TWI667287B - Curable composition, conductive material, and connection structure - Google Patents

Abstract

The present invention provides a curable composition that can improve the adhesion of members to be connected.

The curable composition of the present invention contains a curable compound and at least one of a thermal curing agent and a light curing initiator. The curable compound is obtained by using a compound represented by the following formula (11) and a diol compound. The first compound obtained by the reaction is obtained by reacting a second compound having an isocyanate group and an unsaturated double bond with the first compound.

[化 1] R1OOC-X-COOR2‧‧‧ (11)

In the formula (11), X represents an alkylene group or a phenylene group having 2 to 10 carbon atoms, and R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Description

Curable composition, conductive material, and connection structure

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

The curable composition containing the curable compound is widely used in various applications such as electric, electronic, construction, and vehicles.

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

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

The anisotropic conductive material is used, for example, for connection between flexible printed substrates and glass substrates (FOG (Film on Glass, glass coating)), connection between semiconductor wafers and flexible printed substrates (COF (Chip on Film, film) (Flip-Chip)), the connection between semiconductor wafers and glass substrates (COG (Chip on Glass, glass-on-Chip)), and the connection between flexible printed substrates and glass epoxy substrates (FOB (Film on Board, plate coating)), etc. .

In addition, in recent years, the use of electronic devices equipped with a touch panel has increased. For example, touch panels are used in electronic devices such as mobile phones, smart phones, car navigation systems, and personal computers. Touch panels and the like use polyethylene terephthalate (PET) films Connection to the target component. Specifically, the touch panel may be a case where a PET film having a silver electrode or the like formed therearound and a flexible printed circuit board are joined by a curable composition. In recent years, the market size of connection structures using PET films has expanded.

As an example of the above-mentioned anisotropic conductive material, Patent Document 2 below includes a hardener that generates free radicals upon heating, a hydroxyl-containing resin having a molecular weight of 10,000 or more, a phosphate ester, a radical polymerizable substance, and Anisotropic conductive material (curable composition) of conductive particles. Specific examples of the hydroxyl-containing resin include polymers such as polyvinyl butyral resin, polyvinyl formal, polyvinylamine, polyester, phenol resin, epoxy resin, and phenoxy resin.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-23503

[Patent Document 2] Japanese Patent Laid-Open No. 2005-314696

The conventional curable composition described in Patent Documents 1 and 2 has a problem that the adhesion of the connection target member is low. In particular, the conventional curable composition has a problem that the PET film is easily peeled when the PET film is adhered.

An object of the present invention is to provide a curable composition capable of improving the adhesion of a member to be connected, and to provide a conductive material and a connection structure using the curable composition.

In addition, a limited object of the present invention is to provide a curable composition that can improve the adhesion of a PET film, and can suppress peeling of the PET film even if a PET film is adhered, and to provide a conductive material and a connection using the curable composition. Construct. In addition, the curable composition of the present invention is suitable for bonding PET films, but the use of the curable composition of the present invention is not limited to the bonding of PET films.

According to a broad aspect of the present invention, there is provided a hardenable composition containing a hardenable compound and a heat hardener, and the hardenable compound is a reaction using a compound represented by the following formula (11) and a diol compound The obtained first compound is obtained by reacting a second compound having an isocyanate group and an unsaturated double bond with the first compound.

[化 1] R1OOC-X-COOR2‧‧‧ (11)

In the formula (11), X represents an alkylene group or a phenylene group having 2 to 10 carbon atoms, and R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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

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

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

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

In a specific aspect of the curable composition of the present invention, the second compound has a (meth) acrylfluorenyl group as a group containing an unsaturated double bond, and in another specific aspect, the second compound is ( (Meth) acryloxyalkoxy isocyanate.

In a specific aspect of the curable composition of the present invention, the weight-average molecular weight of the curable compound is 8,000 or more and 50,000 or less.

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 the (meth) acrylic compound having a hydroxyl group.

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

In a specific aspect of the curable composition of the present invention, when the curable composition is cured at 140 ° C. and 10 seconds, the cured product has an elongation at break of 500% or more.

The curable composition of the present invention is preferably used for the adhesion of a polyethylene terephthalate film, and is preferably a curable composition for the subsequent application of a polyethylene terephthalate film. The hardenable composition of the present invention is suitable for the adhesion of a polyethylene terephthalate film in a touch panel, and is preferably a hardenable combination for the adhesion of a polyethylene terephthalate film in a touch panel. Thing.

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

In the above formula (1), R1 and R2 each represent a hydrogen atom or a methyl group, R3 and R4 each represent a hydrogen atom, a methyl group, or a phenyl group, X represents an alkylene or polyether group having 2 to 10 carbon atoms, and Y represents An alkylene group or a phenylene group having 2 to 10 carbon atoms, n1 and n2 represent 1 or 2, respectively, and m represents a weight-average molecular weight of the hardening compound represented by formula (1), which is an integer of 8,000 or more and 50,000 or less.

According to a wider aspect of the present invention, there is provided a conductive material including the above-mentioned curable composition and conductive particles.

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

In a specific aspect of the conductive material of the present invention, the conductive particles have solder on a surface other than the conductive surface.

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

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

According to a broad aspect of the present invention, there is provided a connection structure including: a first connection target member having a first electrode on a surface; a second connection target member having a second electrode on a surface; and a connection portion Wherein the first connection target member and the second connection target member are connected; and the connection portion is formed by hardening the conductive material, and the first electrode and the second electrode are electrically charged by the conductive particles Sexual connection.

The hardenable composition of the present invention contains a hardenable compound and a thermal hardener. The hardenable compound is a first compound obtained by using a reaction of a compound represented by formula (11) and a diol compound, and has an isocyanate. The second compound having a base and an unsaturated double bond is obtained by reacting the first compound with the first compound. Therefore, the adhesion of the member to be connected can be improved.

Since the curable composition of this invention contains the curable compound represented by Formula (1) and a thermosetting agent, the adhesiveness of the connection target member can be improved.

1‧‧‧ conductive particles

2‧‧‧ substrate particles

3‧‧‧ conductive layer

3A‧‧‧Second conductive layer

3B‧‧‧Solder Layer

3Ba‧‧‧ Molten solder layer

11‧‧‧ conductive particles

12‧‧‧ solder layer

21‧‧‧ conductive particles

51‧‧‧ connected structure

52‧‧‧The first connection target component

52a‧‧‧First electrode

53‧‧‧The second connection target component

53a‧‧‧Second electrode

54‧‧‧Connection Department

61‧‧‧ Connected Structure

62‧‧‧The first connection target component

62a‧‧‧first electrode

63‧‧‧The second connection target component

63a‧‧‧Second electrode

64‧‧‧Connection Department

71‧‧‧ connected structure

72‧‧‧The first connection target component

73‧‧‧The second connection target component

74‧‧‧ Connection Department

FIG. 1 is a view schematically showing the use of a hardening group including the first embodiment of the present invention. A front cross-sectional view of a connection structure obtained from a conductive material of a polymer and conductive particles.

FIG. 2 is a schematic front cross-sectional view of a connection structure obtained using a curable composition according to a second embodiment of the present invention.

FIG. 3 is a schematic cross-sectional view showing a front structure of a connection structure obtained using a curable composition according to a third embodiment of the present invention.

FIG. 4 is an enlarged cross-sectional view of a conductive particle and an electrode in the connection structure shown in FIG.

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

FIG. 6 is a cross-sectional view showing a modified example of the conductive particles.

FIG. 7 is a cross-sectional view showing another modified example of the conductive particles.

The details of the present invention will be described below.

(Sclerosing composition)

The curable composition of the present invention preferably contains a curable compound which is a first compound obtained by using a reaction of 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 is obtained by reacting the first compound. By using a reaction for obtaining the curable compound, for example, a curable compound represented by the formula (1) can be obtained. In order to harden the said hardening compound, the hardening composition of this invention contains a thermosetting agent.

[化 4] R1OOC-X-COOR2‧‧‧ (11)

In the formula (11), X represents an alkylene group or a phenylene group having 2 to 10 carbon atoms, and R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Moreover, it is preferable that the curable composition of this invention contains the hardening represented by following formula (1) Sexual compounds. The hardening compound represented by the formula (1) can be obtained, for example, by a method such as using a first compound obtained by reacting a compound represented by the formula (11) with a diol compound, and having an isocyanate group and The second compound having a saturated double bond reacts with the first compound. In order to harden the said hardening compound, the hardening composition of this invention contains a thermosetting agent.

In the above formula (1), R1 and R2 each represent a hydrogen atom or a methyl group, R3 and R4 each represent a hydrogen atom, a methyl group, or a phenyl group, X represents an alkylene or polyether group having 2 to 10 carbon atoms, and Y represents An alkylene group or a phenylene group having 2 to 10 carbon atoms, n1 and n2 represent 1 or 2, respectively, and m represents a weight-average molecular weight of the hardening compound represented by formula (1), which is an integer of 8,000 or more and 50,000 or less.

Since the curable composition of the present invention has the above-mentioned composition, the adhesion of the connection target member can be improved. The reason for this is considered to be that the curable compound contains a skeleton structure having moderate flexibility.

Furthermore, since the curable composition of the present invention has the above-mentioned composition, the adhesion of a polyethylene terephthalate (PET) film can be improved particularly by the structure of the curable compound. The reason is considered to be that the above-mentioned curable compound contains not only a skeleton structure having a moderate flexibility but also a structure similar to PET.

In particular, the curable composition of the present invention can greatly improve the adhesiveness of a PET film, and can also improve the adhesiveness of other members to be connected.

Moreover, when the connection target member is connected using the curable composition of the present invention, the obtained connection structure does not easily peel off even when exposed to high temperature or high humidity.

The said curable composition contains the said thermosetting agent. Hardenability by heating The composition is hardened, thereby improving the adhesion of the connection target member. The said curable composition does not contain or contain the said photohardening initiator. It is preferable that the said hardening composition contains the said light hardening initiator from a viewpoint of hardening by hardening after hardening by irradiation of light, and hardening by hardening. On the other hand, from the viewpoint of increasing the ratio of hardening due to heating to further improve the adhesion of the connection target member, the hardenable composition may not contain the photohardening initiator. If the photo-curing initiator is not used, in order to harden the curable composition, only the heating may be performed without irradiation of light, so that the production efficiency of the connection structure is improved.

