TWI402286B - A hardened composition, an anisotropic conductive material, and a connecting structure - Google Patents

Description

Curable composition, anisotropic conductive material and joint structure

The present invention relates to a curable composition, and more particularly to a curable composition which can obtain a cured product having a low coefficient of linear expansion and which is not easily peeled off from a circuit board or an electronic component or the like even when heated, and The anisotropic conductive material and the bonded structure of the curable composition are used.

Anisotropic conductive pastes, anisotropic conductive pastes, anisotropic conductive adhesives, anisotropic conductive films, or anisotropic conductive sheets, etc., have been widely known.

The anisotropic conductive material is used for connection between an IC (Integrated Circuit) wafer and a flexible printed circuit board, and connection of an IC chip to a circuit board having an ITO (Indium Tin Oxide) electrode. For example, after the conductive conductive material is placed between the electrode of the IC chip and the electrode of the circuit board, heating and pressurization are performed, whereby the electrodes can be connected to each other.

As an example of the above-mentioned anisotropic conductive material, Patent Document 1 listed below discloses an anisotropic conductive adhesive film containing a thermosetting insulating adhesive, conductive particles, an imidazole latent curing agent, and an amine latent curing agent. Patent Document 1 discloses that the connection reliability is excellent even when the anisotropic conductive adhesive film is cured at a relatively low temperature.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-115335

In recent years, in order to package an IC chip on a flexible printed circuit board by reflow soldering, a solder ball in which solder is formed into a spherical shape is used. The solder balls encapsulated on the electrodes of the IC wafer are melted and solidified by reflow soldering, thereby encapsulating the IC chips on the flexible printed circuit board. In addition, the term "reflow soldering" refers to a method in which an electronic component wafer is placed on an electrode of a substrate so as to be in contact with a solder-equipped electronic component wafer, and the solder is melted and solidified by heating to perform soldering.

At the time of reflow soldering, not only the IC chip or the flexible printed circuit board is heated, but also the anisotropic conductive material for connecting the electrodes is heated. In particular, when the cured product of the electrically conductive material is heated, the cured product of the oppositely conductive material may be peeled off from the IC wafer or the flexible printed circuit board. Therefore, there is a strong demand for an anisotropic conductive material which is not easily peeled off from an IC wafer or a flexible printed circuit board even when heated.

In the anisotropic conductive adhesive film described in Patent Document 1, the heating temperature necessary for the start of curing is relatively low. However, there is a problem that the linear expansion coefficient of the cured product of the anisotropic conductive adhesive film is high. Therefore, when the circuit board connected by using the above-described anisotropic conductive adhesive film is heated, the conductive conductive adhesive film may be peeled off from the circuit substrate. Therefore, the connection reliability between the electrodes may be lowered.

Moreover, in recent years, in order to efficiently connect the electrodes of a circuit board or an electronic component, it is required to reduce the heating temperature required for connection and to shorten the pressurization time. Further, since the circuit board or the electronic component is easily deteriorated by heating, it is strongly required to lower the heating temperature.

In the anisotropic conductive adhesive film described in Patent Document 1, the heating temperature necessary for the start of curing is relatively low. However, the anisotropic conductive adhesive film sometimes does not sufficiently perform a hardening reaction at a low temperature. In order to reliably connect the electrodes of the circuit board or the electronic component using the anisotropic conductive adhesive film, it is necessary to increase the heating temperature or heat for a long time. Therefore, it is sometimes impossible to efficiently connect the electrodes.

An object of the present invention is to provide a curable composition which can obtain a cured product which has a low coefficient of linear expansion and which is not easily peeled off from a circuit board or an electronic component even when heated, and an anisotropic conductive material using the curable composition. And the connection structure.

Further, a limited object of the present invention is to provide a cured object which can obtain not only a hardened material having a low coefficient of linear expansion but also can be rapidly hardened at a low temperature, and can be connected to a connecting member to be efficiently connected. A curable composition, and an anisotropic conductive material and a bonded structure using the curable composition.

According to a broader aspect of the present invention, there is provided a curable composition comprising a component having at least one of an epoxy group and a thiopyranyl group, and a hardener, wherein the above has an epoxy group and a thiopyranyl group The at least one component comprises a monomer having a compound represented by the following formula (1), a polymer bonded by at least two of the compounds, or a mixture of the monomer and the polymer:

[Chemical 1]

In the above formula (1), R1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a structure represented by the following formula (2), R2 represents an alkylene group having a carbon number of 1 to 5, and R3 represents a carbon number. It is an alkylene group of 1 to 5, X1 represents an oxygen atom or a sulfur atom, and X2 represents an oxygen atom or a sulfur atom:

[Chemical 2]

In the above formula (2), R4 represents an alkylene group having a carbon number of 1 to 5, and X3 represents an oxygen atom or a sulfur atom.

