KR20170005787A - Curable composition, electroconductive material, and connection structure - Google Patents

Abstract

Provided is a curable composition capable of enhancing adhesiveness of a member to be connected. The curable composition according to the present invention is a curable composition comprising a first compound obtained by a reaction between a compound represented by the following formula (11) and a diol compound, and a second compound having an isocyanate group and an unsaturated double bond And at least one of a thermosetting agent and a photo-curing initiator. In the formula (11), X represents an alkylene group or a phenylene group having 2 to 10 carbon atoms, and R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable composition, a conductive material, and a connection structure,

The present invention relates to a curable composition having excellent adhesiveness. The present invention also relates to a conductive material and a connection structure using the curable composition.

Curable compositions containing a curable compound are widely used in various applications such as electricity, electronics, construction, and vehicles.

As an example of the curable composition, Patent Document 1 below discloses a curable composition comprising (A) a specific phenoxy resin, (B) an inorganic filler, and (C) a silane coupling agent. The content of the silane coupling agent (C) is 1% by mass or more and 10% by mass or less with respect to the entire curable composition.

Conductive particles may be blended in the curable composition. The curable composition containing conductive particles is called an anisotropic conductive material. The anisotropic conductive material is used for connecting various connection target members to obtain various connection structures.

For example, the anisotropic conductive material can be used as a material for the connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass), a connection between a semiconductor chip and a flexible printed circuit (COF (Chip on Film) (COG (Chip on Glass)), and connection of a flexible printed board and a glass epoxy board (FOB (Film on Board)).

Recently, the use of electronic devices equipped with touch panels is increasing. For example, touch panels are used in electronic devices such as cellular phones, smart phones, car navigation systems, and personal computers. In a touch panel or the like, a polyethylene terephthalate (PET) film may be used as a member to be connected. Specifically, in a touch panel, a PET film in which a silver electrode or the like is formed around a flexible printed substrate may be bonded by a curable composition. Recently, the market size of connection structures using PET films is expanding.

As an example of the anisotropic conductive material, Patent Document 2 discloses an anisotropic conductive material comprising a curing agent that generates free radicals by heating, a hydroxyl group-containing resin having a molecular weight of 10,000 or more, a phosphoric acid ester, a radical polymerizable material, (Curable composition) is disclosed. Specific examples of the hydroxyl group-containing resin include polymers such as polyvinyl butyral resin, polyvinyl formal, polyamide, polyester, phenol resin, epoxy resin and phenoxy resin.

Japanese Patent Application Laid-Open No. 2013-23503 Japanese Patent Application Laid-Open No. 2005-314696

In conventional curable compositions as described in Patent Documents 1 and 2, there is a problem that adhesiveness of a member to be connected is low. Particularly, in the conventional curable composition, there is a problem that the PET film is easily peeled off when the PET film is adhered.

It is an object of the present invention to provide a curable composition which can increase the adhesiveness of members to be connected, and to provide a conductive material and a connection structure using the curable composition.

It is a further object of the present invention to provide a curable composition capable of improving adhesion of a PET film and capable of suppressing peeling of a PET film even when a PET film is adhered, To provide a connection structure. Also, the curable composition according to the present invention is suitably used for bonding PET film, but the use of the curable composition according to the present invention is not limited to adhesion of PET film.

According to a broad aspect of the present invention, there is provided a process for producing a second compound having an isocyanate group and an unsaturated double bond by using a first compound obtained by a reaction between a compound represented by the following formula (11) And a thermosetting agent are provided.

In the formula (11), X represents an alkylene group or a phenylene group having 2 to 10 carbon atoms, and R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In a specific aspect of the curable composition according to the present invention, the compound represented by the formula (11) is a compound represented by the following formula (11A).

In the formula (11A), R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In a specific aspect of the curable composition according to the present invention, the compound represented by the formula (11) is terephthalic acid, terephthalic acid alkyl ester, isophthalic acid or isophthalic acid alkyl ester.

In a specific aspect of the curable composition according to the present invention, the diol compound comprises 1,6-hexanediol, and in another specific aspect, the diol compound comprises bisphenol A or bisphenol F, and in another specific aspect, The diol compound includes 1,6-hexanediol and bisphenol A or bisphenol F.

In a specific aspect of the curable composition according to the present invention, the second compound has a (meth) acryloyl group as a group containing an unsaturated double bond, and in another specific aspect, the second compound is a Butyloxy oxy isocyanate.

In a specific aspect of the curable composition according to the present invention, the curable compound has a weight average molecular weight of 8000 to 50,000.

The curable composition preferably contains a quaternary ammonium salt compound or a (meth) acrylic compound having a hydroxyl group. The curable composition preferably contains the quaternary ammonium salt compound. The curable composition preferably contains a (meth) acrylic compound having a hydroxyl group.

In a specific aspect of the curable composition according to the present invention, the thermosetting agent is a thermal radical generator.

In a specific aspect of the curable composition according to the present invention, the cured product obtained by curing the curable composition at 140 캜 and 10 seconds has a breaking elongation of 500% or more.

The curable composition according to the present invention is suitably used for bonding a polyethylene terephthalate film and is preferably a curable composition for bonding a polyethylene terephthalate film. The curable composition according to the present invention is suitably used for adhesion of a polyethylene terephthalate film in a touch panel and is preferably a curable composition for bonding a polyethylene terephthalate film in a touch panel.

According to a broad aspect of the present invention, there is provided a curable composition comprising a curable compound represented by the following formula (1) and a thermosetting agent.

R 1 and R 2 are each a hydrogen atom or a methyl group, R 3 and R 4 are each a hydrogen atom, a methyl group or a phenyl group, X is an alkylene group or a polyether group having 2 to 10 carbon atoms, Y is N1 and n2 each represent 1 or 2, and m represents an integer in which the weight average molecular weight of the curable compound represented by the formula (1) is 8000 or more and 50000 or less .

According to a broad aspect of the present invention, there is provided a conductive material comprising the above-described curable composition and conductive particles.

In a specific aspect of the conductive material according to the present invention, the content of the curable compound is 50% by weight or more.

In a specific aspect of the conductive material according to the present invention, the conductive particles have solder on the conductive outer surface.

According to a broad aspect of the present invention, there is provided a communication device including a first connection object member, a second connection object member, and a connection portion connecting the first connection object member and the second connection object member, Wherein the connecting structure is formed by curing the curable composition.

In a specific aspect of the connection structure according to the present invention, the first connection target member has the first electrode on the surface, the second connection target member has the second electrode on the surface, and the first electrode and the second The electrodes are electrically connected by contact.

According to a broad aspect of the present invention, there is provided a liquid crystal display device including a first connection target member having a first electrode on a surface thereof, a second connection target member having a second electrode on a surface thereof, And the connection portion is formed by curing the above-described conductive material, and the first electrode and the second electrode are electrically connected by the conductive particles.

The curable composition according to the present invention comprises a curable compound and a thermosetting agent, wherein the curable compound is a first compound obtained by a reaction between a compound represented by the formula (11) and a diol compound, Is reacted with a second compound having an isocyanate group and an unsaturated double bond, the adhesiveness of the member to be connected can be enhanced.

Since the curable composition according to the present invention contains the curable compound represented by the formula (1) and a heat curing agent, the adhesion of the member to be connected can be enhanced.

1 is a front sectional view schematically showing a connection structure obtained by using a conductive material including a curable composition and conductive particles according to a first embodiment of the present invention.
2 is a front sectional view schematically showing a connection structure obtained by using the curable composition according to the second embodiment of the present invention.
3 is a front sectional view schematically showing a connection structure obtained using the curable composition according to the third embodiment of the present invention.
Fig. 4 is a front cross-sectional view schematically showing an enlarged connection portion between the conductive particles and the electrode in the connection structure shown in Fig. 1. Fig.
5 is a cross-sectional view showing an example of conductive particles usable in the conductive material used in the first embodiment of the present invention.
6 is a cross-sectional view showing a modified example of the conductive particle.
7 is a cross-sectional view showing another modification of the conductive particle.

Hereinafter, the details of the present invention will be described.

(Curable composition)

The curable composition according to the present invention is a curable composition comprising a first compound obtained by a reaction between a compound represented by the following formula (11) and a diol compound, and a second compound having an isocyanate group and an unsaturated double bond And a curing compound which is obtained by reacting a curing compound. By the reaction for obtaining the curable compound, for example, the curable compound represented by the formula (1) can be obtained. The curable composition according to the present invention comprises a thermosetting agent for curing the curable compound.

In the formula (11), X represents an alkylene group or a phenylene group having 2 to 10 carbon atoms, and R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The curable composition according to the present invention preferably contains a curable compound represented by the following formula (1). The curable compound represented by the formula (1) can be obtained by, for example, using a first compound obtained by a reaction between a compound represented by the formula (11) and a diol compound, and adding an isocyanate group and an unsaturated double bond Or a method of reacting a second compound having a functional group represented by the formula The curable composition according to the present invention comprises a thermosetting agent for curing the curable compound.

R 1 and R 2 are each a hydrogen atom or a methyl group, R 3 and R 4 are each a hydrogen atom, a methyl group or a phenyl group, X is an alkylene group or a polyether group having 2 to 10 carbon atoms, Y is N1 and n2 each represent 1 or 2, and m represents an integer in which the weight average molecular weight of the curable compound represented by the formula (1) is 8000 or more and 50000 or less .

In the curable composition according to the present invention, since the above-mentioned composition is adopted, the adhesiveness of the member to be connected can be enhanced. This is thought to be due to the fact that the curable compound has a skeletal structure with suitable flexibility.

Further, since the above-mentioned composition is employed in the curable composition according to the present invention, the adhesion of the polyethylene terephthalate (PET) film can be enhanced, especially due to the structure of the curable compound. This is considered to be because the curable compound has not only a skeleton structure having suitable flexibility but also a structure similar to that of PET.

In the curable composition according to the present invention, particularly, the effect of improving the adhesiveness of the PET film is largely obtained, but the adhesiveness of other members to be connected can also be improved.

Further, when the connection target member is connected using the curable composition according to the present invention, the resulting connection structure is less prone to peeling even when exposed to high temperature or high humidity.

The curable composition includes the thermosetting agent. By curing the curable composition by heating, adhesiveness of the member to be connected is enhanced. The curable composition does not contain or contain the photocurable initiator. From the standpoint of suppressing excessive flow of the curable composition by curing by irradiation of light and then curing by heating, it is preferable that the curable composition includes the photocurable initiator. On the other hand, from the viewpoint of increasing the rate of curing by heating to further increase the adhesiveness of the member to be connected, the curable composition may not contain the photo-curing initiator. If the photocuring initiator is not used, only the heating can be performed without light irradiation for curing the curable composition, so that the manufacturing efficiency of the connection structure is enhanced.

