the metal layer 2 is electrically connected to the ground portion 4 through the conductive adhesive layer 3 to obtain electromagnetic shielding performance. At that time, the conductive adhesive layer (3) has a satisfactory fluidity, so that the embedding property is good and good electrical connection can be performed in the ground portion (4).

As the adherend capable of adhering the electromagnetic shielding film of the present invention, for example, a flexible substrate subjected to repeated bending can be cited as a representative example. Of course, the present invention is also applicable to a rigid printed wiring board. Further, the present invention is not limited to the single-sided shield, but includes the double-sided shield.

The electromagnetic wave shielding film can be adhered to the substrate by heating and pressing. Such hot pressing under heating and pressing can be carried out under ordinary conditions and can be carried out under the conditions of, for example, 1 to 5 MPa, 140 to 190 DEG C, and 15 to 90 minutes.

(Conductive adhesive film)

The present invention is also a conductive adhesive film having a conductive adhesive layer obtained by using the above-mentioned curable conductive adhesive composition. Such a film can be used to adhere the conductive reinforcing plate and the circuit board main body to give electromagnetic shielding performance to the reinforcing plate.

The conductive adhesive film of the present invention may be a single layer or may be provided with a peelable film and a conductive adhesive layer formed on the surface of the peelable film. The coating method and the drying conditions of the conductive adhesive film of the present invention can be carried out by a known method. The conductive adhesive film of the present invention can be produced by coating a releasable film with a curable conductive adhesive composition to form a conductive adhesive layer. The coating method is not particularly limited, but a coating method used in a method for producing a conductive adhesive layer in the above electromagnetic wave shielding film can be employed.

The releasable film may be a silicone or non-silicone releasing agent coated on a base film such as polyethylene terephthalate or polyethylene naphthalate coated on the surface on which the conductive adhesive layer is formed. In addition, the thickness of the peelable film is not particularly limited, and is determined in consideration of ease of use.

The thickness of the conductive adhesive film is preferably 15 to 100 mu m. With such a thickness, it is preferable that the film is deformed into a shape to fill the concave portion by appropriately flowing when the concavo-convex exists in the base material, so that the film can be adhered with good adhesion.

(Adhesion method)

The conductive adhesive film of the present invention can be used, for example, for bonding a reinforcing plate and a circuit board main body. In particular, when the reinforcing plate is made of metal, it is used not only for bonding the reinforcing plate but also for electrically connecting the ground electrode in the circuit board body. A bonding method in the case of using for such an application will be described in detail below.

The material of the circuit board main body may be any material that has insulating properties and can form an insulating layer, and a representative example thereof is a polyimide resin.

As the reinforcing plate having conductivity, it is preferable to use a metal plate, and as the metal plate, a stainless plate, an iron plate, a copper plate, an aluminum plate, or the like can be used. Of these, stainless steel plates are more preferable. By using a stainless steel plate, even a thin plate thickness has sufficient strength to support the electronic component. The thickness of the conductive reinforcing plate is not particularly limited, but is preferably 0.025 to 2 mm, more preferably 0.1 to 0.5 mm. When the conductive reinforcing plate is within this range, it is possible to carry out the embedding in a small appliance without difficulty and has sufficient strength to support the mounted electronic component.

Examples of the electronic components include chip components such as resistors, capacitors, and camera modules in addition to connectors and ICs.

In the bonding of the present invention, the step (1) of temporarily adhering the above-mentioned conductive adhesive film onto the adherend substrate (X) which is a reinforcing plate or a flexible substrate, and a step (1) of bonding the conductive adhesive film A step (2) of overlapping a substrate (X) with a substrate (Y) which is a flexible substrate or a reinforcing plate and hot pressing.

The above-mentioned conductive adhesive film can be preferably used particularly for bonding a flexible substrate to a reinforcing plate. That is, as described in Patent Document 3, a conductive material such as a metal plate is used as a reinforcing plate, and the reinforcing plate is bonded to the flexible substrate with a conductive adhesive film to obtain electromagnetic shielding performance by the reinforcing plate.

The conductive adhesive film of the present invention has a particularly excellent effect in that good adhesion performance is obtained when the reinforcing plate is bonded by such a method. That is, even when the temporarily adhered adhesive is stored for a certain period of time and then the original adhesive is applied by hot pressing, an appropriate curing reaction proceeds during storage, so that the adhesive performance of the present adhesive does not deteriorate. In addition, even when the flexible substrate has a step, it is possible to obtain a high degree of adhesion without forming a gap by appropriately flowing the resin because of the appropriate fluidity.

In the bonding method of the present invention, first, the conductive adhesive film is temporarily adhered to the adherend substrate (X). The adherend substrate X may be either a reinforcing plate or a flexible substrate, but is preferably a reinforcing plate. The conditions for temporary bonding are not particularly limited, and it is preferable that the conductive adhesive film is fixed on an adherend substrate so as to be adhered without shifting. That is, it is preferable to temporarily adhere to the entire surface of the adhesive surface.

The temporary adhering can be performed by, for example, a press machine (condition temperature: 120 DEG C, pressure: 0.5 MPa, time: 5 seconds).