In a specific aspect of the curable composition of the present invention, the monomer having a compound represented by the above formula (1) in 100% by weight of the component having at least one of an epoxy group and a thiopyranyl group The polymer obtained by bonding at least two of the compounds or the mixture of the monomer and the polymer is in a range of from 5 to 100% by weight.

In the curable composition of the present invention, it is preferred that the component having at least one of an epoxy group and a thiopyranyl group further contains a monomer having an epoxy compound having a structure represented by the following formula (11), a polymer obtained by bonding at least two of the epoxy compounds or a mixture of the monomers and the polymer. At this time, the curable composition can be rapidly cured at a low temperature. Further, when the curable composition is used for the connection between the electrode of the circuit board and the electrode of the electronic component, the electrodes can be efficiently connected:

[Chemical 3]

In the above formula (11), R11 represents an alkylene group having a carbon number of 1 to 10, R12 represents an alkylene group having a carbon number of 1 to 10, and R13 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 10 or the following In the structure represented by the formula (12), R14 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a structure represented by the following formula (13):

[Chemical 4]

In the above formula (12), R15 represents an alkylene group having a carbon number of 1 to 10;

[Chemical 5]

In the above formula (13), R16 represents an alkylene group having a carbon number of 1 to 10.

In another specific aspect of the curable composition of the present invention, in the above formula (11), R13 and R14 are a hydrogen atom.

Further, in another specific aspect of the curable composition of the present invention, the epoxy compound having the structure represented by the above formula (11) in 100% by weight of the component having at least one of an epoxy group and a thiopyranyl group The monomer, the polymer obtained by bonding at least two of the epoxy compounds, or the mixture of the monomer and the polymer is in a range of from 1 to 50% by weight.

In another specific aspect of the curable composition of the present invention, the component having at least one of an epoxy group and a thiopyranyl group further contains an epoxy compound having a hetero ring containing a nitrogen atom.

Further, in another specific aspect of the curable composition of the present invention, the epoxy compound having a hetero ring containing a nitrogen atom is an epoxy compound represented by the following formula (16) or a compound of the following formula (17) Indicated epoxy compound:

[Chemical 6]

In the above formula (16), R21 to R23 each represent an alkylene group having a carbon number of 1 to 5, and Z represents an epoxy group or a hydroxymethyl group;

[Chemistry 7]

In the above formula (17), R24 to R26 each represent an alkylene group having a carbon number of 1 to 5; p, q and r each represent an integer of 1 to 5; and R27 to R29 represent an alkylene having a carbon number of 1 to 5, respectively. base.

In another specific aspect of the curable composition of the present invention, the epoxy compound having a hetero ring containing a nitrogen atom is triglycidyl isocyanurate or trishydroxyethyl triglycidyl triglycidyl ether.

In still another specific aspect of the curable composition of the present invention, the content of the epoxy compound having a nitrogen atom-containing heterocyclic ring in 100% by weight of the component having at least one of an epoxy group and a thiopyranyl group It is in the range of 0.1 to 10% by weight.

In another specific aspect of the curable composition of the present invention, the component having at least one of an epoxy group and a thiopyranyl group further comprises an epoxy compound having an aromatic ring.

In still another specific aspect of the curable composition of the present invention, the aromatic ring is a benzene ring, a naphthalene ring or an anthracene ring.

The anisotropic conductive material of the present invention contains a curable composition composed of the present invention and conductive particles.

The connection structure of the present invention includes a first electrical connection target member, a second electrical connection target member, and a connection portion that electrically connects the first and second electrical connection target members, and the connection portion is based on the present invention. The invention is formed by an anisotropic conductive material.

Further, the connection structure according to the present invention includes the first connection target member, the second connection target member, and a connection portion that connects the first and second connection target members, and the connection portion is formed by the curability according to the present invention. The composition is formed.

(Effect of the invention)

The curable composition of the present invention contains a monomer having a compound represented by the above formula (1), a polymer obtained by bonding at least two of the compounds, or a mixture of the monomer and the polymer. As well as a hardener, a hardened material having a low coefficient of linear expansion can be obtained.

Moreover, since the linear expansion coefficient of the cured product of the anisotropic conductive material of the present invention is low, if the anisotropic conductive material of the present invention is used for the connection between the electrode of the circuit substrate and the electrode of the electronic component, the electrical property can be improved. The reliability of the connection.

The invention is described in detail below.