The cured product obtained by curing the curable composition at 140 캜 for 10 seconds has a breaking elongation of preferably 500% or more, and more preferably 700% or more. The cured composition contained in the conductive material to be described later, when cured at 140 占 폚 for 10 seconds, preferably has a breaking elongation of 500% or more, and more preferably 700% or more. When the breaking elongation is equal to or lower than the lower limit, the adhesiveness of the member to be connected is further increased, and in particular, the adhesion of the PET film can be further enhanced. As the curable composition contained in the conductive material in the measurement of the elongation at break, a curable composition (a mixture of the respective components other than the conductive particles) used for compounding the conductive material may be used, or conductive particles The curable composition may be used.

The breaking elongation is a value of the elongation of the chuck when the cured product is broken when the cured product is stretched under conditions of 23 ° C and a tensile speed of 1 mm / min and a chuck distance of 40 mm using a tensile tester.

In order to further increase the adhesiveness, the curable composition according to the present invention preferably contains a quaternary ammonium salt compound or a (meth) acrylic compound having a hydroxyl group. In order to effectively increase the adhesiveness in this case, the curable composition according to the present invention may contain both the quaternary ammonium salt compound and the (meth) acrylic compound having the hydroxyl group. In order to further increase the adhesiveness and to suppress the peeling at a high temperature, the curable composition according to the present invention preferably contains the quaternary ammonium salt compound. In order to further increase the adhesiveness, the curable composition according to the present invention preferably contains a (meth) acrylic compound having a hydroxyl group.

Hereinafter, details of each component usable in the curable composition according to the present invention will be described.

[Curable compound]

The curable compound is obtained by reacting a first compound obtained by the reaction of a compound represented by the formula (11) with a diol compound and then reacting the first compound with a second compound having an isocyanate group and an unsaturated double bond Loses. The reaction is a dehydration condensation reaction or a deberalcohol reaction. The compound represented by the formula (11) may be used singly or two or more of them may be used in combination. The diol compound may be used alone, or two or more thereof may be used in combination. In order to obtain the curable compound, only one kind of the first compound may be used, or two or more kinds of the first compounds may be used in combination. In order to obtain the curable compound, only one kind of the second compound may be used, or two or more kinds of the second compounds may be used in combination.

The weight average molecular weight of the curable compound is preferably 8000 or more, more preferably 10000 or more, preferably 50000 or less, more preferably 30000 or less. When the weight average molecular weight is not lower than the lower limit, the adhesiveness of the member to be connected is further increased. When the weight average molecular weight is not more than the upper limit, compatibility with other components of the curable compound is enhanced.

The weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). The weight average molecular weight can be measured by "Prominence GPC system" manufactured by Shimadzu Corporation, solvent THF, flow rate 1 ml / min, and detector: differential refraction.

R1 and R2 in the formula (11) each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 1 and R 2 in the formula (11) may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

X is preferably a phenylene group in view of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesion of the PET film, and the compound represented by the formula (11) Is preferably a compound represented by the following formula (11A). From the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesiveness of the PET film, the curable composition can be obtained by reacting the first compound obtained by the reaction of the compound represented by the following formula (11A) , And a curing compound obtained by reacting the first compound with a second compound having an isocyanate group and an unsaturated double bond.

In the formula (11A), R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

From the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesion of the PET film, the compound represented by the formula (11) is terephthalic acid, terephthalic acid alkyl ester, isophthalic acid or isophthalic acid alkyl ester desirable. That is, the compound represented by the formula (11) is preferably a compound represented by the following formula (11AA) or the following formula (11AB).

In the formula (11AA), R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula (11AB), R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

When R1 and R2 in the formulas (11), (11A), (11AA) and (11AB) are each an alkyl group having 1 to 4 carbon atoms, the number of carbon atoms of the alkyl group is , Preferably 3 or less, more preferably 2 or less (methyl group or ethyl group), and more preferably 1 (methyl group).

Examples of the diol compound for obtaining the first compound include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol .

In a specific aspect of the curable composition according to the present invention, the curable composition preferably contains a third compound obtained by reacting a compound represented by the following formula (11B) with a diol compound. The compound represented by the following formula (11B) is a dicarboxylic acid or a dicarboxylic acid ester. The reaction is a dehydration condensation reaction or a deberalcohol reaction. In a specific aspect of the curable composition according to the present invention, the curable composition is obtained by reacting a first compound obtained by the reaction of the compound represented by the formula (11A) with a diol compound, and adding an isocyanate group And a second compound having an unsaturated double bond are reacted with a curing compound obtained by reacting a compound represented by the following formula (11B) with a diol compound to obtain a second compound having an isocyanate group And a curing compound obtained by reacting a fourth compound having an unsaturated double bond (the same as the second compound), or a compound represented by the formula (11A) and a compound represented by the formula (11B) , The isocyanate group and the unsaturated 2 < RTI ID = 0.0 > Preferably it contains a curable compound obtained by reacting the sixth compound (the second compound and the same kind) having a coupling. By using these two kinds of curable compounds, the adhesion of the member to be connected can be effectively enhanced, and in particular, the adhesion of the PET film can be effectively increased.

R1OOC-X-COOR2 ... Equation (11B)

In the formula (11B), R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an alkylene group having 2 to 10 carbon atoms.

The first compound and the third compound may be synthesized and mixed respectively, or the third compound may be reacted with the compound represented by the formula (11A) at the time of the reaction. It is preferable to react with the compound represented by the formula (11A) at the time of the reaction.

More preferred examples of the compound represented by the formula (11B) include compounds wherein R 1 and R 2 represent a hydrogen atom or a methyl group, and X represents an alkylene group having 3 to 5 carbon atoms. More preferable compounds include R 1 and R 2 Represents a methyl group, and X represents an alkylene group having 4 carbon atoms.

The diol compound for obtaining the first compound is preferably a compound represented by the following formula (12), a compound represented by the following formula (12), a A polyester polyol compound or a polyether polyol compound, and more preferably a compound represented by the following formula (12) or a polyether polyol compound. From the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesiveness of the PET film, the diol compound for obtaining the first compound preferably contains a compound represented by the following formula (12) Do.

In the formula (12), R represents an alkylene group or a polyether group having 2 to 10 carbon atoms. In the formula (12), R may represent an alkylene group having 2 to 10 carbon atoms. Examples of R in the formula (12) include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene. The carbon number of R in the formula (12) is preferably 6 from the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesion of the PET film. That is, the compound represented by the formula (12) is preferably a compound represented by the following formula (12A). That is, it is particularly preferable that the diol compound for obtaining the first compound and the diol compound for obtaining the third compound include 1,6-hexanediol.

It is preferable that the second compound has a (meth) acryloyl group as a group containing an unsaturated double bond from the viewpoint of further enhancing the adhesion of the member to be connected and further enhancing the adhesion of the PET film in particular .

Examples of the diol compound for obtaining the first compound include bisphenol A, bisphenol F, and the like. From the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesion of the PET film, it is preferable that the diol compound includes bisphenol A or bisphenol F. From the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesiveness of the PET film, it is preferable that the diol compound includes 1,6-hexanediol and bisphenol A or bisphenol F. In this preferred form, only bisphenol A may be used, only bisphenol F may be used, and bisphenol A and bisphenol F may be used in combination.

Examples of the diol compounds include polyether polyol compounds. As the polyether polyol, propylene glycol and bifunctional alkylene glycol such as ethylene glycol are preferable. The molecular weight of the polyether polyol compound is preferably 500 or more, more preferably 600 or more, preferably 2000 or less, more preferably 1500 or less.

As the diol compound, a polyester polyol compound is also exemplified. The polyester polyol compound is obtained by dehydration condensation of a carboxylic acid and a polyhydric alcohol. As the carboxylic acid, adipic acid and phthalic acid are preferable. As polyhydric alcohols, ethylene glycol, 1,4-butanediol, and 1,6-hexanediol are preferable. The molecular weight of the polyester polyol compound is preferably 500 or more, more preferably 600 or more, preferably 2000 or less, more preferably 1,500 or less.

The diol compound can be reacted with the compound represented by the formula (11A) or the compound represented by the formula (11B), and the compound represented by the formula (11B) ≪ / RTI >

The content of the compound represented by the formula (12) or 1,6-hexanediol in 100 wt% of the diol compound for obtaining the first compound is preferably 0 wt% (unused) or more, More preferably not less than 10% by weight, more preferably not less than 20% by weight, preferably not more than 100% by weight (total amount), more preferably not more than 80% by weight. The content of bisphenol A and bisphenol F in 100 wt% of the diol compound for obtaining the first compound is preferably 0 wt% (unused) or more, more preferably 20 wt% or more, and preferably 100 wt% (Total amount), more preferably not more than 80 wt%.

The second compound is not particularly limited as long as it has an isocyanate group and an unsaturated double bond. Specific examples of the second compound include (meth) acryloyloxyalkyloxy isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate and 2- (2-isocyanatoethyloxy) ethyl methacrylate .

It is preferable that the second compound is at least one member selected from the group consisting of (meth) acryloyloxyalkyloxyisocyanate, 2- (2-isocyanatoethyl Oxy) ethyl methacrylate, and more preferably 2- (2-isocyanatoethyloxy) ethyl methacrylate.

The curable compound represented by the formula (1) can be obtained by, for example, using a first compound obtained by a reaction between a compound represented by the formula (11) and a diol compound, and adding an isocyanate group and an unsaturated double A method in which a second compound having a bond is reacted, or the like. In this case, the compound represented by the formula (11), the diol compound, the second reactant and the like are appropriately selected so as to obtain the curable compound represented by the formula (1). The curable compound represented by the formula (1) can be obtained by, for example, using a first compound obtained by a reaction between a compound represented by the formula (11) and a diol compound, and adding an isocyanate group and an unsaturated double May be obtained by a method other than a method of reacting a second compound having a bond.

X in the above formula (1) is preferably an alkylene group, and is preferably a polyether group. The curable compound represented by the above formula (1) preferably contains an alkylene group as X in the above formula (1), and preferably contains a polyether group.

Examples of the alkylene group represented by X in the above formula (1) include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene or decylene. From the viewpoint of enhancing flexibility, a hexylene group is preferable.

The polyether group represented by X in the formula (1) includes a polyether group represented by the following formula (2).

- (R3-O) q- (2)

In the formula (2), R3 is a straight chain alkylene group having 1 to 6 carbon atoms, and q is an integer in which the weight average molecular weight of the curable compound represented by the formula (1) is 8000 or more and 50000 or less. The molecular weight of q in the formula (2) is preferably 650 or more, more preferably 1000 or more, and preferably 2,000 or less. From the viewpoint of enhancing flexibility, when R3 in the formula (2) is a straight chain alkylene group, the carbon number of R3 is preferably 2 or more, and preferably 4 or less. The plural -R 3 -O- groups may be the same or different.