When the above-mentioned curable composition is cured under the conditions of 140 ° C. and 10 seconds, the elongation at break of the obtained cured product is preferably 500% or more, more preferably 700% or more. In addition, when the curable composition contained in the following conductive material is cured at 140 ° C. and 10 seconds, the elongation at break of the obtained cured product is preferably 500% or more, and more preferably 700% or more. . When the elongation at break is greater than or equal to the above lower limit, the adhesion of members to be connected can be further improved, and in particular, the adhesion of the PET film can be further improved. In addition, regarding the curable composition contained in the conductive material at the time of measuring the elongation at break, the curable composition (a mixture of various formulation components other than the conductive particles) used when the conductive material is prepared, A curable composition that removes conductive particles from a conductive material may also be used.

The elongation at break refers to the value of the elongation at the distance between the chucks when the hardened product is stretched under conditions of 23 ° C., a tensile speed of 1 mm / min, and a distance between the chucks using a tensile tester.

In order to further improve adhesion, the curable composition of the present invention preferably contains a quaternary ammonium salt compound or a (meth) acrylic compound having a hydroxyl group. In this case, in order to effectively improve adhesion, the curable composition of the present invention may include both the above-mentioned quaternary ammonium salt compound and the above-mentioned (meth) acrylic compound having a hydroxyl group. In order to further improve adhesion and to suppress peeling at high temperatures, the curable composition of the present invention preferably contains the above-mentioned quaternary ammonium salt compound. In order to further improve the adhesion, the present invention The chemical composition preferably contains the above-mentioned (meth) acrylic compound having a hydroxyl group.

Hereinafter, details of each component which can be used for the curable composition of this invention are demonstrated.

[Sclerosing compound]

The hardenable compound is obtained by using a first compound obtained by reacting a compound represented by formula (11) with a diol compound, and performing a second compound having an isocyanate group and an unsaturated double bond with the first compound. Obtained by reaction. The above reaction is a dehydration condensation reaction or a dealcoholization reaction. The compound represented by the formula (11) may be used alone or in combination of two or more. These diol compounds may be used alone or in combination of two or more. In order to obtain the curable compound, the first compound may be used alone, or two or more kinds may be used in combination. In order to obtain the curable compound, the second compound may be used alone or in combination of two or more.

The weight-average molecular weight of the curable compound is preferably 8,000 or more, more preferably 10,000 or more, and more preferably 50,000 or less, and more preferably 30,000 or less. When the said weight average molecular weight is more than the said minimum, the adhesiveness of the connection target member will improve further. When the said weight average molecular weight is below the said upper limit, the compatibility of a hardenable compound and another component will improve.

The said weight average molecular weight shows the weight average molecular weight at the time of polystyrene conversion measured by the gel permeation chromatography (GPC). The above-mentioned weight average molecular weight can be measured under conditions of a solvent THF (tetrahydrofuran, tetrahydrofuran), a flow rate of 1 mL / min, and a detector: differential refraction using a "Prominence GPC system" manufactured by Shimadzu Corporation.

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

From the viewpoint of further improving the adhesiveness of the connection target member, especially the PET film, X in the formula (11) is preferably a phenyl group, and the compound represented by the formula (11) is preferably A compound represented by the following formula (11A). To further improve the connection From the standpoint of improving the adhesiveness of the target member, particularly the PET film, the curable composition preferably contains a curable compound represented by the following formula (11A) by using the curable compound. The first compound obtained by the reaction of the compound and the diol compound is obtained by reacting a second compound having an isocyanate group and an unsaturated double bond with the first compound.

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

From the viewpoint of further improving the adhesion of members to be connected, especially the PET film, the compound represented by the formula (11) is preferably terephthalic acid, an alkyl terephthalate, and m-benzene. Dicarboxylic acid, or alkyl isophthalate. 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 the reactivity at the time of obtaining a hardening compound is excellent, when R1 and R2 in the said Formula (11), (11A), (11AA), and (11AB) are an alkyl group of 1-4 carbons, respectively In this case, the number of carbon atoms of the alkyl group is preferably 3 or less, more preferably 2 or less (methyl or ethyl), and even more preferably 1 (methyl).

Examples of the diol compound used to obtain the first compound include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1, 8-octanediol and the like.

In a specific aspect of the curable composition of the present invention, the curable composition preferably contains a third compound obtained by a reaction of a compound represented by the following formula (11B) and a diol compound. The compound represented by the following formula (11B) is a dicarboxylic acid or a dicarboxylic acid ester. The above reaction is a dehydration condensation reaction or a dealcoholization reaction. Moreover, in a specific aspect of the curable composition of the present invention, it is preferable that the curable composition contains a first compound obtained by using a reaction of a compound represented by the formula (11A) and a diol compound. Compounds, and a hardening compound obtained by reacting a second compound having an isocyanate group and an unsaturated double bond with the first compound; and using a compound represented by the following formula (11B) and a diol compound The third compound obtained by the reaction, and a hardening compound obtained by reacting a fourth compound (the same kind as the second compound) having an isocyanate group and an unsaturated double bond with the third compound; or containing a hardening compound A fifth compound obtained by reacting a compound represented by the above formula (11A), a compound represented by the following formula (11B), and a diol compound, and a sixth compound (with an isocyanate group and an unsaturated double bond) The second compound is the same kind) and is a curable compound obtained by reacting with the fifth compound. The use of these two hardening compounds can effectively improve the adhesion of members to be connected, especially the adhesion of PET films.

R1OOC-X-COOR2‧‧‧type (11B)

In the above formula (11B), R1 and R2 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 1 and the third compound may be separately synthesized and mixed, 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 perform the reaction together with the compound represented by the formula (11A) during the reaction.

Regarding the compound represented by the above formula (11B), more preferable compounds are those in which R1 and R2 represent a hydrogen atom or a methyl group, and X represents an alkylene group having 3 to 5 carbon atoms, and further preferable compounds are represented by R1 and R2 Methyl and X represent a compound having an alkylene group having 4 carbon atoms.

From the viewpoint of further improving the adhesiveness of the connection target member, particularly the PET film, the diol compound used to obtain the first compound is preferably a compound represented by the following formula (12), The (meth) acrylfluorenyl compound, polyester polyol compound or polyether polyol compound is more preferably a compound represented by the following formula (12) or a polyether polyol compound. From the viewpoint of further improving the adhesiveness of the connection target member, particularly the PET film, the diol compound used to obtain the first compound preferably contains a compound represented by the following formula (12).

[化 9] HO-R-OH‧‧‧ (12)

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 also represent an alkylene group having 2 to 10 carbon atoms. Examples of R in the formula (12) include ethylene, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. From the viewpoint of further improving the adhesiveness of the connection target member, especially the PET film, the number of carbon atoms of R in the formula (12) is preferably 6. 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 used to obtain the first compound and the diol compound used to obtain the third compound include 1,6-hexanediol.

The second compound preferably has a (meth) acrylfluorenyl group as a group containing an unsaturated double bond from the viewpoint of further improving the adhesiveness of the connection target member, particularly the PET film.

Examples of the diol compound used to obtain the first compound include bisphenol A and bisphenol F. The diol compound preferably contains bisphenol A or bisphenol F from the viewpoint of further improving the adhesiveness of the member to be connected, particularly the adhesiveness of the PET film. From the viewpoint of further improving the adhesiveness of the member to be connected, particularly the adhesiveness of the PET film, the diol compound preferably contains 1,6-hexanediol and bisphenol A or bisphenol F. In this preferred embodiment, only bisphenol A or bisphenol F may be used, and bisphenol A and bisphenol F may be used in combination.

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

Examples of the diol compound include polyester polyol compounds. The polyester polyol compound is obtained by dehydrating and condensing a carboxylic acid and a polyol. The carboxylic acid is preferably adipic acid or phthalic acid. The polyhydric alcohol is preferably ethylene glycol, 1,4-butanediol, or 1,6-hexanediol. The molecular weight of the polyester polyol compound is preferably 500 or more, more preferably 600 or more, and more preferably 2000 or less, and even more preferably 1500 or less.

The diol compound may be reacted with the compound represented by formula (11A) or the compound represented by formula (11B), or may be mixed with the compound represented by formula (11A) or represented by formula (11B). The compounds are reacted.

In 100% by weight of the diol compound used to obtain the first compound, the content of the compound represented by the formula (12) or 1,6-hexanediol is preferably 0% by weight (unused), more preferably It is preferably 10% by weight or more, more preferably 20% by weight or more, still more preferably 100% by weight (total amount) or less, and even more preferably 80% by weight or less. The content of bisphenol A and bisphenol F in 100% by weight of the above-mentioned diol compound used to obtain the first compound is preferably 0% by weight (unused), more preferably 20% by weight, and more preferably The content is 100% by weight or less, and more preferably 80% by weight or less.

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) acryloxyalkoxy isocyanate, 1,1- (bisacryloxymethyl) ethyl isocyanate, and 2- (methacrylic acid) 2-isocyanate ethoxy) ethyl ester and the like.

From the viewpoint of further improving the adhesiveness of the connection target member, and particularly the adhesiveness of the PET film, the second compound is preferably (meth) acryloxyalkoxy isocyanate, or methacrylic acid 2- (2 -Isocyanate ethoxy) ethyl ester, more preferably 2- (2-isocyanate ethoxy) ethyl methacrylate.

The hardening compound represented by the formula (1) can be obtained by, for example, using a first compound obtained by reacting a compound represented by the formula (11) with a diol compound, It is obtained by a method of reacting the 2 compound with the first compound and 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 hardening compound represented by the above formula (1) can be made into an isocyanate group and an unsaturated double bond by, for example, using a first compound obtained by reacting the compound represented by the formula (11) with a diol compound. It is obtained by a method other than a method of reacting the second compound with the first compound.

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

Examples of the alkylene group of X in the above formula (1) include ethylene, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl Wait. From the viewpoint of improving flexibility, hexyl is preferred.

Examples of the polyether group of X in the formula (1) include a polyether group represented by the following formula (2).

-(R3-O) q-‧‧‧ (2)

In the above formula (2), R3 is a linear alkylene group having 1 to 6 carbon atoms, and q represents the formula (1) The weight average molecular weight of the curable compound shown is an integer of 8,000 or more and 50,000 or less. The molecular weight of q in the formula (2) is preferably 650 or more, more preferably 1,000 or more, and more preferably 2,000 or less. From the viewpoint of improving flexibility, when R3 in the formula (2) is a linear alkylene group, the carbon number of R3 is preferably 2 or more, and more preferably 4 or less. Moreover, a plurality of -R3-0- groups may be the same or different.