(sclerosing composition)

The curable composition of the present invention contains a component having at least one of an epoxy group and a thiopyranyl group, and a curing agent. The component having at least one of an epoxy group and a thiopyranyl group contains a component (hereinafter sometimes abbreviated as component A): a monomer having a compound represented by the following formula (1), and at least two of A polymer formed by bonding a compound or a mixture of the monomer and the polymer.

The component A is a monomer having a compound represented by the following formula (1), a polymer obtained by bonding at least two of the compounds, and a mixture of the monomer and the polymer. One:

[化8]

In the above formula (1), R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or a structure represented by the following formula (2), R2 represents an alkylene group having a carbon number of 1 to 5, and R3 represents a carbon number. It is an alkylene group of 1 to 5, X1 represents an oxygen atom or a sulfur atom, and X2 represents an oxygen atom or a sulfur atom:

[Chemistry 9]

In the above formula (2), R4 represents an alkylene group having a carbon number of 1 to 5, and X3 represents an oxygen atom or a sulfur atom.

When the carbon number of the alkyl group exceeds 5, the curing rate of the curable composition may decrease, or the linear expansion coefficient of the cured product may become high. Further, when the carbon number of the alkylene group exceeds 5, the curing rate of the curable composition may decrease. When the carbon number of the alkyl group and the above alkyl group is small, the curing rate of the curable composition becomes high.

R1 in the above formula (1) is preferably an alkyl group having 1 to 3 carbon atoms or a structure represented by the above formula (2), more preferably a structure represented by the above formula (2). Further, the alkyl group may be an alkyl group having a linear structure or an alkyl group having a branched structure.

R2 in the above formula (1) is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group. R3 in the above formula (1) is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group. Further, the above alkylene group may be an alkylene group having a linear structure or an alkylene group having a branched structure. Further, the above R2 and the above R3 may be the same or different.

In the structure represented by the above formula (1), R2 and R3 may be bonded to any portion of the benzene ring of the fluorene structure. The compound having the structure represented by the above formula (1) is preferably a compound having a structure represented by the following formula (1A):

[化10]

In the above formula (1A), R1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a structure represented by the following formula (2), R2 represents an alkylene group having a carbon number of 1 to 5, and R3 represents a carbon number. It is an alkyl group of 1 to 5, X1 represents an oxygen atom or a sulfur atom, and X2 represents an oxygen atom or a sulfur atom.

X1 in the above formula (1) is an oxygen atom or a sulfur atom. X2 in the above formula (1) is an oxygen atom or a sulfur atom. When X1 and X2 in the above formula (1) are oxygen atoms, the melting point of the compound having the structure represented by the above formula (1) can be lowered, and the storage stability of the curable composition can be improved. When X1 and X2 in the above formula (1) are a sulfur atom, the curing rate of the curable composition can be accelerated, and the linear expansion coefficient of the cured product can be lowered. The above X1 and the above X2 may be the same or different.

R4 in the above formula (2) is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group. Further, the above alkylene group may be an alkylene group having a linear structure or an alkylene group having a branched structure. When the carbon number of the alkylene group is small, the curing rate of the curable composition becomes high.

In the structure represented by the above formula (2), R4 may be bonded to any portion of the benzene ring. The structure represented by the above formula (2) is preferably a structure represented by the following formula (2A):

[11]

In the above formula (2A), R4 represents an alkylene group having a carbon number of 1 to 5, and X3 represents an oxygen atom or a sulfur atom.

X3 in the above formula (2) is an oxygen atom or a sulfur atom. When X3 in the above formula (2) is an oxygen atom, the melting point of the compound having the structure represented by the above formula (1) can be lowered, and the storage stability of the curable composition can be improved. When X3 in the above formula (2) is a sulfur atom, the curing rate of the curable composition can be accelerated, and the linear expansion coefficient of the cured product can be lowered. The above X3 may be the same as or different from the above X1 and the above X2.

The compound having the structure represented by the above formula (1) may have a fluorene structure and the total amount of the epoxy group and the thiopyranyl group may be two or more, preferably having a fluorene structure and at least two epoxy groups. And at least one of at least two thiopyran groups. Since the curable composition of the present invention contains the above component A, a cured product having a low coefficient of linear expansion can be obtained.

Further, when conductive particles are added to the curable composition of the present invention, and the composition containing the conductive particles is used for inter-electrode connection between the electrode of the circuit board and the electrode of the electronic component, the electrode can be improved. The reliability of the connection between the two.