From the viewpoint of further lowering the glass transition temperature of the cured product and further sufficiently lowering the tensile elastic modulus at low temperature and further curing at a low temperature, the curable compound represented by the formula (1) , It is preferable that X has a polyether group. The connection structure may be exposed under low temperature. By lowering the tensile elastic modulus at low temperature, the flexibility of the cured product at low temperature is increased, and further less peeling at low temperatures is difficult to occur.

The proportion of the polyether group structure moiety (for example, the proportion of the moiety represented by formula (2)) in 100 wt% of the curable compound represented by the formula (1) is preferably at least 17 wt% By weight is not more than 41% by weight, more preferably not more than 23% by weight.

Y in the formula (1) represents an alkylene group or a phenylene group having 2 to 10 carbon atoms. The plural Ys may be the same or different. From the viewpoint of enhancing the acid resistance, the curable compound represented by the above formula (1) preferably has both of an alkylene group having 2 to 10 carbon atoms and a phenyl group as Y in the formula (1). From the viewpoint of enhancing flexibility, it is preferable that the curable compound represented by the formula (1) has a butylene group as Y in the formula (1). When Y in the formula (1) is a phenylene group, examples of Y include a group represented by the following formula (3A) or the following formula (3B). The curable compound represented by the formula (1) is preferably Y in the formula (1) and has a group represented by the following formula (3A).

[Thermal curing agent]

Examples of the heat curing agent for thermally curing the curing compound include an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, an acid anhydride, a thermal cationic initiator, and a heat radical generator. The thermosetting agent may be used alone or in combination of two or more.

Among them, an imidazole curing agent, a polythiol curing agent or an amine curing agent is preferable because the curable composition can be cured at a lower temperature even more quickly. In addition, when the heat curing agent is mixed with the curable compound which can be cured by heating, the storage stability becomes high, and thus a latent curing agent is preferable. The latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent or a latent amine curing agent. The thermosetting agent may be coated with a high molecular substance such as a polyurethane resin or a polyester resin.

From the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesiveness of the PET film, the thermosetting agent is preferably a heat radical generator. By the use of the heat radical generator, in particular, the adhesion of the PET film is effectively increased.

The one-minute half-life decomposition temperature of the thermal radical generator is preferably 100 占 폚 or higher, more preferably 110 占 폚 or higher, preferably 150 占 폚 or lower, more preferably 130 占 폚 or lower. When the 1-minute half-life temperature is not lower than the lower limit, the storage stability of the composition is further improved. If the one-minute half-life temperature is not more than the upper limit, the PET film as the adherend is hardly deformed or deteriorated by the temperature at the time of curing.

The imidazole curing agent is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl- Imidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl -s- triazine and 2,4- diamino- -Methylimidazolyl- (1 ')] - ethyl-s-triazine isocyanuric acid adduct.

The polythiol curing agent is not particularly limited, and trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate and dipentaerythritol hexa-3-mercaptopropionate And the like.

The amine curing agent is not particularly limited and examples thereof include hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetaspiro [5.5] undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.

Examples of the thermal cationic curing agent include an iodonium-based cationic curing agent, an oxonium-based cationic curing agent, and a sulfonium-based cationic curing agent. Examples of the iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate and the like. Examples of the oxonium-based cation curing agent include trimethyloxonium tetrafluoroborate and the like. Examples of the sulfonium cation-based curing agent include tri-p-tolylsulfonium hexafluorophosphate and the like.

The thermal radical generator is not particularly limited, and examples thereof include azo compounds and organic peroxides. The thermal radical generator may be used alone or in combination of two or more.

Examples of the azo compound include azo compounds such as 2,2'-azobisisobutyronitrile, 1,1 '- (cyclohexane-1-carbonitrile), 2,2'-azobis (2-cyclopropylpropionitrile) , 2'-azobis (2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis (2-methylpropionate).

Examples of the organic peroxide include hydroperoxides and dialkyl peroxides. Examples of the hydroperoxide include diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide and tert-butyl hydroperoxide. . Examples of the dialkyl peroxide include α, α'-bis (tert-butylperoxy-m-isopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert- butylperoxy) , tert-butylcumylperoxide, di-tert-butylperoxide and 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3.

The content of the thermosetting agent is not particularly limited. The content of each of the thermosetting agent and the heat radical generator is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, and preferably 200 parts by weight or less, more preferably 100 parts by weight or less Is not more than 100 parts by weight, more preferably not more than 75 parts by weight. If the content of each of the heat curing agent and the heat radical generator is lower than the lower limit, it is easy to sufficiently cure the curable composition. If the content of each of the heat curing agent and the heat radical generating agent is less than the upper limit, excess curing agent not involved in curing will hardly remain after curing, and the heat resistance of the cured article will be further increased.

[Photo-curing initiator]

The photocuring initiator is not particularly limited, and examples thereof include an acetophenone photo-curing initiator (acetophenone photo-radical generator), a benzophenone photo-curing initiator (benzophenone photo-radical generator), a thioxanthone, a ketal photo- Halogenated ketones, acylphosphine oxides, acylphosphonates, and the like. The photocuring initiator may be used alone or in combination of two or more.

Specific examples of the acetophenone photo-curing initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy- , Methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-hydroxy-2-cyclohexyl acetophenone. Specific examples of the ketal photo-curing initiator include benzyl dimethyl ketal and the like.

The content of the photocuring initiator is not particularly limited. The content of the photocuring initiator is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, preferably 2 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the curable compound to be. When the content of the photo-curing initiator is lower than the lower limit described above, it is easy to sufficiently cure the curable composition. Further, by irradiating the curable composition with light to form a B stage, the flow of the curable composition can be suppressed. If the content of the photo-curing initiator is not more than the upper limit, excess curing initiator not involved in curing will hardly remain after curing.

[Quaternary ammonium salt compound]

By the use of the quaternary ammonium salt compound, the adhesiveness of the member to be connected is further increased. Further, by the use of the above quaternary ammonium salt compound, even if exposed at a high temperature, further peeling becomes less likely to occur. The quaternary ammonium salt compound may be used alone, or two or more quaternary ammonium salt compounds may be used in combination.

The quaternary ammonium salt compound preferably has an alkyl group having 8 to 18 carbon atoms in order to further increase the adhesiveness of the member to be connected and particularly to further improve the adhesiveness of the PET film. From the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesiveness of the PET film, the quaternary ammonium salt compound is preferably a compound represented by the following formula (31).

R1R2R3R4N ⁺ X ^- ... Equation (31)

In the formula (31), R 1, R 2 and R 3 are each a methyl group or an ethyl group, R 4 is an alkyl group having a carbon number of 8 to 18, and X is a bromine atom or a chlorine atom.

Examples of the quaternary ammonium salt compound include n-octyl trimethyl chloride, n-octyl trimethyl bromide, nonyl trimethyl bromide, decyl trimethyl bromide, dodecyl trimethyl bromide, tetradecyl trimethyl chloride, hexadecyl trimethyl chloride, Hexadecyltrimethylbromide, ethylhexadecyldimethylbromide, heptadecyltrimethylbromide, octadecyltrimethylchloride and octadecyltrimethylbromide, and the like.

The total content of the quaternary ammonium salt compound and the (meth) acrylic compound having a hydroxyl group is preferably at least 0.1 part by weight, more preferably at least 3 parts by weight, more preferably at least 3 parts by weight, based on 100 parts by weight of the total amount of the curing compound and the heat curing agent. More preferably 5 parts by weight or more, preferably 50 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, and 8 parts by weight or less, or 5 parts by weight Or less. If the total content of the quaternary ammonium salt compound and the (meth) acrylic compound having a hydroxyl group is lower than or equal to the lower limit and lower than or equal to the upper limit, the adhesiveness of the member to be bonded is further increased.

The content of the quaternary ammonium salt compound is preferably 0 part by weight (not contained) or more, preferably 0.1 parts by weight or more, more preferably 3 parts by weight or more, and more preferably 3 parts by weight or more based on 100 parts by weight of the total amount of the curing compound and the heat curing agent Preferably 50 parts by weight or less, more preferably 8 parts by weight or less, and further preferably 5 parts by weight or less. When the quaternary ammonium salt compound is used and the content of the quaternary ammonium salt compound is not less than the lower limit and not more than the upper limit, the adhesion of the member to be bonded is further enhanced, and the peeling at a high temperature is further suppressed.

[(Meth) acrylic compound having a hydroxyl group]

By the use of the (meth) acrylic compound having a hydroxyl group, adhesiveness of the member to be connected is further increased. The (meth) acrylic compound having a hydroxyl group may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylic compound include hydroxyethyl methacrylate phosphate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) (Meth) acrylamide, N- (hydroxymethyl) (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide or epoxy .

The viscosity of the curable composition using the curable compound tends to be relatively high. From the viewpoint of lowering the viscosity of the curable composition, it is preferable that the curable compound includes an epoxy (meth) acrylate. The epoxy (meth) acrylate may be used alone or in combination of two or more.

Specific examples of the epoxy (meth) acrylate include EBECRYL 3701 (manufactured by Daicel Alnex), Ebecryl 3703 (manufactured by Daicel Alnex) or Ebecryl 3708 And the like. The epoxy acrylate may be an epoxy acrylate having a structure in which 2-hydroxyethyl acrylate is added to caprolactone at the molecular end and a diglycidyl group of bisphenol A is ring-opened as a main skeleton.

(Meth) acrylate 4-hydroxybutyl, Ebecryl 3701 (manufactured by Daicel Alnex Co.) or Ebecryl 3708 (manufactured by Daicel Ornex Co., Ltd.) is preferable from the viewpoint of further improving the adhesion of the member to be bonded Do.

The content of the (meth) acrylic compound having a hydroxyl group is preferably 0 part by weight (not contained) or more, preferably 0.1 parts by weight or more, more preferably 3 parts by weight More preferably not less than 5 parts by weight, preferably not more than 50 parts by weight, more preferably not more than 40 parts by weight, further preferably not more than 30 parts by weight. If the (meth) acrylic compound having a hydroxyl group is used and the content of the (meth) acrylic compound having a hydroxyl group is lower than or equal to the lower limit and below the upper limit, the adhesion of the member to be adhered is further enhanced.