The hardening compound represented by the above formula (1) is preferable from the viewpoints that the glass transition temperature of the hardened material is lowered, the tensile elastic modulus at low temperature is sufficiently low, and the hardening is performed more quickly at low temperature. It has a polyether group as X in said Formula (1). The connection structure may be exposed to a low temperature. By lowering the tensile modulus of elasticity at low temperature, the softness of the hardened material at low temperature becomes higher, and peeling at low temperature is less likely to occur.

In 100% by weight of the curable compound represented by the formula (1), the ratio of the polyether-based structural portion (for example, the ratio of the structural portion represented by the formula (2)) is preferably 17% by weight or more, and more preferably It is 41% by weight or less, and more preferably 23% by weight or less.

Y in the above formula (1) represents an alkylene group or a phenylene group having 2 to 10 carbon atoms. The plurality of Ys may be the same or different. From the viewpoint of improving acid resistance, the hardening compound represented by the formula (1) is preferably both an alkylene group having a carbon number of 2 to 10 and a phenyl group as Y in the formula (1). From the viewpoint of improving flexibility, the hardening compound represented by the formula (1) preferably has a butyl group as Y in the formula (1). When Y in the formula (1) is a phenyl 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) preferably has a group represented by the following formula (3A) as Y in the formula (1).

[Thermal hardener]

Regarding the thermal hardener, examples of the thermal hardener that thermally hardens the hardening compound include an imidazole hardener, an amine hardener, a phenol hardener, a polythiol hardener, an acid anhydride, a thermal cation initiator, and a thermal free agent. Base generator and so on. These thermosetting agents may be used alone or in combination of two or more.

Among them, an imidazole hardener, a polythiol hardener, or an amine hardener is preferable because the hardenable composition can be hardened more quickly at a low temperature. Moreover, since the storage stability improves when the hardening compound which can harden | cure by heating is mixed with the said thermosetting agent, it is preferable that it is a latent hardening agent. 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 polymer material such as a polyurethane resin or a polyester resin.

From the viewpoint of further improving the adhesiveness of the connection target member, particularly the PET film, the thermal curing agent is preferably a thermal radical generator. The use of thermal radical generators is particularly effective in improving the adhesion of PET films.

The 1-minute half-life decomposition temperature of the thermal radical generator is preferably 100 ° C or higher, more preferably 110 ° C or higher, and preferably 150 ° C or lower, and more preferably 130 ° C or lower. When the 1-minute half-life temperature is equal to or higher than the above-mentioned lower limit, the storage stability of the composition becomes better. If the 1-minute half-life temperature is equal to or lower than the above-mentioned upper limit, the PET film as an adherend is less likely to be deformed and deteriorated at the temperature when it is hardened.

The imidazole curing agent is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl 2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-mesanthine And 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-mesanthine Isocyanuric acid adducts and the like.

The polythiol hardener is not particularly limited, and examples thereof include trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .

The amine hardener is not particularly limited, and examples thereof include hexamethylene diamine, octane diamine, secanediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [ 5.5] Undecane, bis (4-aminocyclohexyl) methane, m-phenylenediamine, and diaminodiphenylphosphonium.

Examples of the thermal cationic hardener include a fluorene-based cationic hardener, Based cationic hardeners and fluorene based cationic hardeners. Examples of the fluorene-based cationic hardener include bis (4-thirdbutylphenyl) fluorene hexafluorophosphate and the like. As above Cation hardener, trimethyl Tetrafluoroborate, etc. Examples of the fluorene-based cation hardener include tri-p-tolyl hexafluorophosphate and the like.

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

Examples of the azo compound include 2,2'-azobisisobutyronitrile, 1,1 '-(cyclohexane-1-carbonitrile), and 2,2'-azobis (2-cyclopropyl) Propionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (2-methylpropanoic acid) dimethyl.

Examples of the organic peroxide include hydroperoxide and dialkyl peroxide. Examples of the hydroperoxide include dicumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, third hexyl hydroperoxide, and Third butyl hydroperoxide and the like. Examples of the dialkyl peroxide include α, α'-bis (third butyl peroxide-m-isopropyl) benzene, dicumyl peroxide, and 2,5-dimethyl-2. , 5-bis (tertiary butyl peroxide) hexane, tertiary butyl cumene peroxide, tertiary butyl peroxide, and 2,5-dimethyl-2,5-bis (peroxide Third butyl) hexyne-3 and the like.

The content of the thermosetting agent is not particularly limited. Relative to the above-mentioned hardening compounds 100 parts by weight, each content of the thermal curing agent and the thermal 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, and more preferably 100 parts by weight or less. It is more preferably 75 parts by weight or less. When each content of the said thermosetting agent and the said thermal radical generator is more than the said minimum, it will be easy to fully harden a curable composition. If the respective contents of the thermal curing agent and the thermal radical generator are equal to or less than the upper limit described above, the remaining thermal curing agent that does not participate in curing is hardly left after curing, and the heat resistance of the cured product is further improved.

[Light hardening initiator]

The photo-curing initiator is not particularly limited, and examples thereof include acetophenone photo-curing initiator (acetophenone photo-radical generator) and benzophenone photo-curing initiator (benzophenone photo-curing agent). Free radical generator), 9-oxysulfur , Ketal photohardening initiator (ketal photoradical generator), haloketone, fluorenylphosphine oxide and fluorenylphosphonate. The light curing initiator may be used alone or in combination of two or more.

Specific examples of the acetophenone photocuring initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and 2-hydroxy-2-methyl- 1-phenylpropane-1-one, methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylbenzene Acetone and so on. Specific examples of the ketal photocuring initiator include benzophenone 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, and more preferably 2 parts by weight or less, and more preferably 1 part by weight or less based on 100 parts by weight of the curable compound. . When the content of the photocuring initiator is at least the above lower limit, it is easy to sufficiently harden the curable composition. In addition, the hardening composition is irradiated with light to be B-staged, and the flow of the hardening composition can be suppressed. If the content of the photocuring initiator is below the above upper limit, it is difficult for the remaining photocuring initiator that does not participate in curing to remain after the curing.

[Quaternary ammonium salt compound]

By using the above-mentioned quaternary ammonium salt compound, the adhesion of the connection target member is further improved. In addition, by using the above-mentioned quaternary ammonium salt compound, even if exposed to a high temperature, peeling is less likely to occur. These quaternary ammonium salt compounds may be used alone or in combination of two or more.

From the viewpoint of further improving the adhesiveness of the connection target member, especially the PET film, the above-mentioned quaternary ammonium salt compound is preferably an alkyl group having 8 to 18 carbon atoms. From the viewpoint of further improving the adhesiveness of the connection target member, particularly the PET film, the quaternary ammonium salt compound is preferably a compound represented by the following formula (31).

R1R2R3R4N ⁺ X ^- ... of formula (31)

In the formula (31), R1, R2, and R3 each represent a methyl group or an ethyl group, R4 represents an alkyl group having 8 to 18 carbon atoms, and X represents a bromine atom or a chlorine atom.

Examples of the quaternary ammonium salt compound include n-octyltrimethyl chloride, n-octyltrimethyl bromide, nonyltrimethyl bromide, decyltrimethyl bromide, and dodecyl chloride. Alkyltrimethyl, dodecyltrimethyl bromide, tetradecyltrimethyl chloride, cetyltrimethyl chloride, cetyltrimethyl bromide, ethyl bromide Cetyl dimethyl, heptadecyl trimethyl bromide, octadecyl trimethyl chloride, and octadecyl trimethyl bromide.

The total content of the quaternary ammonium salt compound and the (meth) acrylic compound having a hydroxyl group is preferably 0.1 part by weight or more, more preferably 3 with respect to 100 parts by weight of the total of the curable compound and the thermosetting agent. At least parts by weight, more preferably at least 5 parts by weight, and more preferably at most 50 parts by weight, more preferably at most 40 parts by weight, still more preferably at most 30 parts by weight, may be at most 8 parts by weight, and may also be at least 5 parts by weight. Part by weight or less. When the total content of the quaternary ammonium salt compound and the (meth) acrylic compound having a hydroxyl group is equal to or more than the lower limit and equal to or lower than the upper limit, the adhesion of the target member is further improved.

Based on 100 parts by weight of the total of the curable compound and the thermosetting agent, The content of the quaternary ammonium salt compound is 0 parts by weight (not contained), preferably 0.1 parts by weight or more, more preferably 3 parts by weight or more, and preferably 50 parts by weight or less, and more preferably 8 parts by weight or less. It is more preferably 5 parts by weight or less. When the above-mentioned quaternary ammonium salt compound is used, and the content of the quaternary ammonium salt compound is equal to or higher than the lower limit and lower than the upper limit, the adhesion of the target member is further improved, and peeling at high temperatures is further suppressed.

[(Meth) acrylic compound having a hydroxyl group]

By using the (meth) acrylic compound which has the said hydroxyl group, the adhesiveness of a connection target member is further improved. The (meth) acrylic compound having a hydroxyl group may be used alone or in combination of two or more.

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

The viscosity of the curable composition using the curable compound is relatively high. From the viewpoint of reducing the viscosity of the curable composition, the curable compound preferably contains 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 EBCRYL3701 (manufactured by DAICEL-ALLNEX), EBCRYL3703 (manufactured by DAICEL-ALLNEX), and EBCRYL3708 (manufactured by DAICEL-ALLNEX). The epoxy acrylate may be an epoxy acrylate having a structure in which a 2-hydroxyethyl acrylate is added to caprolactone at a molecular terminal and a diglycidyl ring opening structure of bisphenol A is used as a main skeleton.

From the viewpoint of further improving the adhesion of the target member, 4-hydroxybutyl (meth) acrylate, EBECRYL3701 (manufactured by DAICEL-ALLNEX Corporation), or EBECRYL3708 (manufactured by DAICEL-ALLNEX).

The content of the (meth) acrylic compound having a hydroxyl group is 0 parts by weight (not contained) or more, more preferably 0.1 parts by weight or more, based on 100 parts by weight of the total of the curable compound and the thermosetting agent. It is 3 parts by weight or more, more preferably 5 parts by weight or more, and preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and still more preferably 30 parts by weight or less. When the (meth) acrylic compound having a hydroxyl group is used, and the content of the (meth) acrylic compound having a hydroxyl group is equal to or greater than the lower limit and equal to or lower than the upper limit, the adhesion of the target member is further improved.