The adhesive substrate X to which the conductive adhesive film is temporarily adhered by the above-described step (1) may be provided immediately after the step (2), and it may be stored for about one week before being provided to the step (2) It is good. The conductive adhesive composition of the present invention is preferable in this respect since the adhesive performance is not lowered even after partially curing.

Step (2) is a step of overlapping the adhesive substrate (X) having the conductive adhesive film obtained by the step (1) and the adhesive substrate (Y) as a reinforcing plate and performing hot pressing. In addition, one of the adherend substrate X and the adherend substrate Y is a reinforcing plate and the other is a flexible substrate.

The hot press can be carried out under ordinary conditions and can be carried out under the conditions of, for example, 1 to 5 MPa, 140 to 190 DEG C, and 15 to 90 minutes.

(Circuit board)

The circuit board of the present invention is a circuit board having at least a part where a flexible substrate, a conductive adhesive film and a conductive reinforcing plate are stacked in this order. Such a circuit board may be bonded by the above-described bonding method, or may be obtained by other bonding methods. Fig. 3 shows a schematic view of such a circuit board. In Fig. 3, the circuit board and the reinforcing plate 5 are bonded by the conductive adhesive film of the present invention, and are electrically connected.

In the above circuit board, it is preferable that the conductive reinforcing plate exists only in a part of the circuit board. That is, it is preferable to have a reinforcing plate in a portion having an electronic component.

The circuit board of the present invention may be a circuit board in which a reinforcing plate is bonded to a substrate by the above-described conductive adhesive of the present invention, and the portion where the reinforcing plate is not provided is covered with an electromagnetic wave shielding film. Such a circuit board is also one of the present invention. The electromagnetic wave shielding film used herein may be the above-described electromagnetic wave shielding film of the present invention, but the present invention is not limited thereto, and a known electromagnetic wave shielding film may be used. The electromagnetic wave shield film is preferably connected to a ground circuit (not shown).

≪ Second Embodiment >

In this embodiment, the configuration of the polyurethane resin (A ') and the additive (C') is different from that of the first embodiment, and the other structures are the same as those of the first embodiment. Therefore, description of the same configuration as that of the first embodiment will be omitted.

(Polyurethane resin (A '))

The polyurethane resin (A ') used in the present embodiment has a carboxyl group. By having such a reactive functional group, the resin flow can be controlled by the action that the hot rolling temperature becomes controllable.

The polyurethane resin (A ') used in the present embodiment is obtained by reacting a polyol compound (1) containing a carboxyl group, a polyol (2), a short-chain diol compound (3) And a polyisocyanate compound (5).

More preferably, the polyurethane resin (A ') comprises a polyol compound (1) containing a carboxyl group, a polyol (2), a short chain diol compound (3) and / or an amine compound Is obtained by reacting an active hydrogen-containing group (excluding the carboxyl group of the polyol compound (1)) with an isocyanate group of the polyisocyanate compound (5) in an equivalent ratio of 0.5 to 1.5. As the compounds (1) to (5), those exemplified in the first embodiment are preferably used.

(Method for producing polyurethane resin (A '))

The polyurethane resin (A ') of the present embodiment can be produced by a conventionally known method for producing a polyurethane. Concretely, a polyol compound (1) containing a carboxyl group, a polyol (2), and a short-chain diol optionally used as a chain extender are reacted in the presence or absence of an organic solvent containing no active hydrogen in the molecule A reaction product (for example, a polyurethane resin or a prepolymer) is obtained by reacting a reaction component composed of a compound (3), a polyamine compound (4) used as required, and a polyisocyanate compound (5). The prepolymer generally has a composition in which a prepolymer having a terminal isocyanate group is formed. The reaction may be carried out by a one-shot method or a multistage method usually at 20 to 150 ° C, preferably 60 to 110 ° C until theoretical isocyanate percentage is reached.

The obtained reaction product (prepolymer) may be chain elongated so as to have a desired molecular weight by reacting the diamine compound (4), if necessary. The total active hydrogen-containing group (excluding the carboxyl group of the compound (1)) of the carboxyl group-containing polyol compound (1), polyol (2), short chain diol compound (3) and polyamine compound (4) and polyisocyanate compound (5) is preferably reacted at an equivalent ratio of 0.5 to 1.5.

The weight average molecular weight of the polyurethane resin obtained as described above (M _w) of 1,000 ~ 1,000,000 in that it is preferable, also exhibit more effectively the characteristics, such as 2,000 ~ 1,000,000 in that the flexibility of the polyurethane, the adhesion, heat resistance and coating performance This is more preferable. In addition, "weight-average molecular weight (M _w)" in this specification and the "number average molecular weight (M _n)" is, unless otherwise specified, it means a value in terms of polystyrene as measured by gel permeation chromatography (GPC) do.

The higher the acid value of the urethane resin, the higher the crosslinking point and the higher the heat resistance. However, the urethane resin having an excessively high acid value tends to be too hard to lower the flexibility, or may not react completely with the epoxy resin, the curing agent, etc., and the durability may be lowered. For this reason, the acid value of the urethane resin is preferably 3 to 100 mgKOH / g, more preferably 3 to 50 mgKOH / g.