[Other Ingredients]

In the case where the member to be connected is made of glass or PET (polyethylene terephthalate), it is preferable that the curable compound includes glass (meth) acrylic compound from the viewpoint of further increasing the adhesiveness of PET. Examples of the (meth) acrylic compound include phosphoric ester type (meth) acrylates such as acryloylmorpholine, imide (meth) acrylate and urethane (meth) acrylate. The (meth) acrylic compound is a compound other than the above-mentioned curable compound. The (meth) acryl compound is a compound having a (meth) acryloyl group. The (meth) acrylic compound may be used alone or in combination of two or more.

The curable composition may further contain additives such as fluxes, fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbents, lubricants, antistatic agents and flame retardants It may contain various additives.

The curable composition preferably comprises a flux. By using the flux, the surface oxide film of the electrode can be removed to improve the reliability of conduction between the electrodes. The details of the flux are described in the column of the conductive material to be described later.

The curable composition preferably comprises a filler. The thermal expansion coefficient of the cured product is lowered by the use of the filler. Specific examples of the filler include silica, aluminum nitride, alumina, glass, boron nitride, silicon nitride, silicon, carbon, graphite, graphene and talc. Only one type of filler may be used, or two or more types of fillers may be used in combination. Use of a filler having a high thermal conductivity will shorten the final curing time.

The curable composition may contain a solvent. The viscosity of the curable composition can be easily adjusted by using the solvent. Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran and diethyl ether.

(Conductive material)

The conductive material according to the present invention includes the above-mentioned curable composition and conductive particles. Specifically, the conductive material according to the present invention includes the curable compound obtained by reacting the first compound with the second compound, the heat curing agent, and the conductive particle. In the present specification, a curable composition containing conductive particles is referred to as a conductive material. By using the conductive material according to the present invention, the adhesiveness of the member to be connected and the reliability of conduction between the electrodes can be improved.

The conductive material preferably includes a flux. By using the flux, the surface of the conductive particles and the surface oxide film of the electrode can be removed to improve the reliability of the conduction between the electrodes.

From the viewpoint of more efficiently arranging the conductive particles on the electrode, the viscosity of the conductive material at 25 캜 is preferably 100 Pa · s or more, more preferably 200 Pa · s or more, s or lower, more preferably 600 Pa s or lower.

The viscosity can be easily and appropriately adjusted depending on the type and blending amount of the compounding ingredients. Also, the viscosity can be made relatively high by the use of a filler.

The viscosity can be measured at 25 캜 and 2.5 rpm using, for example, an E-type viscometer TVE-22 apparatus (manufactured by Toki Sangyo Co., Ltd.).

The conductive material is preferably an anisotropic conductive material. The conductive material may be used as a conductive paste and a conductive film. When the conductive material is a conductive film, a film not containing conductive particles may be laminated on the conductive film containing conductive particles. From the viewpoint of further enhancing the adhesiveness of the member to be connected and particularly enhancing the adhesiveness of the PET film, the conductive material is preferably paste-like conductive paste. The conductive material is preferably used for electrical connection between the electrodes. The conductive material is preferably a circuit connecting material.

The content of the curing compound obtained by reacting the first compound with the second compound in 100 wt% of the conductive material is preferably at least 50 wt%, more preferably at least 60 wt%, and still more preferably at least 75 wt% %, Preferably not more than 100 wt%, more preferably not more than 95 wt%. When the content of the curable compound is lower than the lower limit, the adhesiveness of the member to be connected is further increased, and in particular, the adhesion of the PET film is further enhanced. When the content of the curable compound is not more than the upper limit, the content of the conductive particles can be relatively increased, and the reliability of the conduction between the electrodes is further increased.

The content of the conductive particles in 100 wt% of the conductive material is preferably 0.1 wt% or more, more preferably 1 wt% or more, still more preferably 2 wt% or more, still more preferably 10 wt% Still more preferably not less than 20% by weight, particularly preferably not less than 25% by weight, most preferably not less than 30% by weight, preferably not more than 80% by weight, more preferably not more than 60% by weight, 50 wt% or less, particularly preferably 45 wt% or less, and most preferably 35 wt% or less. When the content of the conductive particles is not less than the lower limit and not more than the upper limit, it is easy to arrange a large number of conductive particles between the electrodes, thereby further enhancing the conduction reliability. In addition, since the content of the curable compound and the like becomes appropriate, the reliability of the conduction between the electrodes becomes even higher.

Hereinafter, details of each component usable in the conductive material according to the present invention will be described.

[Conductive particle]

Examples of the conductive particles include conductive particles formed entirely of a conductive material and conductive particles having a base particle and a conductive layer disposed on the surface of the base particle.

It is preferable that the above-mentioned conductive particles are conductive particles whose outer surface is solder. And the outer surface of the conductive portion is preferably solder. In this case, the adhesion between the connection portion formed by hardening the conductive material and the connection target member connected by the connection portion derived from the solder becomes even higher.

As the conductive particles at least the outer surface of which is solder, there can be used solder particles, particles having base particles and a solder layer disposed on the surface of the base particles, or the like. Among them, it is preferable to use solder particles. By using the solder particles, the high-speed transmission and the metal bonding strength can be further improved. Further, in the case of using the conductive particles whose outer surface is solder, the solder particles may be collected between the first electrode, the second electrode and the electrode. The conductive particles having at least the outer surface of the solder may have the property that the conductive particles existing in the region where the electrode is not formed gather at the time of heating between the first electrode and the second electrode.

5 is a cross-sectional view showing an example of conductive particles usable in the conductive material used in the first embodiment of the present invention.

As shown in Fig. 5, the conductive particles are preferably conductive particles 21 that are solder particles. The conductive particles 21 are formed only by solder. The conductive particles 21 do not have the base particles in the core and are not core-shell particles. The conductive particles 21 are formed by solder on both the center portion and the outer surface.

Particles having base particles and a solder layer disposed on the surface of the base particles may be used from the viewpoint of maintaining the connection distance between the connection target members more uniformly.

6, the conductive particles 1 include base particles 2 and a conductive layer 3 disposed on the surface of the base particles 2. In the modified example shown in Fig. The conductive layer (3) covers the surface of the base particle (2). The conductive particles (1) are coated particles in which the surface of the base particles (2) is covered with the conductive layer (3).

The conductive layer 3 has a second conductive layer 3A and a solder layer 3B (first conductive layer) disposed on the surface of the second conductive layer 3A. The conductive particles 1 have a second conductive layer 3A between the base particles 2 and the solder layer 3B. Therefore, the conductive particles 1 include the base particles 2, the second conductive layer 3A disposed on the surface of the base particles 2, and the solder layer 3 disposed on the surface of the second conductive layer 3A, (3B). As described above, the conductive layer 3 may have a multilayer structure or a laminate structure of two or more layers.

As described above, the conductive layer 3 in the conductive particle 1 has a two-layer structure. 7, the conductive particles 11 may have a solder layer 12 as a single-layer conductive layer. The conductive particles 11 include base particles 2 and a solder layer 12 disposed on the surface of the base particles 2. The solder layer 12 may be disposed on the surface of the base particle 2 so as to be in contact with the base particle 2.

The conductive particles (1, 11) among the conductive particles (1, 11, 21) are more preferable because the thermal conductivity of the conductive material tends to be further lowered. It is easy to further lower the thermal conductivity of the conductive material by using the conductive particles including the base particles and the solder layer disposed on the surface of the base particles. From the viewpoint of further improving connection reliability and conduction reliability between the electrodes, the conductive particles 21 are preferable.

Examples of the base particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybridized particles, and metal particles. From the viewpoint of more efficiently arranging the conductive particles on the electrode, the base particles are preferably base particles except metal, and are preferably inorganic particles other than resin particles, metal particles, or organic-inorganic hybridized particles. The base particles may be copper particles. The base particles are preferably not metal particles.

The base particles are preferably resin particles formed by a resin. When the electrodes are connected using the conductive particles, the conductive particles are disposed between the electrodes and then pressed to compress the conductive particles. When the base particles are resin particles, the conductive particles are liable to be deformed at the time of pressing, and the contact area between the conductive particles and the electrode is increased. As a result, the reliability of conduction between the electrodes is further enhanced.

As the resin for forming the resin particles, various organic materials are suitably used. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; Acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Phenol resin, melamine resin, urea resin, urea resin, urea resin, urea resin, urea resin, phenol resin, melamine resin, urea resin, urea resin, urea resin, And examples thereof include epoxy resins, unsaturated polyester resins, saturated polyester resins, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyetheretherketone, polyether sulfone, Vinylbenzene-based copolymer, and the like. Examples of the divinylbenzene-based copolymer and the like include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylate copolymer. It is preferable that the resin for forming the resin particles is a polymer obtained by polymerizing at least one polymerizable monomer having an ethylenic unsaturated group.

When the resin particle is obtained by polymerizing a monomer having an ethylenic unsaturated group, examples of the monomer having the ethylenic unsaturated group include a monomer which is incompatible with the monomer and a monomer which is crosslinkable.

Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and? -Methylstyrene; Carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl Alkyl (meth) acrylates such as acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; (Meth) acrylates such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate; Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; Acid vinyl esters such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene.

Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di Polyfunctional (meth) acrylates such as (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate and 1,4-butanediol di (meth) acrylate; (Meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, trimethylolpropane trimethoxysilane, triallyl trimellitate, divinyl benzene, diallyl phthalate, diallyl acrylamide, diallyl ether, , Silane-containing monomers such as vinyltrimethoxysilane, and the like.

When the base particles are inorganic particles other than metals or organic-inorganic hybridized particles, examples of inorganic substances for forming base particles include silica and carbon black. The inorganic material is preferably not a metal. The particles formed by the silica are not particularly limited. For example, particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, and then firing if necessary, . Examples of the organic-inorganic hybridized particles include crosslinked alkoxysilyl polymers and organic-inorganic hybridized particles formed by an acrylic resin.

In the case where the base particles are metal particles, silver, copper, nickel, silicon, gold, titanium and the like can be given as metals for forming the metal particles. When the base particles are metal particles, the metal particles are preferably copper particles. However, it is preferable that the base particles are not metal particles.

The melting point of the base particles is preferably higher than the melting point of the solder layer. The melting point of the base particles preferably exceeds 160 캜, more preferably exceeds 300 캜, more preferably exceeds 400 캜, and particularly preferably exceeds 450 캜. The melting point of the base particles may be lower than 400 占 폚. The melting point of the base particles may be 160 캜 or lower. The base particles preferably have a softening point of 260 캜 or higher. The softening point of the base particles may be less than 260 캜.

The conductive particles may have a single-layered solder layer. The conductive particles may have a plurality of conductive layers (solder layer, second conductive layer). That is, in the conductive particles, two or more conductive layers may be laminated. In some cases, the solder particles may be particles formed by a plurality of layers.