[Other ingredients]

When the member to be connected includes glass or PET (polyethylene terephthalate), from the viewpoint of further improving the adhesion between glass and PET, the hardening compound preferably contains (meth) acrylic Compound. Examples of the (meth) acrylic compound include phosphate (meth) acrylates such as acrylic morpholine, fluorimine (meth) acrylate, and (meth) acrylate urethane. The (meth) acrylic compound is a compound other than the curable compound. The (meth) acrylic compound is a compound having a (meth) acrylfluorenyl group. These (meth) acrylic compounds may be used alone or in combination of two or more.

The hardenable composition may further include, for example, a flux, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a hardening catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, and ultraviolet rays. Various additives such as absorbents, lubricants, antistatic agents and flame retardants.

The curable composition preferably contains a flux. By using a flux, the oxide film on the electrode surface is removed, and the conduction reliability between the electrodes can be improved. Details of the flux are described in the column of the conductive material described below.

The curable composition preferably contains a filler. By using a filler, the thermal linear expansion rate of a hardened | cured material is reduced. Specific examples of the filler include silicon dioxide and nitride. Aluminum, aluminum oxide, glass, boron nitride, silicon nitride, polysiloxane, carbon, graphite, graphene, and talc. The filler may be used singly or in combination of two or more kinds. If a filler with higher thermal conductivity is used, the formal hardening time is shortened.

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

(Conductive material)

The conductive material of the present invention includes the curable composition and conductive particles. Specifically, the conductive material of the present invention includes the curable compound, the thermosetting agent, and conductive particles obtained by reacting the second compound with the first compound. In this specification, a curable composition containing conductive particles is referred to as a conductive material. By using the conductive material of the present invention, it is possible to improve the adhesiveness of the connection target member and the reliability of conduction between the electrodes.

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

From the viewpoint of more efficiently disposing the conductive particles on the electrode, the viscosity at 25 ° C of the conductive material is preferably 100 Pa · s or more, more preferably 200 Pa · s or more, and preferably 800 Pa · s or less. , More preferably below 600Pa‧s.

The viscosity can be easily and appropriately adjusted by the type and amount of the ingredients. In addition, by using a filler, the viscosity can be relatively increased.

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

The conductive material is preferably an anisotropic conductive material. The above conductive materials can be used as a conductive paste, a conductive film, and the like. When the above-mentioned conductive material is a conductive film, a film containing no conductive particles may be laminated on a conductive film containing conductive particles. To further improve the connection object From the viewpoint of further improving the adhesiveness of the members, especially the PET film, the conductive material is preferably a paste-like conductive paste. The conductive material is preferably used for electrical connection between electrodes. The conductive material is preferably a circuit connection material.

The content of the curable compound obtained by reacting the second compound with the first compound in 100% by weight of the conductive material is preferably 50% by weight or more, more preferably 60% by weight or more, It is preferably 75% by weight or more, more preferably 100% by weight or less, and even more preferably 95% by weight or less. When the content of the curable compound is greater than or equal to the above lower limit, the adhesion of the connection target member is further improved, and in particular, the adhesion of the PET film is further improved. When the content of the curable compound is equal to or less than the above upper limit, the content of the conductive particles can be relatively increased, and the reliability of conduction between the electrodes can be further improved.

In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, still more preferably 10% by weight or more, It is more preferably 20% by weight or more, particularly preferably 25% by weight or more, most preferably 30% by weight or more, and preferably 80% by weight or less, more preferably 60% by weight or less, and even more preferably 50% by weight or less, It is particularly preferably 45% by weight or less, and most preferably 35% by weight or less. When the content of the conductive particles is equal to or more than the lower limit and equal to or less than the upper limit, it is easy to arrange a large number of conductive particles between the electrodes, and the conduction reliability is further improved. In addition, since the content of the hardenable compound and the like becomes moderate, the conduction reliability between the electrodes is further improved.

Hereinafter, details of each component of the conductive material that can be used in the present invention will be described.

[Conductive particles]

Examples of the conductive particles include conductive particles formed of a conductive material as a whole, and conductive particles having a substrate particle and a conductive layer disposed on a surface of the substrate particle.

The conductive particles are preferably conductive particles having at least an outer surface of solder. Conductive The outer surface of the sexual 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 is further improved by solder.

As the conductive particles having at least an outer surface of the solder, solder particles, particles having a base material particle, and a solder layer disposed on the surface of the base material particle can be used. Among these, it is preferable to use solder particles. By using solder particles, high-speed transfer or metal bonding strength can be further improved. When using conductive particles whose solder is at least on the outer surface, the solder particles may be collected between the first electrode and the second electrode. The conductive particles whose solder is at least on the outer surface may have the property that, when heated, the conductive particles existing in the region where the electrode is not formed are concentrated between the first electrode and the second electrode.

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

As shown in FIG. 5, the conductive particles are preferably conductive particles 21 as solder particles. The conductive particles 21 are formed of only solder. The conductive particles 21 do not have substrate particles at the core, and are not core-shell particles. Both the central portion and the outer surface of the conductive particles 21 are formed of solder.

From the viewpoint of more uniformly maintaining the connection distance between the members to be connected, particles having substrate particles and a solder layer disposed on the surface of the substrate particles may be used.

In the modified example shown in FIG. 6, the conductive particles 1 include a substrate particle 2 and a conductive layer 3 disposed on the surface of the substrate particle 2. The conductive layer 3 covers the surface of the substrate particles 2. The conductive particles 1 are coated particles whose surfaces are covered with the conductive layer 3 on the surface of the substrate particles 2.

The conductive layer 3 includes 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 include a second conductive layer 3A between the substrate particles 2 and the solder layer 3B. Therefore, the conductive particle 1 includes the substrate particles 2, the second conductive layer 3A disposed on the surface of the substrate particle 2, and the solder layer 3B disposed on the surface of the second conductive layer 3A. In this way, the conductive layer 3 may have a multi-layer structure or a multilayer structure of two or more layers. Made.

As described above, the conductive layer 3 in the conductive particles 1 has a double-layered structure. As another modified example shown in FIG. 7, the conductive particles 11 may have a solder layer 12 as a single-layer conductive layer. The conductive particles 11 include substrate particles 2 and a solder layer 12 disposed on the surface of the substrate particles 2. The solder layer 12 may be arranged on the surface of the substrate particles 2 so as to contact the substrate particles 2.

Among the conductive particles 1, 11, 21, the conductive particles 1 and 11 are more preferable because the thermal conductivity of the conductive material is easily lowered. By using the conductive particles provided with the substrate particles and the solder layer disposed on the surface of the substrate particles, it is easy to lower the thermal conductivity of the conductive material. From the viewpoint of further improving connection reliability and conduction reliability between electrodes, the conductive particles 21 are preferred.

Examples of the substrate particles include resin particles, inorganic particles other than metal particles, organic-inorganic mixed particles, and metal particles. From the viewpoint of efficiently disposing the conductive particles on the electrode, the substrate particles are preferably substrate particles other than metal, and are preferably resin particles, inorganic particles other than metal particles, or an organic-inorganic mixture. particle. The substrate particles may be copper particles. The substrate particles are preferably not metal particles.

The substrate particles are preferably resin particles made of a resin. When the electrodes are connected using conductive particles, the conductive particles are compressed by disposing the conductive particles between the electrodes and then crimping them. When the substrate particles are resin particles, the conductive particles are easily deformed during the compression bonding, and the contact area between the conductive particles and the electrode becomes large. Therefore, the conduction reliability between the electrodes is further improved.

As the resin for forming the resin particles, various organic substances 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; polymethacrylic acid Acrylic resins such as methyl ester and polymethyl acrylate; polyterephthalate Acid alkyl diesters, polycarbonates, polyamides, phenol formaldehyde resins, melamine-formaldehyde resins, benzoguanaldehyde formaldehyde resins, urea formaldehyde resins, phenol resins, melamine resins, benzoguanide resins, urea resins, epoxy resins, Saturated polyester resin, saturated polyester resin, polyethylene terephthalate, polyfluorene, polyphenylene ether, polyacetal, polyimide, polyimide, imine, polyetheretherketone, polyether , Divinylbenzene polymers, and divinylbenzene copolymers. Examples of the divinylbenzene-based copolymer and the like include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylate copolymer. Since the hardness of the resin particles can be easily controlled to an appropriate range, the resin used to form the resin particles is preferably a polymer obtained by polymerizing one or two or more polymerizable monomers having an ethylenically unsaturated group. Thing.

When the above-mentioned resin particles are obtained by polymerizing a monomer having an ethylenically unsaturated group, examples of the monomer having an ethylenically unsaturated group include a non-crosslinkable monomer and a crosslinkable monomer.

Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and α-methylstyrene; carboxyl groups such as (meth) acrylic acid, maleic acid, and maleic anhydride Monomers; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (formyl) Base) lauryl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid alkyl esters; 2-hydroxyethyl (meth) acrylate, glyceryl (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc. (Meth) acrylates containing oxygen atoms; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; vinyl acetate, butyric acid Vinyl esters, vinyl laurate, vinyl stearate and other acid vinyl esters; unsaturated hydrocarbons such as ethylene, propylene, isoprene, butadiene; trifluoromethyl (meth) acrylate, (methyl) Halogen-containing monomers such as pentafluoroethyl acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene.

Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, and tetramethylolmethane di (meth) acrylic acid. Ester, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glyceryl tri (meth) acrylate, di (meth) acrylic acid Glyceride, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) 1,4-butanediol di (meth) acrylate, 1,4 -Multifunctional (meth) acrylates such as butanediol di (meth) acrylate; (iso) triallyl cyanurate, triallyl trimellitate, divinylbenzene, phthalic acid Diallyl ester, diallyl allylamine, diallyl ether, γ- (meth) acryl methoxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane, etc. Silane-containing monomers, etc.

When the substrate particles are inorganic particles or organic-inorganic mixed particles other than metals, examples of the inorganic substance used to form the substrate particles include silicon dioxide and carbon black. The inorganic substance is preferably not a metal. The particles formed from the above-mentioned silicon dioxide are not particularly limited, and examples thereof include hydrolysis of a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, and calcination if necessary. And obtained particles. Examples of the organic-inorganic mixed particles include organic-inorganic mixed particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

When the substrate particles are metal particles, examples of the metal used to form the metal particles include silver, copper, nickel, silicon, gold, and titanium. When the substrate particles are metal particles, the metal particles are preferably copper particles. However, it is preferred that the substrate particles are not metal particles.