In the present embodiment, a catalyst may be used as needed for urethane synthesis. For example, salts of metals such as dibutyltin laurate, dioctyltin laurate, stannas octoate, zinc octylate and tetra n-butyl titanate with organic acids and inorganic acids, and organic metal derivatives, such as triethylamine Organic amines, diazabicycloundecene-based catalysts, and the like.

The polyurethane resin may be synthesized without using a solvent, or may be synthesized using an organic solvent. As the organic solvent, an organic solvent inert to the isocyanate group or an organic solvent less active than the reaction component relative to the isocyanate group may be used. Specific examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Aromatic hydrocarbon solvents such as toluene, xylene, swazol (trade name, manufactured by Cosmo Sekiyu K.K.) and sorbesso (trade name, manufactured by Ekuson Kagaku Kogyo Co., Ltd.); aliphatic hydrocarbon solvents such as n-hexane; Alcohol solvents such as methanol, ethanol and isopropyl alcohol; Ether solvents such as dioxane and tetrahydrofuran; Ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate; Glycol ether ester type solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate and ethyl-3-ethoxypropionate; Amide solvents such as dimethylformamide and dimethylacetoamide; And lactam-based solvents such as N-methyl-2-pyrrolidone.

When the isocyanate group remains at the terminal of the polymer in the urethane synthesis, it is also preferable to perform the termination reaction of the isocyanate group. The termination reaction of the isocyanate group can be carried out using a compound having reactivity with an isocyanate group. Examples of such a compound include monofunctional compounds such as monoalcohol and monoamine; A compound having two kinds of functional groups having different reactivities with respect to isocyanate can be used. Specific examples of such a compound include monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol.

(Additive (C '))

The additive (C ') of the present embodiment is a compound which does not correspond to the polyurethane resin (A') or the epoxy resin (B) described above and is a compound having a functional group participating in the curing reaction of the curable conductive adhesive composition of the present embodiment Lt; / RTI > In particular, it is preferable that a carboxyl group in the polyurethane resin (A ') and a hydroxyl group in the epoxy resin (B) can react with each other in view of improvement in heat resistance and adhesion.

The compound that can be used as such an additive (C ') is not particularly limited, and examples thereof include conventionally known additives such as an isocyanate compound, a block isocyanate compound, a carbodiimide compound, an oxazoline compound, a melamine, Can be used. Among these additives, an isocyanate compound, a block isocyanate compound, a carbodiimide compound, and an oxazoline compound are preferable. These are compounds having two or more reactive groups such as an isocyanate group, a block isocyanate group, a carbodiimide group, and an oxazoline group. Examples of commercially available isocyanate compounds usable as additives include dyrenate (manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like. Commercially available products of carbodiimide compounds include carbodiite (manufactured by Nisshinbo Chemical Industries, Ltd.) and the like. Examples of commercial products of the oxazoline compounds include Epocross (manufactured by Nippon Shokubai Co., Ltd.) and the like. Two or more of these compounds may be used in combination.

Examples of the isocyanate compound include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, Butylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylene bis (phenylene isocyanate) (MDI), duylene diisocyanate, tri Aromatic diisocyanates such as xylylene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate and 4,4'-diisocyanate dibenzyl; Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate and 1,10-decamethylene diisocyanate; Alicyclic diisocyanates such as 1,4-cyclohexylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI and hydrogenated XDI; And polyurethane prepolymers obtained by reacting these diisocyanates with low molecular weight polyols or polyamines so as to be isocyanates at the ends. The isocyanate compounds may be isocyanurate, burette, adduct, polymer Known isocyanate group having a polyfunctional isocyanate group can be used and is not particularly limited.

As the above-mentioned block isocyanate compound, a compound obtained by blocking the isocyanate compound of the above-mentioned isocyanate compound by a known method can be used. The blocking compound is not particularly limited, and phenol compounds such as phenol, cresol, xylenol, chlorophenol and ethylene phenol; lactam systems such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propiolactam; Active methylenes such as ethyl acetoacetate and acetylacetone; Butanol, isobutanol, t-butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono 2-ethylhexyl ether, propylene Alcohols such as glycol monomethyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate, and furfuryl alcohol; Oxime compounds such as formaldehyde, formaldehyde, acetaldehyde, acetoxime, methylethylketooxime, diacetylmonooxime and cyclohexaneoxime; Mercaptan systems such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol and ethylthiophenol; Acid amides such as acetic acid amide and benzamide; Imide systems such as succinic acid imide and maleic acid imide; Imidazole compounds such as imidazole and 2-ethylimidazole; Secondary amines such as dimethylamine, diethylamine and dibutylamine; And pyrazole such as pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

The carbodiimide compound is not particularly limited, and examples thereof include those obtained by the decarbonation condensation reaction of the above-mentioned isocyanate compound.

The oxazoline compound is not particularly limited and includes, for example, 2,2'-bis- (2-oxazoline), 2,2'-methylene-bis- Bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4- , 2,2 '- (1,3-phenylene) -bis- (4,4-dimethyl-2-oxazoline) , 2,2 '- (1,4-phenylene) -bis- (2- oxazoline), bis- (2-oxazolinylcyclohexane) sulfide, bis- (2-oxazolinylnorbornane) Dioxazoline compounds such as sulfide; Trioxazoline compounds such as 2,2 '- (1,2,4-phenylene) -tris- (2-oxazoline); And oxazoline group-containing polymers such as styrene / 2-isopropenyl-2-oxazoline copolymer.