The solder for forming the solder layer and the solder for forming the solder particles are preferably a low melting point metal having a melting point of 450 캜 or lower. The solder layer is preferably a low melting point metal layer having a melting point of 450 캜 or lower. The low melting point metal layer is a layer containing a low melting point metal. The solder particles are preferably low melting point metal particles having a melting point of 450 캜 or lower. The low melting point metal particles are particles containing a low melting point metal. The low melting point metal means a metal having a melting point of 450 캜 or lower. The melting point of the low melting point metal is preferably 300 DEG C or lower, more preferably 160 DEG C or lower. It is also preferable that the solder layer and the solder particles contain tin. The content of tin in 100 wt% of the metal contained in the solder layer and 100 wt% of the metal contained in the solder particles is preferably 30 wt% or more, more preferably 40 wt% or more, Is at least 70% by weight, particularly preferably at least 90% by weight. When the content of tin in the solder layer and the solder particles is not lower than the lower limit, the connection reliability between the conductive particles and the electrode is further increased.

The content of the tin may be determined by a high frequency inductively coupled plasma emission spectrochemical analyzer ("ICP-AES" manufactured by Horiba Seisakusho Co., Ltd.) or a fluorescent X-ray analyzer ("EDX-800HS" manufactured by Shimadzu Corporation) Can be measured using.

By using the solder particles and the conductive particles having the solder on the conductive surface, the solder is melted and bonded to the electrodes, and the solder makes the electrodes conductive. For example, if the solder and the electrode are not in point contact, they are likely to come into contact with each other, thereby lowering the connection resistance. Further, by the use of the conductive particles having the solder on the conductive surface, the bonding strength between the solder and the electrode is increased. As a result, the solder and the electrode are less likely to be peeled off, and the conduction reliability and the connection reliability are effectively increased.

The solder layer and the low melting point metal constituting the solder particle are not particularly limited. The low melting point metal is preferably an alloy containing tin or tin. Examples of the alloy include tin-silver alloy, tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy, tin-zinc alloy and tin-indium alloy. Among them, it is preferable that the low melting point metal is tin, a tin-silver alloy, a tin-silver-copper alloy, a tin-bismuth alloy, and a tin-indium alloy from the viewpoint of excellent wettability to electrodes. Tin-bismuth alloy, and tin-indium alloy.

The material constituting the solder (the solder layer and the solder particles) is preferably a filler material having a liquidus line of 450 DEG C or less based on JIS Z3001: welding terminology. Examples of the composition of the solder include a metal composition including zinc, gold, silver, lead, copper, tin, bismuth, indium and the like. Among them, tin-indium based (117 占 폚 eutectic), which is a low melting point and lead-free, or tin-bismuth system (139 占 폚) is preferable. That is, it is preferable that the solder does not contain lead, and is preferably solder containing tin and indium, or solder containing tin and bismuth.

In order to further increase the bonding strength between the solder and the electrode, the solder layer and the solder particle may include phosphorus, tellurium, nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, germanium , Cobalt, bismuth, manganese, chromium, molybdenum, palladium, and the like. From the viewpoint of further increasing the bonding strength between the solder and the electrode, it is preferable that the solder layer and the solder particle include nickel, copper, antimony, aluminum or zinc. From the viewpoint of further increasing the bonding strength between the solder layer or the solder particles and the electrode, the content of these metals for increasing the bonding strength is preferably 0.0001 wt% or more, more preferably 0.0001 wt% or more of 100 wt% of the solder layer or 100 wt% Preferably 1% by weight or less.

The melting point of the second conductive layer is preferably higher than the melting point of the solder layer. The melting point of the second conductive layer is preferably more than 160 DEG C, more preferably more than 300 DEG C, more preferably more than 400 DEG C, still more preferably more than 450 DEG C, Preferably greater than 500 캜, and most preferably greater than 600 캜. Since the solder layer has a low melting point, it is melted at the time of conductive connection. It is preferable that the second conductive layer is not melted at the time of conductive connection. It is preferable that the conductive particles are used by melting the solder. Preferably, the conductive particles are used by melting the solder layer. It is preferable that the conductive particles are used without melting the solder layer and melting the second conductive layer. The melting point of the second conductive layer is higher than the melting point of the solder layer so that only the solder layer can be melted without melting the second conductive layer at the time of conductive connection.

The absolute value of the difference between the melting point of the solder layer and the melting point of the second conductive layer is more than 0 DEG C, preferably 5 DEG C or more, more preferably 10 DEG C or more, still more preferably 30 DEG C or more, 50 DEG C or higher, and most preferably 100 DEG C or higher.

The second conductive layer preferably includes a metal. The metal constituting the second conductive layer is not particularly limited. As the metal, for example, gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, . As the metal, tin-doped indium oxide (ITO) may also be used. These metals may be used singly or two or more of them may be used in combination.

The second conductive layer is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and more preferably a copper layer. The conductive particles preferably have a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and more preferably a copper layer. By using the conductive particles having these preferable conductive layers for connection between the electrodes, the connection resistance between the electrodes is further lowered. In addition, a solder layer can be formed more easily on the surface of these preferable conductive layers.

The average particle diameter of the conductive particles is preferably 0.1 mu m or more, more preferably 1 mu m or more, preferably 100 mu m or less, more preferably 80 mu m or less, further preferably 50 mu m or less, Is 40 mu m or less. When the average particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the contact area between the conductive particles and the electrode becomes sufficiently large, and the conductive particles aggregated when the conductive layer is formed are difficult to form. In addition, the conductive particles become a size suitable for the conductive particles in the conductive material, the gap between the electrodes connected via the conductive particles does not become excessively large, and the conductive layer becomes difficult to peel off from the surface of the base particles.

The particle diameter of the conductive particles indicates the number average particle diameter. The average particle diameter of the conductive particles is obtained by observing 50 conductive particles of any given type with an electron microscope or an optical microscope and calculating an average value.

The thickness of the solder layer is preferably at least 0.005 탆, more preferably at least 0.01 탆, preferably at most 10 탆, more preferably at most 1 탆, further preferably at most 0.3 탆. When the thickness of the solder layer is not less than the lower limit and not more than the upper limit, sufficient conductivity is obtained and the conductive particles are not excessively hardened, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. Further, the thinner the solder layer, the easier it is to lower the thermal conductivity of the conductive material. From the viewpoint of sufficiently lowering the thermal conductivity of the conductive material, the thickness of the solder layer is preferably 4 占 퐉 or less, and more preferably 2 占 퐉 or less.

The thickness of the second conductive layer is preferably at least 0.005 탆, more preferably at least 0.01 탆, preferably at most 10 탆, more preferably at most 1 탆, further preferably at most 0.3 탆. When the thickness of the second conductive layer is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes is further lowered. Also, the thinner the thickness of the second conductive layer, the easier it is to lower the thermal conductivity of the conductive material. From the viewpoint of sufficiently lowering the thermal conductivity of the conductive material, the thickness of the second conductive layer is preferably 3 占 퐉 or less, and more preferably 1 占 퐉 or less.

When the conductive particles have only a solder layer as a conductive layer, the thickness of the solder layer is preferably 10 占 퐉 or less, and more preferably 5 占 퐉 or less. When the conductive particles have a conductive layer different from the solder layer and the solder layer (the second conductive layer or the like) as the conductive layer, the total thickness of the solder layer and the different conductive layers different from the solder layer, Preferably 10 mu m or less, more preferably 5 mu m or less.

[Flux]

The conductive material preferably includes a flux. The flux is not particularly limited. As the flux, a flux generally used for soldering or the like can be used. The flux may be used alone or in combination of two or more.

Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, a phosphoric acid, a derivative of phosphoric acid, an organic halide, a hydrazine, an organic acid, Examples of the molten salt include ammonium chloride and the like. Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid and glutaric acid. Examples of the papermaking papers include activated papermaking and inactive papermaking. It is preferable that the flux is an organic acid having two or more carboxyl groups, and a feedstock. The flux may be an organic acid having two or more carboxyl groups, or may be tanned. The use of an organic acid having two or more carboxyl groups and a transfer paper makes the reliability of conduction between the electrodes even higher.

The above paper is a rosin mainly containing abietic acid. The flux is preferably rosin, more preferably abietic acid. By using this preferable flux, the reliability of conduction between the electrodes is further enhanced.

The melting point of the flux is preferably 50 占 폚 or higher, more preferably 70 占 폚 or higher, even more preferably 80 占 폚 or higher, preferably 200 占 폚 or lower, more preferably 160 占 폚 or lower, even more preferably 150 Lt; 0 > C, more preferably 140 < 0 > C or less. When the melting point of the flux is higher than or equal to the lower limit and lower than or equal to the upper limit, the flux effect is more effectively exhibited, and the solder particles are more efficiently arranged on the electrode. The melting point of the flux is preferably 80 ° C or higher and 190 ° C or lower. The melting point of the flux is particularly preferably from 80 캜 to 140 캜.

Examples of the flux having a melting point of 80 캜 to 190 캜 include succinic acid having a melting point of 186 캜, glutaric acid having a melting point of 96 캜, adipic acid having a melting point of 152 캜, pimelic acid having a melting point of 104 캜, (Melting point: 142 占 폚), benzoic acid (melting point: 122 占 폚) and malic acid (melting point: 130 占 폚).

From the viewpoint of more efficiently placing the solder on the electrode, the melting point of the flux is preferably lower than the melting point of the solder in the solder particle, more preferably 5 deg. C or lower, more preferably 10 deg. Do.

From the viewpoint of more efficiently placing the solder on the electrode, the melting point of the flux is preferably lower than the reaction initiation temperature of the thermosetting agent, more preferably 5 deg. C or lower, still more preferably 10 deg.

The flux may be dispersed in the curable composition or the conductive material, or may be attached on the surface of the conductive particles or the solder particles.

The content of the flux in 100 wt% of the conductive material is 0 wt% (unused) or more, preferably 0.5 wt% or more, preferably 30 wt% or less, and more preferably 25 wt% or less. The conductive material may not contain a flux. If the content of the flux is lower than or equal to the lower limit and lower than or equal to the upper limit described above, an oxide film is less likely to be formed on the surface of the solder and the electrode, and the oxide film formed on the surface of the solder and the electrode can be removed more effectively.

(Connection structure)

The connection structure can be obtained by connecting the connection target members using the above-described curable composition or the conductive material.

The connection structure includes a first connection target member, a second connection target member, and a connection unit connecting the first connection target member and the second connection target member. The connecting portion is formed by curing the above-mentioned curable composition or by curing the conductive material.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front sectional view schematically showing a connection structure obtained by using a conductive material including a conductive particle and a curable composition according to a first embodiment of the present invention. FIG.