The melting point of the substrate particles is preferably higher than the melting point of the solder layer. The melting point of the substrate particles is preferably more than 160 ° C, more preferably more than 300 ° C, even more preferably more than 400 ° C, and even more preferably more than 450 ° C. The melting point of the substrate particles may not reach 400 ° C. The melting point of the substrate particles may be 160 ° C or lower. The softening point of the substrate particles is preferably 260 ° C or higher. The softening point of the substrate particles may not reach 260 ° C.

The conductive particles may have a single-layer solder layer. The conductive particles may have a plurality of conductive layers (a solder layer and a second conductive layer). That is, two or more conductive layers may be laminated on the conductive particles. Optionally, the solder particles may be particles formed of a plurality of layers.

The solder forming the solder layer and the solder particles forming the solder are preferably low-melting metals having a melting point of 450 ° C or lower. The solder layer is preferably a low-melting metal layer having a melting point of 450 ° C or lower. The low melting point metal layer is a layer containing a low melting point metal. The solder particles are preferably low-melting metal particles having a melting point of 450 ° C or lower. The low-melting metal particles are particles containing a low-melting metal. The low melting point metal refers to a metal having a melting point of 450 ° C or lower. The melting point of the low melting point metal is preferably 300 ° C or lower, and more preferably 160 ° C or lower. The solder layer and the solder particles preferably contain tin. The content of tin in 100% by weight of the metal contained in the solder layer and 100% by weight of the metal contained in the solder particles is preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 70% by weight or more, particularly preferably 90% by weight or more. When the content of tin in the solder layer and the solder particles is at least the above lower limit, the connection reliability between the conductive particles and the electrode is further improved.

In addition, the above-mentioned tin content can be measured by a high-frequency inductively coupled plasma emission spectrophotometer ("ICP-AES" manufactured by HORIBA, Ltd.) or a fluorescent X-ray analyzer ("EDX-800HS" manufactured by Shimadzu Corporation). ) And so on.

By using the above-mentioned solder particles and conductive particles having solder on a conductive surface, the solder melts and joins the electrodes, and the solder conducts electricity between the electrodes. For example, since the solder and the electrode are likely to make surface contact instead of point contact, the connection resistance becomes low. In addition, by using conductive particles having solder on a conductive surface, the bonding strength between the solder and the electrode becomes higher, and as a result, peeling of the solder and the electrode is less likely to occur, and the conduction reliability and connection reliability are effectively improved.

The low-melting-point metal constituting the solder layer and the solder particles is not particularly limited. The low melting point metal is preferably tin or an alloy containing tin. Examples of the alloy include a tin-silver alloy, Tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy, tin-zinc alloy, tin-indium alloy, etc. Among them, in terms of excellent wettability to the electrode, the above-mentioned low melting point metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy, and tin-indium alloy. More preferred are tin-bismuth alloys and tin-indium alloys.

The material constituting the solder (the solder layer and the solder particles) is preferably a filler material based on JIS Z3001: soldering term and having a liquidus of 450 ° C. or lower. Examples of the composition of the solder include metal compositions containing zinc, gold, silver, lead, copper, tin, bismuth, and indium. Among them, a low melting point and lead-free tin-indium based (117 ° C eutectic) or tin-bismuth based (139 ° C eutectic) is preferred. That is, the solder is preferably lead-free, and is preferably a solder containing tin and indium, or a solder containing tin and bismuth.

In order to further improve the bonding strength between the solder and the electrode, the solder layer and the solder particles may contain phosphorus, tellurium, and nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, germanium, cobalt, bismuth, and manganese. , Chromium, molybdenum, palladium and other metals. From the viewpoint of further improving the bonding strength between the solder and the electrode, the solder layer and the solder particles preferably contain nickel, copper, antimony, aluminum, or zinc. From the viewpoint of further improving the bonding strength between the solder layer or the solder particles and the electrode, the content of these metals for improving the bonding strength is preferably 0.0001% by weight or more in 100% by weight of the solder layer or 100% by weight of the solder particles. And is 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 ° C, more preferably more than 300 ° C, still more preferably more than 400 ° C, still more preferably more than 450 ° C, even more preferably more than 500 ° C, and most preferably more than 600 ° C. . Since the solder layer has a relatively low melting point, it melts during conductive connection. The second conductive layer is preferably not melted during conductive connection. The conductive particles are preferably used by melting solder, preferably used by melting the solder layer, and preferably used by melting the solder layer without melting the second conductive layer. Since the melting point of the second conductive layer is higher than the melting point of the solder layer, it is possible to prevent the second conductive layer from being melted during the conductive connection, and only the soldering can be performed. The material layer is melted.

The absolute value of the difference between the melting point of the solder layer and the melting point of the second conductive layer exceeds 0 ° C, preferably 5 ° C or more, more preferably 10 ° C or more, still more preferably 30 ° C or more, and even more preferably 50 ° C or more , Preferably 100 ° C or more.

The second conductive layer preferably contains a metal. The metal constituting the second conductive layer is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. Also, as the metal, tin-doped indium oxide (ITO) may be used. These metals may be used alone or in combination of two or more.

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 even 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 have a nickel layer or a gold layer, and even more preferably have a copper layer. By using conductive particles having these preferred conductive layers for connection between electrodes, the connection resistance between the electrodes is further reduced. In addition, a solder layer can be more easily formed on the surfaces of these preferred conductive layers.

The average particle diameter of the conductive particles is preferably 0.1 μm or more, more preferably 1 μm or more, and more preferably 100 μm or less, more preferably 80 μm or less, still more preferably 50 μm or less, and even more preferably 40 μm or less. When the average particle diameter of the conductive particles is greater than or equal to the above lower limit and less than or equal to the above upper limit, the contact area between the conductive particles and the electrode becomes sufficiently large, and it is not easy to form aggregated conductive particles when forming the conductive layer. In addition, the size is suitable for the conductive particles in the conductive material, the interval between the electrodes connected via the conductive particles does not become too large, and the conductive layer is not easily peeled from the surface of the substrate particles.

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

The thickness of the solder layer is preferably 0.005 μm or more, and more preferably 0.01 μm or more. The thickness is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 0.3 μm or less. When the thickness of the solder layer is greater than or equal to the above lower limit and less than or equal to the above upper limit, sufficient conductivity can be obtained, and the conductive particles will not become too hard, and the conductive particles will be sufficiently deformed during the connection between the electrodes. The thinner the thickness of 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 μm or less, and more preferably 2 μm or less.

The thickness of the second conductive layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, and more preferably 10 μm or less, more preferably 1 μm or less, and further preferably 0.3 μm or less. When the thickness of the second conductive layer is equal to or greater than the lower limit and equal to or lower than the upper limit, the connection resistance between the electrodes is further reduced. The thinner the second conductive layer is, 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 μm or less, and more preferably 1 μm or less.

When the conductive particles have only a solder layer as a conductive layer, the thickness of the solder layer is preferably 10 μm or less, and more preferably 5 μm or less. When the above conductive particles have a solder layer and another conductive layer (second conductive layer, etc.) different from the solder layer as the conductive layer, the total thickness of the solder layer and the other conductive layer different from the solder layer is preferably 10 μm. Hereinafter, it is more preferably 5 μm or less.

[Flux]

The conductive material preferably contains a flux. The flux is not particularly limited. As the flux, a flux generally used for soldering or the like can be used. These fluxes 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, phosphoric acid, a derivative of phosphoric acid, an organic halide, hydrazine, an organic acid, and Rosin, etc. Examples of the molten salt include ammonium chloride. Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid, and glutaric acid. Examples of the turpentine include activated turpentine and non-activated turpentine. The above flux Organic acids and turpentine having two or more carboxyl groups are preferred. The flux may be an organic acid having two or more carboxyl groups, or may be turpentine. By using an organic acid or rosin having two or more carboxyl groups, the reliability of conduction between electrodes is further improved.

The rosin is a rosin containing rosin acid as a main component. The flux is preferably rosin, and more preferably rosin acid. By using the better flux, the conduction reliability between the electrodes is further improved.

The melting point of the above-mentioned flux is preferably 50 ° C or higher, more preferably 70 ° C or higher, further preferably 80 ° C or higher, and more preferably 200 ° C or lower, more preferably 160 ° C or lower, even more preferably 150 ° C or lower, The temperature is more preferably 140 ° C or lower. If the melting point of the flux is above the lower limit and below the upper limit, the flux effect is more effectively exerted, 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 above-mentioned flux is particularly preferably 80 ° C to 140 ° C.

Examples of the above-mentioned flux having a melting point of 80 ° C to 190 ° C include succinic acid (melting point 186 ° C), glutaric acid (melting point 96 ° C), adipic acid (melting point 152 ° C), and pimelic acid (melting point 104). ℃), dicarboxylic acid such as suberic acid (melting point 142 ° C), benzoic acid (melting point 122 ° C), malic acid (melting point 130 ° C), and the like.

From the viewpoint of more efficiently disposing the solder on the electrode, the melting point of the above-mentioned flux is preferably lower than the melting point of the solder in the above-mentioned solder particles, more preferably 5 ° C or higher, and further preferably 10 ° C or lower. the above.

From the viewpoint of more efficiently disposing the solder on the electrode, the melting point of the above-mentioned flux is preferably lower than the reaction starting temperature of the above-mentioned thermosetting agent, more preferably 5 ° C or higher, and further preferably 10% lower. Above ℃.

The said flux may be disperse | distributed in the said hardenable composition or the said conductive material, and may adhere to the surface of electroconductive particle or solder particle.

In 100% by weight of the conductive material, the content of the flux is 0% by weight (unused), preferably 0.5% by weight or more, and preferably 30% by weight or less, more preferably 25% by weight. % By weight or less. The conductive material may also include a flux. If the content of the flux is above the above lower limit and below the above upper limit, it is more difficult to form an oxide film 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 more effectively removed.

(Connection structure)

By connecting the connection target members using the curable composition or the conductive material, a connection structure can be obtained.

The connection structure includes a first connection target member, a second connection target member, and a connection portion that connects the first connection target member and the second connection target member. The connection portion is formed by curing the curable composition or curing the conductive material.

FIG. 1 is a front cross-sectional view schematically showing a connection structure obtained using a conductive material containing a curable composition according to a first embodiment of the present invention and a conductive particle.