Further, it is preferable that the additive (C ') is not an aziridine compound. That is, the aziridine compound is preferably not used because it is positive for mutagenicity (Ames).

The amount of the additive (C ') to be used is preferably 0.1 to 200 parts by mass or less, more preferably 0.2 to 100 parts by mass based on 100 parts by mass of the resin component of the polyurethane resin (A'). Within the above range, it is preferable that the adjustment of the heat resistance is facilitated.

The curable conductive adhesive composition according to the second embodiment can also be used in an electromagnetic wave shielding film, a circuit board and a bonding method in the same manner as in the first embodiment.

Example

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, " part " and "% " are based on mass unless otherwise specified.

≪ First Embodiment >

[Synthesis Example A-1: carboxyl group-containing polyurethane resin (double bond introduction)]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 6.0 g of dimethylolpropionic acid (DMPA), 6.0 g of polyhexamethylene carbonate diol (trade name " Fraxel CD220 ", manufactured by Dicer GmbH, number average molecular weight 2000 ), 12.0 g of glycerin monomethacrylate (trade name " Brena GLM ", Niche-like agent, molecular weight 160) and 75.0 g of dimethylformamide (DMF). Subsequently, 57.0 g of hexamethylene diisocyanate (HDI) (equivalent to 2 times the NCO group with respect to the OH group) was added and the reaction was carried out at 90 占 폚 until the NCO value of the resin became 5.7%, which is theoretical value, to obtain a urethane prepolymer solution. To the obtained urethane prepolymer solution, 400.5 g of DMF was added, and after cooling to 40 캜, 28.8 g of isophoronediamine (IPDA) was added dropwise to react with the NCO group of the urethane prepolymer. (A-1) having an acid value of 12.3 mgKOH / g and a double bond equivalent of 2700 g / eq, as measured by infrared absorption spectrometry until absorption at 2,270 cm ^-1 by the free isocyanate group was lost. DMF solution (solid concentration 30%).

[Synthesis Example A-2: carboxyl group-containing polyurethane resin (hydroxyl group introduction)]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 6.0 g of DMPA, 100 g of CD220 and 59.1 g of DMF were added. Subsequently, 31.8 g of HDI (2 equivalents of NCO group with respect to the OH group) was added, and the reaction was carried out at 90 占 폚 until the NCO group of the resin became 4.0% as the theoretical value to obtain a urethane prepolymer solution. To the resultant urethane prepolymer solution, 285.3 g of DMF was added, and after cooling to 40 캜, 9.8 g of N- (aminoethyl) ethanolamine was added dropwise to react with the NCO group of the urethane prepolymer. (A-2) having an acid value of 17.0 mgKOH / g and a hydroxyl value of 35.8 mgKOH / g, until absorption of 2,270 cm ^-1 by the free isocyanate group, as measured by infrared absorption spectrum analysis, Of DMF solution (solid concentration 30%).

[Synthesis Example A-3: carboxyl group-containing polyurethane resin (methoxysilyl group introduction)]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 6.0 g of DMPA, 100 g of CD220 and 59.1 g of DMF were added. Subsequently, 31.8 g of HDI (2 equivalents of NCO group with respect to the OH group) was added, and the reaction was carried out at 90 占 폚 until the NCO group of the resin became 4.0% as the theoretical value to obtain a urethane prepolymer solution. To the obtained urethane prepolymer solution, 311.4 g of DMF was added and the mixture was cooled to 40 캜. N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (trade name: KBM-603, manufactured by Shin- Were added dropwise, and reacted with the NCO group of the urethane prepolymer. (A-3) having an acid value of 15.8 mgKOH / g and a silicon content of 1.7% by weight until the absorption of 2,270 cm ^-1 by the free isocyanate group disappears, as measured by infrared absorption spectrum analysis, Solution (solid concentration 30%).

[Comparative Synthesis Example A-4: carboxyl group-free polyurethane resin]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 4.0 g of 1,4-butanediol, 100 g of CD220 and 58.2 g of DMF were added. Subsequently, 31.7 g of HDI (2 equivalents of NCO group with respect to the OH group) was added, and the reaction was carried out at 90 占 폚 until the NCO group of the resin became 4.1%, which is the theoretical value, to obtain a urethane prepolymer solution. 295.8 g of DMF was added to the obtained urethane prepolymer solution, and after cooling to 40 캜, 16.0 g of IPDA was added dropwise to react with the NCO group of the urethane prepolymer. (DMF solution (solid content concentration: 30%) of a polyurethane resin (A-4) containing no carboxyl group was obtained by stirring until the absorption of 2,270 cm ^-1 by the free isocyanate group, as measured by infrared absorption spectrum analysis, disappeared .