The connection structure 51 shown in Fig. 1 has the first connection target member 52, the second connection target member 53, the first connection target member 52 and the second connection target member 53 And a connecting portion 54 connected thereto. The connecting portion 54 is a cured layer and is formed by curing a conductive material containing the conductive particles 1. [ Instead of the conductive particles 1, the conductive particles 11 or the conductive particles 21 may be used. Further, conductive particles other than the conductive particles (1, 11, 21) may be used.

The first connection target member 52 has a plurality of first electrodes 52a on its surface (upper surface). The second connection target member 53 has a plurality of second electrodes 53a on its surface (lower surface). The first electrode 52a and the second electrode 53a are electrically connected to each other by one or more conductive particles 1. [ Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1. [

Fig. 4 is an enlarged front sectional view of the connecting portion between the conductive particles 1 and the first and second electrodes 52a and 53a in the connection structure 51 shown in Fig. 4, in the connection structure 51, after the solder layer 3B in the conductive particles 1 is melted, the melted solder layer portion 3Ba contacts the first and second electrodes 52a , And 53a. That is, by using the conductive particles 1 whose surface layer is the solder layer 3B, compared with the case where the surface layer of the conductive layer is made of metal such as nickel, gold or copper, 1, the contact area of the second electrodes 52a, 53a is increased. Thus, the conduction reliability and the connection reliability of the connection structure 51 can be improved. Further, when flux is used, the flux generally gradually deactivates due to heating. It is preferable to bring the second conductive layer 3A into contact with the first electrode 52a and to bring the second conductive layer 3A into contact with the second electrode 53a from the viewpoint of further enhancing conduction reliability Do.

2 is a front sectional view schematically showing a connection structure obtained by using the curable composition according to the second embodiment of the present invention.

The connecting structure 61 shown in Fig. 2 has a first connecting object member 62, a second connecting object member 63, a first connecting object member 62 and a second connecting object member 63 And a connecting portion 64 connected thereto. The connection portion 64 is a cured layer, which is formed by curing a curable composition containing no conductive particles.

The first connection target member 62 has a plurality of first electrodes 62a on its surface (upper surface). The second connection target member 63 has a plurality of second electrodes 63a on its surface (lower surface). The first electrode 62a and the second electrode 63a are, for example, bump electrodes. The first electrode 62a and the second electrode 63a are electrically connected by being in contact with each other without interposing the conductive particles. Therefore, the first and second connection target members 62 and 63 are electrically connected.

3 is a front sectional view schematically showing a connection structure obtained by using the curable composition according to the third embodiment of the present invention.

The connecting structure 71 shown in Fig. 3 has a first connecting object member 72, a second connecting object member 73, a first connecting object member 72 and a second connecting object member 73 And a connecting portion 74 connected thereto. The connection portion 74 is a cured layer, which is formed by curing a curable composition containing no conductive particles. In the connection structure 71, the electrodes are not electrically connected. The use of the curable composition is not limited to the use to which the electrodes are electrically connected.

The manufacturing method of the connection structure is not particularly limited. As an example of a method of manufacturing the connection structure, a method of arranging the conductive material or the curable composition between the first connection target member and the second connection target member to obtain a laminate, heating and pressing the laminate And the like. The pressure for this pressurization is about 9.8 x 10 ⁴ to 4.9 x 10 ⁶ Pa. The temperature of the heating is about 120 to 220 占 폚.

The first and second connection target members are not particularly limited. Specifically, examples of the first and second connection target members include electronic and electric parts such as a metal member, a resin member and a film member, electronic and electric parts such as an electric semiconductor chip, a capacitor and a diode, a printed board, And electronic and electric parts such as a substrate, a glass epoxy substrate, a flexible flat cable (FFC), and a circuit board such as a glass substrate. It is preferable that the first and second connection target members are electronic and electric parts. The electronic / electric component is a member constituting an electronic / electric device. The connection structure is preferably an electronic / electrical component connection structure. Preferably, the connection structure is an electronic or electric appliance.

The first and second connection target members are preferably touch panel connection target members. It is preferable that at least one of the first and second connection target members is a PET film in that the adhesive property improving effect can be largely obtained by use of the curable composition and the conductive material.

The curable composition and the conductive material are suitably used for bonding a PET film and an FFC (flexible flat cable), and are preferably a curable composition for bonding a PET film and an FFC (flexible flat cable). The curable composition and the conductive material are suitably used for bonding a PET film in a touch panel, and are preferably a curable composition for bonding a PET film in a touch panel.

In addition, the curable composition and the conductive material are suitably used for adhesion of a PET film, and also for bonding a display resin film and a flexible printed substrate.

The curable composition and the conductive material are suitably used not only for bonding an FFC (flexible flat cable) but also for bonding a rigid substrate and an FFC (flexible flat cable).

Examples of the electrode provided on the member to be connected include a metal electrode such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode. When the connection target member is a flexible printed circuit board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. When the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of the metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al and Ga.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. The present invention is not limited to the following embodiments.

(First Test Example)

(Synthesis Example 1)

Synthesis of Curable Compound (1):

40 g of dimethylisophthalic acid, 100 g of 1,6-hexanediol, and 0.2 g of dibutyltin oxide as a catalyst were weighed into a three-necked flask, and reacted at 120 DEG C for 4 hours while being dehydrated by a Dean Stark trap under a vacuum condition. Thereafter, 9 g of 2-isocyanatomethyl methacrylate and 0.05 g of dibutyl tin dibutyllaurate were added and reacted at 120 ° C for 4 hours to obtain a curable compound. The weight average molecular weight of the obtained curable compound was 15,000.

(Synthesis Example 2)

Synthesis of Curable Compound (2):

37 g of dimethylisophthalic acid, 3 g of dimethylterephthalic acid, 100 g of 1,6-hexanediol and 0.2 g of dibutyltin oxide as a catalyst were weighed into a three-necked flask and dehydrated under a vacuum condition by a Dean Stark trap at 120 DEG C for 4 hours Lt; / RTI > Thereafter, 9 g of 2-isocyanatomethyl methacrylate and 0.05 g of dibutyl tin dibutyllaurate were added and reacted at 120 ° C for 4 hours to obtain a curable compound. The weight average molecular weight of the obtained curable compound was 15,000.

(Synthesis Example 3)

Synthesis of Curable Compound (3):

40 g of dimethylisophthalic acid, 20 g of 1,6-hexanediol, 15 g of bisphenol F and 0.2 g of dibutyl tin oxide as a catalyst were weighed in a three-necked flask and dehydrated by a Dean Stark trap under a vacuum condition. Lt; / RTI > Thereafter, 9 g of 2-isocyanatomethyl methacrylate and 0.05 g of dibutyl tin dibutyllaurate were added and reacted at 120 ° C for 4 hours to obtain a curable compound. The weight average molecular weight of the obtained curable compound was 12,000.

(Synthesis Example 4)

Synthesis of Curable Compound (4)

15 g of dimethyl isophthalic acid, 25 g of dimethyladipic acid, 20 g of 1,6-hexanediol, 15 g of bisphenol F and 0.2 g of dibutyltin oxide as a catalyst were weighed into a three-necked flask, And then reacted at 120 ° C for 4 hours while dewatering. Thereafter, 9 g of 2-isocyanatomethyl methacrylate and 0.05 g of dibutyl tin dibutyllaurate were added and reacted at 120 ° C for 4 hours to obtain a curable compound. The weight average molecular weight of the obtained curable compound was 16,000.

(Synthesis Example 5)

Synthesis of Curable Compound (5)

15 g of dimethyl isophthalic acid, 25 g of dimethyladipic acid, 20 g of 1,6-hexanediol, 15 g of polytetramethylene glycol having a molecular weight of 650 and 0.2 g of dibutyltin oxide as a catalyst were weighed and placed in a vacuum condition , And reacted at 120 DEG C for 4 hours while being dehydrated by Dean Stark trap. Thereafter, 9 g of 2-isocyanatomethyl methacrylate and 0.05 g of dibutyl tin dibutyllaurate were added and reacted at 120 ° C for 4 hours to obtain a curable compound. The weight average molecular weight of the obtained curable compound was 20,000.

(Example 1)

(1) Preparation of conductive paste

90 parts by weight of the curing compound (1) obtained in Synthesis Example 1, 10 parts by weight of acrylic compound (1) ("ACMO" manufactured by Kojin Films Chemical Co., Ltd.) and 10 parts by weight of solder particles (DS- 30 parts by weight of a thermosetting agent ("perocta O" manufactured by Niche-like, 1 minute half-life temperature 124.3 ° C.), 30 parts by weight of a silane , And 0.2 part by weight of a coupling agent (X-12-972A polymer-type polyfunctional amino silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) were blended to obtain an anisotropic conductive paste.

(2) Fabrication of the connection structure 1

As the adherend 1, a circuit board on which 40 aluminum wires with L / S = 200/200 占 퐉 were formed on the base PET film was prepared. As the adherend 2, on the base polyimide film, an FPC having 40 wires formed by electroless plating of Au as underlying Ni on a Cu wire of L / S = 200/200 mu m was prepared.

3 mg of anisotropic conductive paste was applied to the adherend 1 with an air dispenser. The adherend 2 and the adherend 2 were overlapped with each other with an anisotropic conductive paste interposed therebetween so that the electrode pattern of the adherend 1 and the adherend 2 fit with each other. Thereafter, the laminate was joined at 140 캜 for 10 seconds under a pressure of 1 MPa to obtain a connection structure (1).

(Example 2)

Anisotropic conductive paste and connection structure (1) were obtained in the same manner as in Example 1 except that the curable compound (1) obtained in Synthesis Example 1 was changed to the curable compound (2) obtained in Synthesis Example 2.

(Example 3)

Fabrication of the connection structure 2:

The connection structure 1 was produced in the same manner as in Example 1 except that an anisotropic conductive paste obtained in Example 1 was used to form an adherend having an FFC (Flexible Flat Cable) and 40 lines of L / S = 200 / The connection structure 2 was obtained.

(Examples 4 to 11)

(1) Preparation of conductive paste

Anisotropic conductive paste was obtained in the same manner as in Example 1, except that the kinds and blending amounts of the blending components were changed as shown in Table 1 below.

Details of the (meth) acrylic compound are as follows.

(Meth) acrylic compound (2): "Ebecryl 8413" manufactured by Daicel-Allenx, aliphatic urethane acrylate

(Meth) acrylic compound (3): "Ebecryl 3708" manufactured by Daicel Ornex Co., Ltd., a compound having a structure in which 2-hydroxyethyl acrylate is added to caprolactone at the molecular end and diglycidyl Epoxy acrylate having a structure in which a divalent group is ring-opened as a main skeleton

(Meth) acrylic compound (4): "Ebecryl 168" manufactured by Daicel-Allenx, phosphate ester type (meth) acrylate such as hydroxyethyl methacrylate phosphate

(Meth) acrylic compound (5): "M-140" manufactured by Toagosei Co., Ltd., imide (meth) acrylate

(2) Fabrication of the connection structure 3

The connection structure 3 was obtained in the same manner as the connection structure 1 except that the obtained anisotropic conductive paste was used for bonding at 140 占 폚 for 5 seconds and a pressure of 1 MPa.