The connection structure 51 shown in FIG. 1 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 that connects the first connection target member 52 and the second connection target member 53. The connection portion 54 is a hardened material layer, and is formed by hardening a conductive material including the conductive particles 1. In addition to the conductive particles 1, the conductive particles 11 or the conductive particles 21 may be used. In addition, conductive particles other than the conductive particles 1, 11, and 21 may be used.

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

In FIG. 4, the connection portion between the conductive particles 1 and the first and second electrodes 52 a and 53 a in the connection structure 51 shown in FIG. 1 is enlarged and shown in a front cross-sectional view. As shown in FIG. 4, in the connection structure 51, after the solder layer 3B in the conductive particles 1 is melted, the molten solder layer portion 3Ba is brought into full contact with the first and second electrodes 52a and 53a. That is, by using the conductive particles 1 whose surface layer is the solder layer 3B and the surface layer using the conductive layer is nickel, gold, or copper The contact area between the conductive particles 1 and the first and second electrodes 52a and 53a is larger than that in the case of metal conductive particles. Therefore, the conduction reliability and connection reliability of the connection structure 51 can be improved. Furthermore, in the case of using a flux, generally, the flux is gradually deactivated by heating. From the viewpoint of further improving the conduction reliability, the second conductive layer 3A is preferably in contact with the first electrode 52a, and the second conductive layer 3A is preferably in contact with the second electrode 53a.

FIG. 2 is a schematic front cross-sectional view of a connection structure obtained using a curable composition according to a second embodiment of the present invention.

The connection structure 61 shown in FIG. 2 includes a first connection target member 62, a second connection target member 63, and a connection portion 64 that connects the first connection target member 62 and the second connection target member 63. The connection portion 64 is a cured material layer, and 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 a surface (upper surface). The second connection target member 63 has a plurality of second electrodes 63a on the 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 contacting each other without using conductive particles. Therefore, the first and second connection target members 62 and 63 are electrically connected.

FIG. 3 is a schematic cross-sectional view showing a front structure of a connection structure obtained using a curable composition according to a third embodiment of the present invention.

The connection structure 71 shown in FIG. 3 includes a first connection target member 72, a second connection target member 73, and a connection portion 74 that connects the first connection target member 72 and the second connection target member 73. The connection portion 74 is a hardened material layer, and is formed by hardening a hardening 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 for the electrical connection of electrodes.

The manufacturing method of the said connection structure is not specifically limited. As an example of a method of manufacturing the connection structure, there may be mentioned a method in which the conductive material or the hardenable composition is arranged between the first connection target member and the second connection target member, and a laminated body is obtained. This laminated body is heated and pressurized. The aforementioned pressure is about 9.8 × 10 ⁴ to 4.9 × 10 ⁶ Pa. The heating temperature is about 120 to 220 ° C.

The first and second connection target members are not particularly limited. Specific examples of the first and second connection target members include electronic / electrical components such as metal members, resin members, and film members, electronic / electrical components such as electrical semiconductor wafers, capacitors, and diodes, and printed boards. Electronic / electrical components such as flexible printed boards, glass epoxy substrates, circuit boards such as FFC (flexible flat cable) and glass substrates. The first and second connection target members are preferably electronic / electrical components. The above-mentioned electronic / electrical components are members constituting electronic / electrical equipment. The connection structure is preferably an electronic / electrical component connection structure. The connection structure is preferably an electronic / electrical device.

The first and second connection target members are preferably connection target members for a touch panel. It is preferable that at least one of the said 1st and 2nd connection object members is a PET film in order to obtain the improvement effect of adhesiveness largely by using the said curable composition and the said conductive material.

The above-mentioned curable composition and the above-mentioned conductive material are suitably used for the adhesion of PET film and FFC (flexible flat cable), and are preferably those of PET film and FFC (flexible flat cable). The above-mentioned curable composition and the above-mentioned conductive material are suitable for the adhesion of a PET film in a touch panel, and are preferably a curable composition for the adhesion of a PET film in a touch panel.

The curable composition and the conductive material are not only suitable for bonding a PET film, but also suitable for bonding a resin film for a display and a flexible printed circuit board.

In addition, the hardenable composition and the conductive material are not only suitable for bonding FFC (flexible flat cable), but also suitable for bonding rigid substrates and FFC (flexible flat cable).

Examples of the electrode provided on the connection target member include a gold electrode and a nickel electrode. Electrode, tin electrode, aluminum electrode, copper electrode, silver electrode, molybdenum electrode and 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 above-mentioned electrode is an aluminum electrode, it may be an electrode formed of only aluminum or an electrode having an aluminum layer on the surface area 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 specifically described with examples and comparative examples. The present invention is not limited to the following examples.

(First test example) (Synthesis example 1)

Synthesis of hardenable compound (1): 40 g of dimethyl isophthalic acid, 100 g of 1,6-hexanediol, and 0.2 g of dibutyltin oxide as a catalyst were weighed and placed in a three-necked flask under vacuum The reaction was carried out at 120 ° C. for 4 hours while dehydrating by a Dean-Stark trap. Thereafter, 9 g of 2-isocyanate ethyl methacrylate and 0.05 g of dibutyltin dilaurate 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 hardenable compound (2): Weigh 37 g of dimethyl isophthalic acid, 3 g of dimethyl terephthalic acid, 100 g of 1,6-hexanediol, and 0.2 g of dibutyltin oxide as a catalyst. In a three-necked flask, the reaction was performed at 120 ° C. for 4 hours while dehydrating through a Dean-Stark separator under vacuum. Thereafter, 9 g of 2-isocyanate ethyl methacrylate and 0.05 g of dibutyltin dibutyl laurate were added and reacted at 120 ° C. for 4 hours to obtain a hardenable compound. Thing. The weight-average molecular weight of the obtained curable compound was 15,000.

(Synthesis example 3)

Synthesis of hardening compound (3): 40 g of dimethyl isophthalic acid, 20 g of 1,6-hexanediol, 15 g of bisphenol F, and 0.2 g of dibutyltin oxide as a catalyst were weighed and placed in a three-necked flask Under a vacuum condition, the reaction was performed at 120 ° C for 4 hours while dehydration was performed by a Dean-Stark separator. Thereafter, 9 g of 2-isocyanate ethyl methacrylate and 0.05 g of dibutyltin dilaurate 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 hardening compound (4): 15 g of dimethyl isophthalic acid, 25 g of dimethyl adipic acid, 20 g of 1,6-hexanediol, 15 g of bisphenol F, and dibutyltin oxide 0.2 as a catalyst g was weighed and placed in a three-necked flask, and reacted at 120 ° C. for 4 hours while dehydrating with a Dean-Stark separator under vacuum. Thereafter, 9 g of 2-isocyanate ethyl methacrylate and 0.05 g of dibutyltin dilaurate 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 hardening compound (5): 15 g of dimethyl isophthalic acid, 25 g of dimethyl adipate, 20 g of 1,6-hexanediol, 15 g of poly 1,4-butanediol having a molecular weight of 650, and As a catalyst, 0.2 g of dibutyltin oxide was weighed and placed in a three-necked flask, and reacted at 120 ° C. for 4 hours while dehydrating with a Dean-Stark separator under vacuum. Thereafter, 9 g of 2-isocyanate ethyl methacrylate and 0.05 g of dibutyltin dilaurate 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 hardening compound (1) obtained in Example 1 and 10 parts by weight of the acrylic compound (1) ("ACMO" manufactured by KOHJIN FILM & CHEMICALS) were blended, and solder particles ("Mitsubishi Metal Mining Corporation" " DS-10 ", SnBi eutectic, melting point 139 ° C, average particle size 12 μm) 30 parts by weight, thermosetting agent (" PEROCTA O "manufactured by Nippon Oil Corporation, 1 minute half-life temperature 124.3 ° C), and 0.2 parts by weight of silane coupling agent (Shin-Etsu Chemical Industry Co., Ltd., polymer-type polyfunctional amine-based silane coupling agent "X-12-972A") 0.2 parts by weight to obtain an anisotropic conductive paste.

(2) Production of connection structure (1)

As the adherend 1, a circuit board having 40 aluminum wirings with L / S = 200/200 μm formed on a base PET film was prepared. As the adherend 2, a FPC (Flexible Print Circuit, FPC) with 40 wirings was prepared on a base polyimide film with Cu wiring of L / S = 200/200 μm and base Ni by electroless plating Au. Flexible printed circuit board).

3 mg of an anisotropic conductive paste was applied to the adherend 1 through an air dispenser. The adherend 2 was set to have an overlap width of 3 mm, and the anisotropic conductive paste was used to overlap the adherend 1 and the adherend 2 in such a manner that the electrode patterns of the adherend 1 and the adherend 2 coincide. Then, it joined at 140 degreeC for 10 second under the pressure of 1 MPa, and obtained the connection structure (1).

(Example 2)

An anisotropic conductive paste and a connection 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. Construct (1).

(Example 3)

Production of connection structure (2): The anisotropic conductive paste obtained in Example 1 was used, and as the adherend 1, FFC (flexible flat cable) was used, and 40 was formed at L / S = 200/200 μm. Wiring Except for the body, the connection structure (2) was obtained in the same manner as the connection structure (1).

(Examples 4 to 11) (1) Preparation of conductive paste

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

The details of the (meth) acrylic compound are as follows.

(Meth) acrylic compound (2): "Ebecryl8413" manufactured by DAICEL-ALLNEX, aliphatic acrylic urethane

(Meth) acrylic compound (3): "Ebecryl 3708" manufactured by DAICEL-ALLNEX Corporation, which has a structure in which 2-hydroxyethyl acrylate is added to caprolactone at the molecular terminal, and has a diglycidyl group of bisphenol A Ring-opening structure epoxy acrylate as main skeleton

(Meth) acrylic compound (4): "Ebecryl168" manufactured by DAICEL-ALLNEX, phosphate ester (meth) acrylate such as hydroxyethyl methacrylate phosphate

(Meth) acrylic compound (5): "M-140" manufactured by Toya Synthesis Co., Ltd.

(2) Production of connection structure (3)

A connection structure (3) was obtained in the same manner as the connection structure (1), except that the obtained anisotropic conductive paste was bonded at 140 ° C for 5 seconds under a pressure of 1 MPa.

(3) Production of connection structure (4)

A connection structure (4) was obtained in the same manner as the connection structure (2), except that the obtained anisotropic conductive paste was bonded at a pressure of 1 MPa at 140 ° C for 5 seconds.