[Comparative Synthesis Example A-5: carboxyl group-containing polyurethane resin]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 6.0 g of DMPA, 100 g of CD220 and 59.0 g of DMF were added. Subsequently, 31.9 g of HDI (2 equivalents of NCO group with respect to the OH group) was added, and the reaction was carried out at 90 占 폚 until the NCO group of the resin became 4.0%, which is theoretical, to obtain a urethane prepolymer solution. To the obtained urethane prepolymer solution, 298.5 g of DMF was added, and after cooling to 40 캜, 16.1 g of IPDA was added dropwise to react with the NCO group of the urethane prepolymer. G of a polyurethane resin (A-5) having an acid value of 16.4 mgKOH / g (solid content concentration: 30%) was stirred until absorption of 2,270 cm ^-1 by a free isocyanate group, as measured by infrared absorption spectrum analysis, ).

Table 1 below shows the raw material blending ratio of each resin obtained by the above and the characteristic values of the resin.

Blenmer GLM: Niceth-like glycerin monomethacrylate

KBM-603: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co.,

Average molecular weight: GPC measurement, polystyrene conversion

The number average molecular weight and the weight average molecular weight in Table 1 are values measured under the following conditions.

1) Device Apparatus: HLC-8020 (manufactured by Tosoh Corporation)

2) Column (manufacturer, column name): (TSKgel G2000HXL, G3000HXL, G4000GXL)

3) Solvent: THF

4) Flow rate: 1.0 ml / min

5) Sample concentration: 2 g / l

6) Injection amount: 100 μl

7) Temperature: 40 ° C

8) Detector: RI-8020

Standard substance: TSK standard polystyrene (manufactured by Tosoh Corporation)

(Electromagnetic wave shield film)

The releasable film coated with the releasing agent was coated with a protective layer resin and dried to form a protective layer having a thickness of 5 탆. On the other hand, each material was blended as shown in Table 2 to prepare a curable conductive adhesive composition. The curable conductive adhesive composition was hand-coated on the protective layer using a doctor blade (plate-shaped knife), and dried at 100 占 폚 for 3 minutes to prepare a conductive adhesive layer. In addition, the doctor blade appropriately selects 1 miI to 5 miI products depending on the thickness of the conductive adhesive layer to be manufactured. Also, 1 miI = 1/1000 inch = 25.4 占 퐉. In each of the Examples and Comparative Examples, the conductive adhesive layer was formed so as to have a predetermined thickness. The thicknesses of the protective layer and the conductive adhesive layer are measured by micrometers.

The epoxy resins shown in Table 2 were used in Table 2. The same also applies to the following tables.

As the conductive filler in Table 2, the following were used.

Conductive filler D-1: silver powder (average particle diameter 5 탆, Fukuda Ginzoku Co., Ltd.)

Conductive filler D-2: Silver-coated copper alloy (average particle diameter 12 占 퐉, manufactured by Fukuda Kikkun Co., Ltd.)

Conductive filler D-3: silver-coated copper alloy (average particle diameter: 18 탆, manufactured by Fukuda Kikkun Co., Ltd.)

As the additives in Table 2, the following were used.

Additive C-1: Pakumil H (manufactured by Nichiyu K.K.)

Additive C-2: Dyuranate 24A-100 (manufactured by Asahi Chemical Industry Co., Ltd.)

Additive C-3: Stannot (manufactured by Epi-A Corporation)

The obtained electromagnetic wave shielding film was evaluated based on the following evaluation criteria. The results are shown in Table 4.

(180 ° peel strength)

6, the conductive adhesive layer side of the electromagnetic wave shielding film 27 was bonded to a test plate (width: 10 mm, thickness: 10 mm) via a polyimide film 26 (CAPTON 100H (trade name) Length 100 mm), and the polyimide film 26 (the same capton 100H) was adhered to the protective layer side with the adhesive layer interposed therebetween, and peeled off from the polyimide film at 50 mm / min. The average value of the number of tests is n = 5. If it is 3 N / cm or more, it can be used without any problem.

(Connection resistance value)

The electromagnetic wave shielding film was placed on a flexible substrate simulating a ground having an opening diameter of 1.0 mm in diameter and 37.5 mu m in step size and heated at 170 DEG C for 30 minutes under pressure at a pressure of 3 MPa to prepare an evaluation sample, The connection resistance was measured. If it is 1Ω or less, the electromagnetic shielding performance can be ensured.

(Reflow resistance)

Evaluation after reflow was carried out. As a temperature condition of reflow, a temperature profile of 265 캜 at the maximum was set on the assumption of lead-free solder. A test piece of a circuit board with a metal reinforcing plate pressed between a conductive adhesive film and a reinforcing plate was passed through an IR reflow five times and the presence or absence of swelling was observed.

From the results shown in Table 4, it is clear that the electromagnetic shielding film of the present invention is excellent in workability, and the wiring board obtained by using the electromagnetic shielding film has good embeddability and good properties.

(Electromagnetic wave shielding film having a metal thin film layer)

The releasable film coated with the releasing agent was coated with a protective layer resin and dried to form a protective layer having a thickness of 5 탆. A silver thin film layer of about 0.1 탆 was formed on the protective layer by vacuum deposition. Each material was compounded as shown in Table 5 to prepare a curable conductive adhesive composition. This was hand-coated on the metal thin film layer using a doctor blade (plate-shaped knife), and dried at 100 占 폚 for 3 minutes to prepare a conductive adhesive layer. In addition, the doctor blade appropriately selects 1 miI to 5 miI products depending on the thickness of the conductive adhesive layer to be manufactured. Also, 1 miI = 1/1000 inch = 25.4 占 퐉. In each of the Examples and Comparative Examples, the conductive adhesive layer had a predetermined thickness. The thicknesses of the protective layer and the conductive adhesive layer are measured by micrometers.