(3) Fabrication of the connection structure 4

Using the resulting anisotropic conductive paste, the connection structure 4 was obtained in the same manner as the connection structure 2 except that the connection was performed at 140 캜 for 5 seconds and under a pressure of 1 MPa.

(Comparative Example 1)

Anisotropic conductive paste was obtained in the same manner as in Example 1 except that the kind of the curable compound was changed to a bisphenol A type epoxy compound. Using the obtained anisotropic conductive paste, a connection structure 1 was obtained in the same manner as in Example 1, and a connection structure 2 was obtained in the same manner as in Example 3. The connection structure 3 was obtained in the same manner as in Examples 4 to 11, And the connection structure 4 were obtained.

(evaluation)

(1) Initial adhesion

The resulting connection structure was subjected to peeling using " Micro Autograph MST-I " manufactured by Shimadzu Seisakusho Co., Ltd., and 90 DEG peel strength C was measured at a tensile rate of 50 mm / min under an atmosphere of 23 캜. The initial adhesion was determined based on the following criteria.

[Initial Adhesion Judgment Criteria]

OO: 90 DEG Peel strength C is 20 N / cm or more

?: 90 占 peel strength C of 15 N / cm or more and less than 20 N / cm

DELTA: 90 DEG Peel strength C was 10 N / cm or more and less than 15 Ncm

X: 90 DEG Peel strength C was less than 10 N / cm

(2) Adhesion under high temperature and high humidity

The resulting connection structure was left to stand at 85 캜 and 85% humidity for 500 hours. The 90 ° peel strength D was measured for the connection structure after left standing in the same manner as in the above (1) evaluation of the adhesiveness. The adhesion under high temperature and high humidity was judged based on the following criteria.

[Judgment criteria of adhesiveness under high temperature and high humidity]

OO: 90 DEG peel strength C is 20 N / cm or more, and peel strength D / peel strength C x 100 is 80% or more

?: 90 占 peeling strength C was 15 N / cm or more and less than 20 N / cm, and peel strength D / peeling strength C 占 100 was 80% or more

DELTA: 90 DEG peel strength C is 10 N / cm or more and less than 15 Ncm, and peel strength D / peel strength C x 100 is 80% or more

X: 90 DEG Peel strength C was less than 10 N / cm

(3) Reliability of conduction between the upper and lower electrodes

In the obtained connecting structures (n = 15), the connection resistances between the upper and lower electrodes were measured by the four-terminal method, respectively. And the average value of the connection resistance was calculated. From the relationship of voltage = current x resistance, the connection resistance can be obtained by measuring the voltage when a constant current flows. The conduction reliability was judged to be the criterion below. The obtained connection resistance was defined as the resistance of a connection portion in which one pair of electrodes overlapped.

[Criteria for reliability of conduction]

○○: Average value of connection resistance is less than 50mΩ

○: Average value of connection resistance is more than 50 mΩ and less than 75 mΩ

?: Average value of connection resistance is more than 75 m? And not more than 100 m?

X: Average value of connection resistance exceeds 100m?

(4) Elongation at break

A curable composition containing no conductive particles was prepared in the same manner as in the preparation of each of the conductive pastes of Examples and Comparative Examples except that only the conductive particles were not mixed. The obtained curable composition was cured at 140 캜 for 10 seconds to obtain a cured product. The obtained cured product was subjected to tensile elongation at a temperature of 23 캜 and a tensile speed of 1 mm / min and a chuck distance of 40 mm to measure the elongation at break.

The composition and results are shown in Table 1 below.

(Second Test Example)

(Synthesis Example 6)

Synthesis of Curable Compound (6):

A three-necked flask was charged with 64 g of dimethylisophthalic acid, 19 g of dimethyladipic acid, 38 g of 1,6-hexanediol, 90 g of polytetramethylene glycol having a molecular weight of 650 and 2 g of tetrabutoxy titanium as a catalyst, The reaction was carried out at 120 DEG C for 4 hours while removing methanol by a Dean Stark trap. Thereafter, 6 g of 2-isocyanatoethyl acrylate and 0.6 g of dibutyl tin dibutyl taurate were added and reacted at 120 ° C. for 4 hours to obtain a curable compound. The weight average molecular weight of the obtained curable compound was 27000.

(Synthesis Example 7)

Synthesis of Curable Compound (7):

58 g of dimethylisophthalic acid, 17 g of dimethyl adipic acid, 40 g of 1,6-hexanediol, 94 g of polytetramethylene glycol having a molecular weight of 650 and 2 g of tetrabutoxy titanium as a catalyst were weighed into a three-necked flask, The reaction was carried out at 120 DEG C for 4 hours while removing methanol by a Dean Stark trap. Thereafter, 23 g of 2-isocyanatoethyl acrylate and 0.6 g of dibutyl tin dibutyl taurate were added and reacted at 120 DEG C for 4 hours to obtain a curable compound. The weight average molecular weight of the obtained curable compound was 8300.

(Example 12)

88.5 parts by weight of the curing compound (6) obtained in Synthesis Example 6, 10 parts by weight of 4-hydroxybutyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 10 parts by weight of a thermosetting agent 124.3 占 폚) were mixed, followed by mixing and de-mixing with a planetary stirring apparatus to obtain a curable composition.

(Examples 13 to 35)

A curable composition was obtained in the same manner as in Example 1 except that the kind and blending amount of the compounding ingredients were changed as shown in Tables 2 and 3 below.

(evaluation)

(1) Adhesiveness

The adhesive test pieces were produced by the following procedure. A curable composition was applied on an SUS substrate (2 cm x 7 cm), a PET film was placed thereon, and a flat plate was pressed thereon so that the curable composition had a constant thickness (80 mu m) to obtain a laminate .

The obtained laminate was thermally cured at 130 DEG C for 10 seconds under a pressure of 1 MPa to obtain an adhesive test piece.

Using the obtained adhesive test piece, the 180 占 peel strength was measured at a tensile rate of 300 mm / min under an atmosphere of 23 占 폚 or 100 占 폚 by carrying out peeling by "Micro Autograph MST-I" manufactured by Shimadzu Seisakusho . The initial adhesion was determined based on the following criteria.

[Initial Adhesion Judgment Criteria]

OOX: 180 DEG peel strength is 1.5 N / mm or more

OO: 180 DEG peel strength is 1.0 / mm or more and less than 1.5N / mm

?: 180 占 peel strength was 0.5 N / mm or more and 1.0 N / mm or less

DELTA: 180 DEG peel strength is 0.25 N / mm or more and less than 0.5 N / mm

X: 180 DEG peel strength is less than 0.25 N / mm

(2) Curability

A test piece was prepared in the same manner as in the evaluation of the adhesiveness except that a test piece was produced under the two conditions of the curing time of 10 seconds and 30 seconds, and the 180 degree peel strength was measured. The curability was evaluated according to the following formula.

Curing property (%) = (180 占 peeling strength at 10 sec of curing time) 占 100/180 占 peeling strength at 30 sec of curing time

[Criteria for determination of hardenability]

○○: 95% or more

○: 90% or more and less than 95%

?: 85% or more and less than 90%

×: less than 85%

The composition and the results are shown in Tables 2 and 3 below.

(Third Test Example)

(Synthesis Example 8) Synthesis of a curing compound which does not correspond to the curing compound represented by the formula (1)

Synthesis of Curable Compound (8) (Straight Polyester Compound)

64.0 g of dimethyladipic acid, 24.0 g of dimethylisophthalic acid, 61.4 of 1,6-hexanediol and 0.05 g of tetrabutoxy titanium as a catalyst were weighed in a three-necked flask and reacted at 140 DEG C for 4 hours while removing methanol , And then reacted at 140 DEG C for 12 hours under reduced pressure. Thereafter, 6.3 g of 2-isocyanatoethyl acrylate and 0.6 g of dibutyl tin dibutyl taurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 8,000.

(Synthesis Example 9)

Synthesis of Curable Compound (9) (Straight Polyester Compound)

56.8 g of dimethyl adipic acid, 21.1 g of dimethylisophthalic acid, 51.2 of 1,6-hexanediol, 14.8 g of polytetramethylene glycol (PTMG650) having a molecular weight of 650 and 0.05 g of tetrabutoxy titanium as a catalyst were charged into a three-necked flask , And reacted at 140 DEG C for 4 hours while removing methanol in the system, followed by reaction at 140 DEG C for 12 hours under reduced pressure. Thereafter, 6.4 g of 2-isocyanatoethyl acrylate and 0.6 g of dibutyl tin dibutyl taurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 8,500.

(Synthesis Example 10)

Synthesis of Curable Compound (10) (straight chain polyester compound)

56.1 g of dimethylisophthalic acid, 20.1 g of dimethyladipic acid, 50.6 g of 1,6-hexanediol, 22.5 g of polytetramethylene glycol (PTMG1000) having a molecular weight of 1000, and 0.05 g of tetrabutoxy titanium as a catalyst The flask was weighed and reacted at 140 DEG C for 4 hours while removing methanol, and then reacted at 140 DEG C for 12 hours under reduced pressure. Thereafter, 6.4 g of 2-isocyanatoethyl acrylate and 0.6 g of dibutyl tin dibutyl taurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 12,000.

(Synthesis Example 11)

Synthesis of Curable Compound (11) (straight chain polyester compound)

47.0 g of dimethylisophthalic acid, 17.5 g of dimethyladipic acid, 42.4 g of 1,6-hexanediol, 37.8 g of polytetramethylene glycol (PTMG2000) having a molecular weight of 2000, and 0.05 g of tetrabutoxy titanium as a catalyst The flask was weighed and reacted at 140 DEG C for 4 hours while removing methanol, and then reacted at 140 DEG C for 12 hours under reduced pressure. Thereafter, 5.3 g of 2-isocyanatoethyl acrylate and 0.65 g of dibutyl tin dilaurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 18,000.

(Synthesis Example 12)

Synthesis of Curable Compound (12) (Straight Polyester Compound)

A mixture of 41.8 g of dimethylisophthalic acid, 15.5 g of dimethyladipic acid, 37.7 g of 1,6-hexanediol, 50.3 g of polytetramethylene glycol (PTMG3000) having a molecular weight of 3000, and 0.05 g of tetrabutoxy titanium The flask was weighed and reacted at 140 DEG C for 4 hours while removing methanol, and then reacted at 140 DEG C for 12 hours under reduced pressure. Thereafter, 4.7 g of 2-isocyanatoethyl acrylate and 0.4 g of dibutyl tin dilaurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 30000.