(Comparative example 1)

An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the type of the curable compound was changed to a bisphenol A type epoxy compound. Use the anisotropic guide obtained An electric paste was used to obtain a connection structure (1) in the same manner as in Example 1, a connection structure (2) was obtained in the same manner as in Example 3, and a connection structure was obtained in the same manner as in Examples 4 to 11 ( 3) and connection structure (4).

(Evaluation) (1) Initial adhesion

Using the obtained connection structure, peeling was performed using "Micro Autograph MST-I" manufactured by Shimadzu Corporation, and the 90 ° peel strength C was measured at 23 ° C at a tensile speed of 50 mm / minute. The initial adherence was determined based on the following criteria.

[Judgment Criteria for Initial Adhesion]

○○: 90 ° peel strength C is 20N / cm or more

○: 90 ° peel strength C is 15 N / cm or more and less than 20 N / cm

△: 90 ° peel strength C is 10N / cm or more and less than 15Ncm

×: 90 ° peel strength C is less than 10 N / cm

(2) Adhesion under high temperature and humidity

The obtained connection structure was left to stand in an environment of 85 ° C. and 85% humidity for 500 hours. With respect to the connection structure after being left to stand, the 90 ° peel strength D was measured in the same manner as in the evaluation of the adhesiveness (1) above. Adhesion under high temperature and high humidity was determined according to the following criteria.

[Criterion for Adhesion under High Temperature and High Humidity]

○○: 90 ° peel strength C is 20 N / cm or more and peel strength D / peel strength C × 100 is 80% or more

○: 90 ° peel strength C is 15 N / cm or more and less than 20 N / cm, and peel strength D / peel strength C × 100 is 80% or more

△: 90 ° peel strength C is 10 N / cm or more and less than 15 Ncm, and peel strength D / peel strength C × 100 is 80% or more

×: 90 ° peel strength C is less than 10 N / cm

(3) Reliability between the upper and lower electrodes

In the obtained connection structures (n = 15), the connection resistance between the upper and lower electrodes was measured by the four-terminal method, respectively. Calculate the average connection resistance. Furthermore, based on the relationship of voltage = current × resistance, the connection resistance can be obtained by measuring the voltage when a fixed current flows. The conduction reliability was determined based on the following criteria. The obtained connection resistance is a resistance of a connection portion in which a pair of electrodes are superposed.

[Judgment Criteria for Continuity Reliability]

○○: The average value of the connection resistance is 50mΩ or less

○: The average value of the connection resistance exceeds 50 mΩ and is 75 mΩ or less

△: The average value of the connection resistance exceeds 75 mΩ and is less than 100 mΩ

×: The average value of the connection resistance exceeds 100 mΩ

(4) Elongation at break

In the preparation of each of the conductive pastes of the Examples and Comparative Examples, except that no conductive particles were prepared, a curable composition containing no conductive particles was prepared in the same manner. The obtained curable composition was cured at 140 ° C and 10 seconds to obtain a cured product. The obtained cured product was stretched under conditions of 23 ° C., a stretching speed of 1 mm / minute, and a distance between chucks of 40 mm, and the elongation at break was measured.

The composition and results are shown in Table 1 below.

(Second Test Example) (Synthesis example 6)

Synthesis of hardenable compound (6): 64 g of dimethyl isophthalic acid, 19 g of dimethyl adipate, 38 g of 1,6-hexanediol, 90 g of poly 1,4-butanediol having a molecular weight of 650, and As a catalyst, 2 g of titanium tetrabutoxide was weighed and placed in a three-necked flask. The reaction was performed at 120 ° C. for 4 hours while the methanol was removed by a Dean-Stark separator under vacuum. Then, 6 g of 2-isocyanate ethyl acrylate and 0.6 g of dibutyltin dibutyl laurate were added, and it reacted at 120 degreeC for 4 hours, and obtained the hardening compound. The weight-average molecular weight of the obtained curable compound was 27,000.

(Synthesis example 7)

Synthesis of hardening compound (7): 58 g of dimethyl isophthalic acid, 17 g of dimethyl adipate, 40 g of 1,6-hexanediol, 94 g of poly 1,4-butanediol having a molecular weight of 650, and As a catalyst, 2 g of titanium tetrabutoxide was weighed and placed in a three-necked flask. The reaction was performed at 120 ° C. for 4 hours while the methanol was removed by a Dean-Stark separator under vacuum. Thereafter, 23 g of 2-isocyanate ethyl acrylate and 0.6 g of dibutyltin dilaurate were added and reacted at 120 ° C. for 4 hours to obtain a hardenable compound. The weight-average molecular weight of the obtained curable compound was 8,300.

(Example 12)

88.5 parts by weight of the hardenable compound (6) obtained in Preparation Example 6, 10 parts by weight of 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and a thermosetting agent ("PEROCTA O" manufactured by Nippon Oil Corporation) (1 minute half-life temperature: 124.3 ° C) 1.5 parts by weight, and then mixed and defoamed with a planetary stirring device to obtain a hardenable composition.

(Examples 13 to 35)

A curable composition was obtained in the same manner as in Example 1 except that the types and blending amounts of the blending components were changed to those shown in Tables 2 and 3 below.

(Evaluation) (1) Adherence

The test pieces were then produced in the following order. A hardening composition was coated on a SUS substrate (2cm × 7cm), and a PET film was placed thereon, and a smooth plate was pressed thereon to make the hardening composition a fixed thickness (80 μm) to obtain a laminated body. .

The obtained laminated body was heat-cured under conditions of 130 ° C. for 10 seconds and a pressure of 1 MPa to obtain a subsequent test piece.

Using the obtained test piece, peeling was performed with "Micro Autograph MST-I" manufactured by Shimadzu Corporation, and a 180 ° peel strength was measured at an extension speed of 300 mm / min in an environment of 23 ° C or 100 ° C. The initial adherence was determined based on the following criteria.

[Judgment Criteria for Initial Adhesion]

○○○: 180 ° peel strength is 1.5N / mm or more

○○: 180 ° peel strength is 1.0 / mm or more and less than 1.5N / mm

○: 180 ° peel strength is 0.5N / mm or more and less than 1.0N / mm

△: 180 ° peel strength is 0.25N / mm or more and less than 0.5N / mm

×: 180 ° peel strength is less than 0.25N / mm

(2) Hardenability

A test piece was prepared under the two conditions of a hardening time of 10 seconds and 30 seconds, and a test piece was produced in the same manner as the above-mentioned evaluation method of adhesiveness, and the 180 ° peel strength was measured. The hardenability was evaluated according to the following formula.

Hardness (%) = (180 ° peel strength at 10 seconds of hardening time) × 100/180 ° peel strength at 30 seconds of hardening time

[Critical criteria for 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 Tables 2 and 3 below.

(Third Test Example)

(Synthesis Example 8) Synthesis of hardenable compound which is not a hardenable compound represented by formula (1)

Synthesis of hardenable compound (8) (straight-chain polyester compound): 64.6 g of dimethyl adipate, 24.0 g of dimethyl isophthalic acid, 61.4 hexanediol, and as a catalyst 0.05 g of titanium tetrabutoxide was weighed and placed in a three-necked flask, and the reaction was carried out at 140 ° C for 4 hours while removing methanol, followed by a reaction at 140 ° C for 12 hours under reduced pressure. Thereafter, 6.3 g of 2-isocyanate ethyl acrylate and 0.6 g of dibutyltin dilaurate were added and reacted at 70 ° C. for 4 hours to obtain a curable compound (straight-chain polyester compound). The weight-average molecular weight of the obtained curable compound was 8,000.

(Synthesis example 9)

Synthesis of hardening compound (9) (straight-chain polyester compound): 56.7 g of dimethyl adipate, 21.1 g of dimethyl isophthalic acid, 51.2 of 1,6-hexanediol, and a molecular weight of 650 14.8 g of 1,4-butanediol (PTMG650) and 0.05 g of titanium tetrabutoxide as a catalyst were weighed and placed in a three-necked flask. The methanol was removed from the system while reacting at 140 ° C for 4 hours. The reaction was carried out under reduced pressure at 140 ° C for 12 hours. Thereafter, 6.4 g of 2-isocyanate ethyl acrylate and 0.6 g of dibutyltin dilaurate were added and reacted at 70 ° C. for 4 hours to obtain a curable compound (straight-chain polyester compound). The weight-average molecular weight of the obtained curable compound was 8,500.

(Synthesis example 10)

Synthesis of hardenable compound (10) (straight-chain polyester compound): 56.1 g of dimethyl isophthalic acid, 20.1 g of dimethyl adipate, 50.6 g of 1,6-hexanediol, and a molecular weight of 1,000 22.5 g of poly 1,4-butanediol (PTMG1000) and 0.05 g of titanium tetrabutoxide as a catalyst were weighed and placed in a three-necked flask, and the reaction was carried out at 140 ° C for 4 hours while removing methanol, and then under reduced pressure. The reaction was carried out at 140 ° C for 12 hours. Thereafter, 6.4 g of 2-isocyanate ethyl acrylate and 0.6 g of dibutyltin dibutyl laurate were added, and the mixture was reacted at 70 ° C. It should take 4 hours to obtain a curable compound (straight-chain polyester compound). The weight-average molecular weight of the obtained curable compound was 12,000.

(Synthesis example 11)

Synthesis of hardening compound (11) (straight-chain polyester compound): 47.0 g of dimethyl isophthalic acid, 17.5 g of dimethyl adipate, 42.4 g of 1,6-hexanediol, and a molecular weight of 2000 37.8 g of poly 1,4-butanediol (PTMG2000) and 0.05 g of titanium tetrabutoxide as a catalyst were weighed and placed in a three-necked flask. The reaction was carried out at 140 ° C for 4 hours while removing methanol, and then under reduced pressure. The reaction was carried out at 140 ° C for 12 hours. Thereafter, 5.3 g of 2-isocyanate ethyl acrylate and 0.65 g of dibutyltin dilaurate were added and reacted at 70 ° 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 hardenable compound (12) (straight-chain polyester compound): 41.8 g of dimethyl isophthalic acid, 15.5 g of dimethyl adipate, 37.7 g of 1,6-hexanediol, and a molecular weight of 3000 50.3 g of poly 1,4-butanediol (PTMG3000) and 0.05 g of titanium tetrabutoxide as a catalyst were weighed and placed in a three-necked flask. The reaction was carried out at 140 ° C for 4 hours while removing methanol, and then under reduced pressure. The reaction was carried out at 140 ° C for 12 hours. Thereafter, 4.7 g of 2-isocyanate ethyl acrylate and 0.4 g of dibutyltin dilaurate were added and reacted at 70 ° C. for 4 hours to obtain a curable compound (straight-chain polyester compound). The weight-average molecular weight of the obtained curable compound was 30,000.