As the conductive filler in Table 5, the same materials as those used in Table 2 were used.

Evaluation was carried out by the same evaluation method as that of the electromagnetic shielding film having no metal thin film layer described above, and the results are shown in Table 6. < tb > < TABLE >

From the results shown in Table 6, it is clear that the electromagnetic shielding film of the present invention is excellent in workability and the wiring board obtained using the electromagnetic shielding film has good properties.

(Method for producing conductive adhesive film)

The conductive adhesive films of the respective examples and comparative examples will be described. Each material was compounded as shown in Table 7 to prepare a curable conductive adhesive composition. This was hand-coated on a polyethylene terephthalate film subjected to release treatment using a doctor blade (plate-type applicator), and dried at 100 ° C for 3 minutes to produce a conductive adhesive film. Also, the doctor blade appropriately selects 1 miI to 5 miI products depending on the thickness of the conductive adhesive film to be produced. Also, 1 miI = 1/1000 inch = 25.4 占 퐉. In each of the Examples and Comparative Examples, the conductive adhesive film was formed so as to have a predetermined thickness. The thickness of the conductive adhesive film is measured by a micrometer.

As the conductive filler in Table 7, the following were used.

Conductive filler D-4: silver powder (average particle diameter: 12 탆, Fukuda Ginzoku Kogyo K.K.)

Conductive filler D-5: silver-coated copper alloy (average particle diameter: 20 탆, Fukuda Ginzoku Kogyo K.K.)

Conductive filler D-6: silver-coated copper alloy (average particle diameter 25 m, Fukuda Ginzoku Kogyo K.K.)

The obtained conductive adhesive film was evaluated based on the following evaluation criteria.

(Peel strength)

The adhesion to the reinforcing plate was measured using a 90 ° peel test. Specifically, as shown in Fig. 4, a stainless steel plate 24 (10 mm in width, 100 mm in length) and the surface of the polyimide layer in the copper-clad laminate 22, 23 having a copper- And the copper clad laminate was peeled off in the vertical direction after press bonding as described in the method of using the conductive adhesive film of the above embodiment with the conductive adhesive film 21 of this embodiment interposed therebetween. If it is 10 N / cm or more, it can be used without any problem.

(Connection resistance value)

Electrical evaluation was performed on the circuit board on which the metal plate 5 fabricated by the above method was attached. When the conductive adhesive film was pressed between the reinforcing plate and a flexible substrate simulating a ground having a diameter of 1.0 mm and a step of 37.5 占 퐉, the connection resistance of the circuit board with the metal reinforcing plate (8)) was measured. If it is 1? Or less, it is judged that the shielding performance is secured and the embeddability is good.

(Reflow resistance)

Evaluation after reflow was carried out. As a temperature condition of reflow, a temperature profile of 265 캜 at the maximum was set on the assumption of lead-free solder. A test piece of a circuit board with a metal reinforcing plate pressed between a conductive adhesive film and a reinforcing plate was passed through an IR reflow five times to observe whether or not it swelled up.

(Resin flow)

Resin flow distance was measured on the circuit board having the metal reinforcing plate manufactured by the above method. When the circuit board with the manufactured metal reinforcing plate was observed from the side of the reinforcing plate, the distance between the conductive adhesive and the reinforcing plate was measured. If it is 300 μm or less, it can be used without problems (see FIG. 7).

Table 8 shows the evaluation results of the obtained functional films.

≪ Second Embodiment >

A curable conductive adhesive composition was prepared in the same manner as in the first embodiment except that the polyurethane resin (A ') and the additive (C') were used instead of the polyurethane resin (A) and the additive (C) . Unless otherwise specified, various measurement conditions and evaluation conditions are the same as those in the first embodiment.

(Polyurethane resin (A '))

[Synthesis Example A'-1: carboxyl group-containing polyurethane (with urea bond)]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 6.0 g of dimethylol propionic acid (DMPA), 100 g of polyhexamethylene carbonate diol (trade name " Fraxel CD220 ", number average molecular weight 2000 determined by terminal functional group determination) 59.1 g of formamide (DMF) are added. Subsequently, 31.8 g of hexamethylene diisocyanate (HDI) (equivalent to 2 times the NCO group with respect to the OH group) was added and the reaction was carried out at 90 ° C until the NCO value of the resin became 4.0%, which is the theoretical value, to obtain a urethane prepolymer solution. 300.0 g of DMF was added to the resulting urethane prepolymer solution, and after cooling to 40 캜, 16.1 g of isophoronediamine (IPDA) was added dropwise to react with the NCO group of the urethane prepolymer. Stirred until the, free isocyanate groups by absorption of 2,270㎝ ^-1 as measured by infrared absorption spectrum analysis to be lost, and an acid value of 16.3 DMF solution of ㎎KOH / g the polyurethane resin (A'-1) of the (solid content concentration: 30 %).