(Synthesis Example 13)

Synthesis of Curable Compound (13) (Straight Polyester Compound)

56.1 g of dimethylisophthalic acid, 20.1 g of dimethyladipic acid, 50.6 g of 1,6-hexanediol, 22.5 g of polyethylene glycol (PEG1000) having a molecular weight of 1000, and 0.05 g of tetrabutoxy titanium as a catalyst were placed in a three-necked flask The mixture was weighed and reacted at 140 DEG C for 4 hours while removing methanol, and then reacted at 140 DEG C for 12 hours under reduced pressure. Thereafter, 6.4 g of 2-isocyanatoethyl acrylate and 0.6 g of dibutyl tin dibutyl taurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 12,000.

(Synthesis Example 14)

Synthesis of Curable Compound (14) (Straight Polyester Compound)

, 51.9 g of dimethylisophthalic acid, 19.3 g of dimethyladipic acid, 47.8 g of 1,6-hexanediol, 25.0 g of polytetramethylene glycol (PTMG2000) having a molecular weight of 2000, and 0.05 g of tetrabutoxy titanium as a catalyst The flask was weighed and reacted at 140 DEG C for 4 hours while removing methanol, and then reacted at 140 DEG C for 12 hours under reduced pressure. Then, 5.9 g of 2-isocyanatoethyl acrylate and 0.65 g of dibutyl tin dilaurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 18,000.

(Synthesis Example 15)

Synthesis of Curable Compound (15) (Straight Polyester Compound)

38.0 g of dimethylisophthalic acid, 14.1 g of dimethyladipic acid, 32.5 g of 1,6-hexanediol, 61.1 g of polytetramethylene glycol (PTMG2000) having a molecular weight of 2000, and 0.05 g of tetrabutoxy titanium as a catalyst The flask was weighed and reacted at 140 DEG C for 4 hours while removing methanol, and then reacted at 140 DEG C for 12 hours under reduced pressure. Then, 4.3 g of 2-isocyanatoethyl acrylate and 0.4 g of dibutyl tin dibutyl taurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 18,000.

(Synthesis Example 16)

Synthesis of Curable Compound (16) (straight chain polyester compound)

47.5 g of dimethyl terephthalic acid, 17.5 g of dimethyladipic acid, 42.4 g of 1,6-hexanediol, 37.8 g of polytetramethylene glycol (PTMG2000) having a molecular weight of 2000, and 0.05 g of tetrabutoxy titanium as a catalyst were charged into a three- And reacted at 140 DEG C for 4 hours while removing methanol, followed by reaction at 140 DEG C for 12 hours under reduced pressure. Thereafter, 5.3 g of 2-isocyanatoethyl acrylate and 0.65 g of dibutyl tin dilaurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 18,000.

(Synthesis Example 17)

Synthesis of Curable Compound (17) (Straight Polyester Compound):

63.4 g of dimethyladipic acid, 42.9 g of 1,6-hexanediol, 38.2 g of polytetramethylene glycol (PTMG2000) having a molecular weight of 2000 and 0.05 g of tetrabutoxy titanium as a catalyst were weighed into a three-necked flask, and methanol The reaction was carried out at 140 ° C for 4 hours, and then the reaction was carried out at 140 ° C for 12 hours under reduced pressure. Then, 5.4 g of 2-isocyanatoethyl acrylate and 0.65 g of dibutyl tin dilaurate were added and reacted at 70 DEG C for 4 hours to obtain a curable compound (linear polyester compound). The weight average molecular weight of the obtained curable compound was 18,000.

(Example 36)

98.5 parts by weight of the curing compound (9) obtained in Synthesis Example 9 and 1.5 parts by weight of a thermosetting agent (perocta O "produced by Nichiai Co., Ltd., 1 minute half life temperature 124.3 ° C) were mixed and then mixed and de- To obtain a curable composition.

(Examples 37 to 45)

A curable composition was obtained in the same manner as in Example 1 except that the kind and blending amount of the compounding ingredients were changed as shown in the following Table 4.

(evaluation)

(1) Glass transition temperature (Tg)

A 0.5 mm thick spacer and a hot press machine were used to produce a cured product having a thickness of 0.5 mm. The glass transition temperature of the obtained cured product was determined by DMA (viscoelasticity measuring apparatus) under a temperature elevation condition of 10 ° C / min.

(2) Tensile modulus at -30 캜

A 0.5 mm thick spacer and a hot press machine were used to produce a cured product having a thickness of 0.5 mm. The cured product was cut into a predetermined size (5.0 mm x 50 mm x 0.5 mm t). The tensile modulus of elasticity was determined at -30 캜 by using a universal material tester ("Tensilon" manufactured by AND Co.).

(2) Adhesiveness

The adhesive test pieces were produced by the following procedure. A curable composition was applied on an SUS substrate (2 cm x 7 cm), a PET film was placed thereon, and a flat plate was pressed thereon so that the curable composition had a constant thickness (80 mu m) to obtain a laminate .

The obtained laminate was thermally cured at 130 DEG C for 10 seconds under a pressure of 1 MPa to obtain an adhesive test piece.

The obtained adhesive test piece was peeled off by "Micro-Autograph MST-I" manufactured by Shimadzu Seisakusho Co., Ltd., and the 180 ° peel strength was measured at a tensile rate of 300 mm / min under an atmosphere of 23 ° C. The initial adhesion was determined based on the following criteria.

[Initial Adhesion Judgment Criteria]

OOX: 180 DEG peel strength is 1.5 N / mm or more

OO: 180 DEG peel strength is 1.0 / mm or more and less than 1.5N / mm

?: 180 占 peel strength was 0.5 N / mm or more and 1.0 N / mm or less

DELTA: 180 DEG peel strength is 0.25 N / mm or more and less than 0.5 N / mm

X: 180 DEG peel strength is less than 0.25 N / mm

(4) Curability

A test piece was prepared in the same manner as in the evaluation of the adhesiveness except that a test piece was produced under two conditions of a curing time of 10 seconds and 30 seconds, and the 180 占 peel strength was measured. The curability was evaluated according to the following formula.

Curing property (%) = (180 占 peeling strength at 10 sec of curing time) 占 100/180 占 peeling strength at 30 sec of curing time

[Criteria for determination of hardenability]

○○: 95% or more

○: 90% or more and less than 95%

?: 85% or more and less than 90%

×: less than 85%

The composition and results are shown in Table 4 below.

1: conductive particles
2: Base particles
3: conductive layer
3A: second conductive layer
3B: solder layer
3Ba: Melted solder layer portion
11: conductive particles
12: solder layer
21: conductive particles
51, 61, 71: connection structure
52, 62, 72: first connection object member
52a, 62a: a first electrode
53, 63, 73: second connection object member
53a, 63a:
54, 64, 74:

Claims (23)

A curing compound obtained by reacting the first compound with a second compound having an isocyanate group and an unsaturated double bond using a first compound obtained by a reaction between a compound represented by the following formula (11) and a diol compound,
A curable composition comprising a thermosetting agent.

In the formula (11), X represents an alkylene group or a phenylene group having 2 to 10 carbon atoms, and R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The curable composition according to claim 1, wherein the compound represented by the formula (11) is a compound represented by the following formula (11A).

In the formula (11A), R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The curable composition according to claim 1, wherein the compound represented by the formula (11) is terephthalic acid, terephthalic acid alkyl ester, isophthalic acid or isophthalic acid alkyl ester. 4. The curable composition according to any one of claims 1 to 3, wherein the diol compound comprises 1,6-hexanediol. 5. The curable composition according to any one of claims 1 to 4, wherein the diol compound comprises bisphenol A or bisphenol F. 6. The curable composition according to any one of claims 1 to 5, wherein the diol compound comprises 1,6-hexanediol and bisphenol A or bisphenol F. The curable composition according to any one of claims 1 to 6, wherein the second compound has a (meth) acryloyl group as a group containing an unsaturated double bond. 8. The curable composition of claim 7, wherein said second compound is (meth) acryloyloxyalkyloxyisocyanate. 9. The curable composition according to any one of claims 1 to 8, wherein the curable compound has a weight average molecular weight of 8000 to 50,000. 10. The curable composition according to any one of claims 1 to 9, comprising a quaternary ammonium salt compound or a (meth) acrylic compound having a hydroxyl group. 11. The curable composition of claim 10, comprising the quaternary ammonium salt compound. 12. The curable composition according to claim 10 or 11, which comprises a (meth) acrylic compound having a hydroxyl group. 13. The curable composition according to any one of claims 1 to 12, wherein the thermosetting agent is a thermal radical generator. 14. The curable composition according to any one of claims 1 to 13, wherein the cured product obtained by curing at 140 DEG C and 10 seconds has a breaking elongation of 500% or more. 15. The film according to any one of claims 1 to 14, which is used for bonding of a polyethylene terephthalate film,
A curable composition which is a curable composition for bonding a polyethylene terephthalate film. 16. The touch panel according to claim 15, which is used for adhesion of a polyethylene terephthalate film,
A curable composition which is a curable composition for bonding a polyethylene terephthalate film in a touch panel. A curable compound represented by the following formula (1)
A curable composition comprising a thermosetting agent.

R 1 and R 2 are each a hydrogen atom or a methyl group, R 3 and R 4 are each a hydrogen atom, a methyl group or a phenyl group, X is an alkylene group or a polyether group having 2 to 10 carbon atoms, Y is N1 and n2 each represent 1 or 2, and m represents an integer in which the weight average molecular weight of the curable compound represented by the formula (1) is 8000 or more and 50000 or less . A curable composition as claimed in any one of claims 1 to 16,
A conductive material comprising conductive particles. 19. The conductive material according to claim 18, wherein the content of the curable compound is 50% by weight or more. The conductive material according to claim 18 or 19, wherein the conductive particles have solder on a conductive outer surface. A first connection object member,
A second member to be connected,
And a connection unit connecting the first connection target member and the second connection target member,
Wherein the connecting portion is formed by curing the curable composition according to any one of claims 1 to 16. 22. The method of claim 21,
The first connection target member has a first electrode on its surface,
The second connection target member has a second electrode on a surface thereof,
And the first electrode and the second electrode are electrically connected by being in contact with each other. A first connection target member having a first electrode on its surface,
A second connection target member having a second electrode on its surface,
And a connection unit connecting the first connection target member and the second connection target member,
Wherein the connecting portion is formed by curing the conductive material according to any one of claims 18 to 20,
Wherein the first electrode and the second electrode are electrically connected by the conductive particles.

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