(Synthesis example 13)

Synthesis of hardening compound (13) (straight-chain polyester compound): 56.1 g of dimethyl isophthalic acid, 20.1 g of dimethyl adipate, 50.6 g of 1,6-hexanediol, and a molecular weight of 1,000 22.5 g of polyethylene glycol (PEG1000) and 0.05 g of titanium tetrabutoxide as a catalyst were weighed and placed in a three-necked flask. The reaction was carried out at 140 ° C for 4 hours while removing methanol, and then at 140 ° C under reduced pressure. The reaction was continued for 12 hours. Thereafter, acrylic acid 2-isocyanate was added 6.4 g of ester-based ethyl esters and 0.6 g of dibutyltin dilaurate were reacted at 70 ° C. for 4 hours to obtain a hardenable compound (straight-chain polyester compound). The weight-average molecular weight of the obtained curable compound was 12,000.

(Synthesis example 14)

Synthesis of hardening compound (14) (straight-chain polyester compound): 51.9 g of dimethyl isophthalic acid, 19.3 g of dimethyl adipate, 47.8 g of 1,6-hexanediol, and a molecular weight of 2000 25.0 g of poly 1,4-butanediol (PTMG2000) and 0.05 g of titanium tetrabutoxide as a catalyst were weighed and placed in a three-necked flask, and the reaction was carried out at 140 ° C for 4 hours while removing methanol, and then under reduced pressure. The reaction was carried out at 140 ° C for 12 hours. Thereafter, 5.9 g of 2-isocyanate ethyl acrylate and 0.65 g of dibutyltin dilaurate were added and reacted at 70 ° C. for 4 hours to obtain a curable compound (straight-chain polyester compound). The weight-average molecular weight of the obtained curable compound was 18,000.

(Synthesis example 15)

Synthesis of hardening compound (15) (straight-chain polyester compound): 38.0 g of dimethyl isophthalic acid, 14.1 g of dimethyl adipate, 32.5 g of 1,6-hexanediol, and a molecular weight of 2000 61.1 g of poly 1,4-butanediol (PTMG2000) and 0.05 g of titanium tetrabutoxide as a catalyst were weighed and placed in a three-necked flask, and the reaction was carried out at 140 ° C for 4 hours while removing methanol, and then under reduced pressure. The reaction was carried out at 140 ° C for 12 hours. Thereafter, 4.3 g of 2-isocyanate ethyl acrylate and 0.4 g of dibutyltin dilaurate were added and reacted at 70 ° 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 hardening compound (16) (straight-chain polyester compound): 47.0 g of dimethyl terephthalic acid, 17.5 g of dimethyl adipate, 42.4 g of 1,6-hexanediol, and a molecular weight of 2000 37.8 g of poly 1,4-butanediol (PTMG2000) and 0.05 g of titanium tetrabutoxide as a catalyst were weighed and placed in a three-necked flask, while removing methanol at 140 ° C After the reaction was carried out for 4 hours, the reaction was carried out under reduced pressure at 140 ° C for 12 hours. Thereafter, 5.3 g of 2-isocyanate ethyl acrylate and 0.65 g of dibutyltin dilaurate were added and reacted at 70 ° 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 hardenable compound (17) (straight-chain polyester compound): 63.4 g of dimethyl adipate, 42.9 g of 1,6-hexanediol, and poly 1,4-butanediol (PTMG2000 with a molecular weight of 2000) 38.2 g, and 0.05 g of tetrabutoxytitanium as a catalyst were weighed and placed in a three-necked flask, and reacted at 140 ° C for 4 hours while removing methanol, and then reacted at 140 ° C for 12 hours under reduced pressure. Thereafter, 5.4 g of 2-isocyanate ethyl acrylate and 0.65 g of dibutyltin dilaurate were added and reacted at 70 ° 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)

After mixing 98.5 parts by weight of the hardenable compound (9) obtained in Preparation Example 9 with 1.5 parts by weight of a thermal hardener ("PEROCTA O" manufactured by Nippon Oil Corporation, 1 minute half-life temperature 124.3 ° C), the mixture was carried out using a planetary stirring device By mixing and defoaming, a curable composition is obtained.

(Examples 37 to 45)

A curable composition was obtained in the same manner as in Example 1 except that the types and blending amounts of the blending components were changed as shown in Table 4 below.

(Evaluation) (1) Glass transition temperature (Tg)

A 0.5mm thickness hardened product was made using a 0.5mm spacer and a hot press. About the obtained hardened | cured material, the glass transition temperature was calculated | required by DMA (Dynamic Mechanical Analyzer) (viscoelasticity measuring device) under the temperature rising condition of 10 degree-C / min. degree.

(2) Tensile elastic modulus at -30 ℃

Using a 0.5mm spacer and a hot press, a hardened material with a thickness of 0.5mm is made. The hardened | cured material was cut | disconnected to specific size (5.0 mm * 50 mm * 0.5 mmt). The tensile elastic modulus was determined at -30 ° C using a universal material testing machine ("Tensilon" manufactured by AND Corporation).

(2) Adherence

The test pieces were then produced in the following order. A hardening composition is coated on a SUS (Steel Use Stainless) substrate (2cm × 7cm), a PET film is placed thereon, and a smooth plate is pressed thereon to make the hardening composition a fixed thickness ( 80 μm) to obtain a laminate.

The obtained laminated body was heat-cured under conditions of 130 ° C. for 10 seconds and a pressure of 1 MPa to obtain a subsequent test piece.

Using the obtained test piece, peeling was performed with "Micro Autograph MST-I" manufactured by Shimadzu Corporation, and the 180 ° peel strength was measured at a tensile speed of 300 mm / minute under an environment of 23 ° C. The initial adherence was determined based on the following criteria.

[Judgment Criteria for Initial Adhesion]

○○○: 180 ° peel strength is 1.5N / mm or more

○○: 180 ° peel strength is 1.0 / mm or more and less than 1.5N / mm

○: 180 ° peel strength is 0.5N / mm or more and less than 1.0N / mm

△: 180 ° peel strength is 0.25N / mm or more and less than 0.5N / mm

×: 180 ° peel strength is less than 0.25N / mm

(4) Hardenability

A test piece was prepared under the two conditions of a hardening time of 10 seconds and 30 seconds, and a test piece was produced in the same manner as the above-mentioned evaluation method of adhesiveness, and the 180 ° peel strength was measured. The hardenability was evaluated according to the following formula.

Hardness (%) = (180 ° peel strength at 10 seconds of hardening time) × 100/180 ° peel strength at 30 seconds of hardening time

[Critical criteria for 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.

Claims (22)

A curable composition comprising a curable compound, which is a first compound obtained by using a reaction of a compound represented by the following formula (11) and a diol compound, and has an isocyanate group and an unsaturated group. The second compound having a double bond is obtained by reacting with the above-mentioned first compound, and a thermosetting agent. The weight-average molecular weight of the above-mentioned hardening compound is 8,000 or more and 50,000 or less. In the formula (11), X represents an alkylene group having 2 to 10 carbon atoms or represents a phenylene group, and R1 and R2 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 above formula (11) is a compound represented by the following formula (11A), In the formula (11A), R1 and R2 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, an alkyl terephthalate, isophthalic acid, or an alkyl isophthalate. The sclerosing composition according to any one of claims 1 to 3, wherein the diol compound comprises 1,6-hexanediol. The curable composition according to any one of claims 1 to 3, wherein the diol compound contains bisphenol A or bisphenol F. The curable composition according to any one of claims 1 to 3, 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 3, wherein the second compound has a (meth) acrylfluorenyl group as a group containing an unsaturated double bond. The curable composition according to claim 7, wherein the second compound is a (meth) acryloxyalkoxy isocyanate. The curable composition according to any one of claims 1 to 3, which comprises a quaternary ammonium salt compound or a (meth) acrylic compound having a hydroxyl group. The curable composition according to claim 9, comprising the above-mentioned quaternary ammonium salt compound. The curable composition according to claim 9, comprising the above-mentioned (meth) acrylic compound having a hydroxyl group. The curable composition according to any one of claims 1 to 3, wherein the thermal curing agent is a thermal radical generator. The hardenable composition according to any one of claims 1 to 3, wherein when the hardened composition is cured at 140 ° C and 10 seconds, the elongation at break of the hardened material obtained is 500% or more. The curable composition according to any one of claims 1 to 3, which is a curable composition for subsequent use of a polyethylene terephthalate film. The curable composition as claimed in claim 14, which is a curable composition for subsequent use of a polyethylene terephthalate film in a touch panel. A curable composition comprising a curable compound represented by the following formula (1) and a thermosetting agent, In the above formula (1), R1 and R2 each represent a hydrogen atom or a methyl group, R3 and R4 each represent a hydrogen atom, a methyl group or a phenyl group, X is an alkylene group having 2 to 10 carbon atoms or a polyether group, and It represents an alkylene group having 2 to 10 carbon atoms or represents a phenylene group, n1 and n2 represent 1 or 2, respectively, and m represents a weight-average molecular weight of the hardenable compound represented by formula (1), which is an integer of 8,000 to 50,000. A conductive material including the curable composition according to any one of claims 1 to 15 and conductive particles. The conductive material according to claim 17, wherein the content of the hardenable compound contained in the hardenable composition is 50% by weight or more. The conductive material according to claim 17 or 18, wherein the conductive particles have solder on an outer surface. A connection structure includes a first connection target member, a second connection target member, and a connection portion that connects the first connection target member and the second connection target member, and the connection portion is used by request The curable composition according to any one of items 1 to 15 is formed by curing. The connection structure of claim 20, wherein the first connection target member has a first electrode on the surface, the second connection target member has a second electrode on the surface, and the first electrode and the second electrode are brought into contact by Electrical connection. A connection structure comprising: a first connection target member having a first electrode on a surface; a second connection target member having a second electrode on a surface; and a connection portion that connects the first connection target member to the above The second connection target member; and the connection portion is formed by hardening the conductive material according to any one of claims 17 to 19, and the first electrode and the second electrode are electrically connected by the conductive particles. .