[Synthesis Example A'-2: carboxyl group-containing polyurethane (without urea bond)]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 6.0 g of DMPA, 6.0 g of 1,4-butanediol, 100 g of Fraxel CD220 and 139.1 g of DMF were added. Then, 27.1 g of HDI (equivalent to the NCO group with respect to the OH group) was added and stirred at 90 DEG C until absorption of 2,270 cm < ^-1 > by the free isocyanate group measured by infrared absorption spectroscopy disappeared. 185.5 g of DMF And a DMF solution (solid concentration 30%) of a polyurethane resin (A'-2) having an acid value of 18.1 mgKOH / g was obtained. It was confirmed by the infrared absorption spectrum that the polyurethane resin (d2) had no urea bond.

[Synthesis Example A'-3: carboxyl group-containing polyurethane (with urea bond)]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 6.0 g of DMPA, 100 g of Fraxel CD220 and 70.8 g of DMF were added. Subsequently, 42.1 g of isophorone diisocyanate (IPDI) (equivalent to 2 times the NCO group with respect to the OH group) was added, and the reaction was carried out at 90 DEG C until the NCO group of the resin became 4.0% as a theoretical value to obtain a urethane prepolymer solution . To the resulting urethane prepolymer solution, 312.3 g of DMF was added, and after cooling to 40 캜, 16.1 g of IPDA was added dropwise to react with the NCO group of the urethane prepolymer. (A'-3) having an acid value of 16.3 mgKOH / g (solids concentration 30 (mass%)) of the polyurethane resin (A'-3), which was measured by infrared absorption spectrum analysis until the absorption of 2,270 cm ^-1 by the free isocyanate group disappeared, %).

[Comparative Synthesis Example A'-4: No carboxyl group]

A reaction vessel equipped with a stirrer, a reflux condenser tube, a thermometer, a nitrogen atomizer tube and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 4.0 g of 1,4-butanediol, 100 g of CD220 and 58.2 g of DMF were added. Subsequently, 31.7 g of HDI (2 equivalents of NCO group with respect to the OH group) was added, and the reaction was carried out at 90 占 폚 until the NCO group of the resin became 4.1%, which is a theoretical value, to obtain a urethane prepolymer solution. To the resulting urethane prepolymer solution, 295.8 g of DMF was added, and after cooling to 40 캜, 16.0 g of IPDA was added dropwise to react with the NCO group of the urethane prepolymer. The mixture was stirred until the absorption of 2,270 cm ^-1 by the free isocyanate group, which was measured by infrared absorption spectrum analysis, disappeared, and a DMF solution (solid content concentration: 30%) of the carboxyl group-free polyurethane resin (A'- .

The composition of the obtained polyurethane resin is shown in Table 9.

(Electromagnetic wave shield film)

An electromagnetic wave shielding film was produced in the same manner as in the production method of the electromagnetic wave shielding film of the first embodiment except that the mixing ratio of each material of the conductive adhesive composition was changed to that shown in Table 10.

The epoxy resins shown in Table 10 were used in Table 10. The same is true in the following table.

As the crosslinking agent in Table 10, the following were used.

Cross-linking agent C'-1: carbodiimide compound; Carbodite V-07 (manufactured by Nisshinbo Chemical Co., Ltd.)

Cross-linking agent C'-2: oxazoline compound; Epocross RPS-1005 (available from Nippon Shokubai Co., Ltd.)

Cross-linker C'-3: isocyanate compound; Dyuranate 24A-1000 (manufactured by Asahi Kasei Chemicals Co., Ltd.)

Cross-linker C'-4: Block isocyanate compound; Dyuranate 17B-60PX (manufactured by Asahi Kasei Chemicals Co., Ltd.)

As the conductive filler in Table 10, the following were used.

Conductive filler D-1: silver powder (average particle diameter 5 탆, Fukuda Ginzoku Kogyo K.K.)

Conductive filler D-2: Silver-coated copper alloy (average particle diameter 12 占 퐉, Fukuda Ginzoku Kogyo K.K.)

Conductive filler D-3: silver-coated copper alloy (average particle diameter 18 탆, Fukuda Ginzoku Kogyo K.K.)

The thus obtained electromagnetic shielding film was evaluated on the basis of the same evaluation criteria as those of the first embodiment, with respect to the 180 degree of brass strength, connection resistance value and bottom flowability. The results are shown in Table 12.

From the results of Table 12, it can be seen that the electromagnetic shielding film of the present embodiment is excellent in workability, and the wiring board obtained by using the electromagnetic shielding film has good embeddability and good properties.

(Electromagnetic wave shielding film having a metal thin film layer)

An electromagnetic wave shielding film having a metal thin film layer was obtained by the same method as that of the electromagnetic shielding film having the metal thin film layer in the first embodiment except that the combination of each material of the curable conductive adhesive composition was changed to that shown in Table 13 .

The crosslinking agent and conductive filler in Table 13 were the same as those in Table 10.

Evaluation was carried out by the same evaluation method as that of the electromagnetic wave shielding film having no metal thin film layer described above. Table 14 shows the results.

From the results of Table 14, it is clear that the electromagnetic shielding film of this embodiment has excellent workability and the wiring board obtained by using the electromagnetic shielding film has good properties.

(Method for producing conductive adhesive film)

A conductive adhesive film was produced in the same manner as in the production of the conductive adhesive film in the first embodiment except that the combination of each material of the curable conductive adhesive composition is shown in Table 15. [

The additives shown in Table 15 were the same as those used in Table 13.

As the conductive filler in Table 15, the following were used.

Conductive filler D-4: Silver powder (average particle diameter 12 占 퐉, Fukuda Ginzoku Kogyo)

Conductive filler D-5: silver-coated copper alloy (average particle diameter: 20 탆, Fukuda Ginzoku Kogyo)

Conductive filler D-6: silver-coated copper alloy (average particle diameter 25 mu m, Fukuda Ginzoku Kogyo)

The bond strength, connection resistance value, underflow property and resin flow of the obtained conductive adhesive film were evaluated based on the same evaluation criteria as in the first embodiment.

Table 16 shows the evaluation results of the obtained functional films.

(Industrial availability)

The curable conductive adhesive composition of the present invention can be particularly preferably used particularly in the field of bonding a metal reinforcing plate to a flexible substrate or an electromagnetic wave shielding film.

1: protective layer 2: metal layer
3: conductive adhesive layer 4: ground portion (Ni-Au electroless plating treatment)
5: Steel sheet (made of Ni-SUS) 6: Coverlay film
7. Copper-clad laminate 8: Electrode (Ni-Au electroless plating treatment)
9: Connection resistance measuring part 13: Resin flow
21: conductive adhesive film 22, 23: copper clad laminate
24: Stainless steel plate 26: Polyimide film
27: electromagnetic wave shield film

Claims (17)

At least one functional group selected from the group consisting of a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group; And a polyurethane resin (A) having a carboxyl group,
An epoxy resin (B) having two or more epoxy groups per molecule,
At least one additive (C) selected from the group consisting of a crosslinking agent, a polymerization initiator and a tin-based metal catalyst, and
, And a conductive filler (D). The method according to claim 1,
The epoxy resin (B)
An epoxy resin (B1) having an epoxy equivalent of 800 to 10000 and
And an epoxy resin (B2) having an epoxy equivalent of 90 to 300. The curable conductive adhesive composition according to claim 1, A polyurethane resin (A ') having a carboxyl group,
An epoxy resin (B) having two or more epoxy groups per molecule,
At least one additive (C ') selected from the group consisting of an isocyanate compound, a block isocyanate compound and an oxazoline compound, and
And a conductive filler (D)
The epoxy resin (B) contains an epoxy resin (B1) having an epoxy equivalent of 800 to 10,000 and an epoxy resin (B2) having an epoxy equivalent of 90 to 300,
The mixing ratio of the polyurethane resin (A ') and the epoxy resin (B) is 70:30 to 30:70 by mass ratio of the polyurethane resin (A') and the epoxy resin (B)
Wherein the additive (C ') is 0.1 to 200 parts by mass based on 100 parts by mass of the resin component of the polyurethane resin (A'). 4. The method according to any one of claims 1 to 3,
Wherein at least one of the polyurethane resin (A) and the polyurethane resin (A ') has an acid value of 3 to 100 mgKOH / g. 4. The method according to any one of claims 1 to 3,
Wherein at least one of the polyurethane resin (A) and the polyurethane resin (A ') has a weight average molecular weight of 1,000 to 1,000,000. The method according to claim 2 or 3,
The epoxy resin (B1) is a bisphenol type epoxy resin,
Wherein the epoxy resin (B2) is a novolak type epoxy resin. 4. The method according to any one of claims 1 to 3,
The conductive filler (D) is at least one selected from the group consisting of silver powder, silver-coated copper powder and copper powder. 4. The method according to any one of claims 1 to 3,
The conductive filler (D) has an average particle diameter of 3 to 50 mu m. An electromagnetic wave shielding film characterized by laminating a conductive adhesive layer using the curable conductive adhesive composition according to any one of claims 1 to 3 and a protective layer. An electromagnetic shielding film characterized by laminating a conductive adhesive layer, a metal layer, and a protective layer using the curable conductive adhesive composition according to any one of claims 1 to 3 in this order. 10. The method of claim 9,
Wherein the thickness of the conductive adhesive layer is 3 to 30 占 퐉. The circuit board according to claim 9, wherein the conductive adhesive layer of the electromagnetic shielding film is connected to the ground of the printed circuit board by heating and pressing. A conductive adhesive film characterized by having a conductive adhesive layer obtained by using the curable conductive adhesive composition according to any one of claims 1 to 3. 14. The method of claim 13,
Wherein the thickness of the conductive adhesive layer is 15 to 100 占 퐉. (1) of temporarily adhering the conductive adhesive film according to claim 13 onto an adherend substrate (X) which is a reinforcing plate or a flexible substrate and a step of adhering an adherend substrate (X) having the conductive adhesive film obtained by the step (2) of laminating an adhesive substrate (Y) which is a flexible substrate or a reinforcing plate to the substrate (1) and hot pressing the substrate (Y). A circuit board having at least a portion where a flexible substrate, a conductive adhesive layer, and a conductive reinforcing plate are stacked in this order,
Wherein the conductive adhesive layer is formed by the conductive adhesive film according to claim 13. 17. The method of claim 16,
Characterized in that the surface of the flexible substrate other than the reinforcing plate is covered with an electromagnetic wave shielding film.

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