More specifically, the compound represented by the above formula (1) is a compound represented by the following formula (1B). The compound represented by the following formula (1B) is that R2 in the above formula (1A) is a methylene group, R3 is a methylene group, X1 is an oxygen atom, X2 is an oxygen atom, and R1 is represented by the above formula (2A). The structure is such that R4 in the above formula (2A) is a methylene group and X3 is an oxygen atom. Since X1, X2 and X3 in the above formulas (1) and (2) are oxygen atoms, the compound represented by the following formula (1B) is an epoxy compound:

[化12]

In addition, as a compound which has a structure represented by the above formula (1), a compound represented by the following formula (1C) is more specifically mentioned. The compound represented by the following formula (1C) is that R2 in the above formula (1A) is a methylene group, R3 is a methylene group, X1 is a sulfur atom, X2 is a sulfur atom, and R1 is represented by the above formula (2A). The structure is such that R4 in the above formula (2A) is a methylene group and X3 is a sulfur atom. Since X1, X2 and X3 in the above formulas (1) and (2) are sulfur atoms, the compound represented by the following formula (1C) is a compound containing a thiopyranyl group having a three-membered ring structure:

[Chemistry 13]

The compound having the structure represented by the above formula (1) is a monomer. In the present invention, a monomer having a compound represented by the above formula (1) or a monomer having the structure represented by the above formula (1) may be used instead of the monomer represented by the above formula (1). A polymer in which a compound is bonded. Among them, the component A is preferably a monomer having a compound represented by the above formula (1), a polymer obtained by bonding 2 to 10 of the compounds, or a monomer and a polymer thereof. The mixture is more preferably a monomer of the above compound, a polymer obtained by bonding 2 to 3 of the compound, or a mixture of the monomer and the polymer, and particularly preferably the monomer and the monomer. a mixture of polymers. When a polymer composed of more than 10 compounds having a structure represented by the above formula (1) is used, the viscosity of the curable composition may become too high. Further, when a monomer having a compound having the structure represented by the above formula (1) is synthesized, a polymer obtained by bonding two or three of the above monomers as a by-product, or two may be contained. The above monomers are bonded by the storage conditions.

The epoxy compound corresponding to the compound having the structure represented by the above formula (1) can be synthesized, for example, as follows.

The hydrazine compound having a hydroxyl group as a raw material compound, epichlorohydrin, sodium hydroxide, and methanol are mixed, cooled, and reacted. Thereafter, an aqueous sodium hydroxide solution was added dropwise. Further, the reaction was carried out after the dropwise addition to obtain a reaction liquid. Next, water and toluene were added to the reaction liquid, and the toluene layer was taken out. The toluene layer was washed with water and then dried to remove water and solvent. In this manner, an epoxy compound equivalent to the compound having the structure represented by the above formula (1) can be easily obtained. Further, a hydrazine compound having a hydroxyl group as a raw material compound can be purchased, for example, from JFE Chemical Co., Ltd. or the like.

Further, the thiopyranyl group-containing compound corresponding to the compound having the structure represented by the above formula (1) can be an epoxy group of an epoxy compound corresponding to the compound having the structure represented by the above formula (1). It is converted into a thiopyranyl group to synthesize. For example, after adding an epoxy compound as a raw material compound or a solution containing the epoxy compound to a solution containing a thiocyanate, a solution containing a thiocyanate is further added, whereby the epoxy group can be easily converted into Thiantyl.

In 100% by weight of the curable composition of the present invention, the content of the component A is preferably in the range of 5 to 60% by weight, more preferably 10 to 50% by weight. When the content of the above component A is too small, a cured product having a sufficiently low linear expansion coefficient may not be obtained. When the content of the component A is too large, the content of the curing agent is relatively small, and the component A or the like may not be sufficiently cured.

The content of the component A in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is preferably in the range of 5 to 100% by weight. Further, when the component A and the epoxy component other than the component A are used in combination, the content of the component A in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is preferably It is in the range of 5 to 90% by weight. When the content of the above component A is within the above preferred range, a cured product having a lower coefficient of linear expansion can be obtained. A more preferred lower limit of the content of the component A in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is 10% by weight, particularly preferably a lower limit of 15% by weight, and a higher upper limit is 80% by weight, particularly preferably, the upper limit is 60% by weight, and further preferably the upper limit is 30% by weight, and the particularly preferred upper limit is 20% by weight.

The component having at least one of an epoxy group and a thiopyranyl group preferably further contains an epoxy component (hereinafter sometimes referred to simply as an epoxy component B) as an epoxy component other than the component A: A monomer of an epoxy compound having a structure represented by the formula (11), a polymer obtained by bonding at least two of the epoxy compounds, or a mixture of the monomer and the polymer. The epoxy component B is a monomer having an epoxy compound having a structure represented by the following formula (11), a polymer obtained by bonding at least two epoxy compounds, and the monomer and the polymerization. Any of a mixture of things:

[Chemistry 14]

In the above formula (11), R11 represents an alkylene group having a carbon number of 1 to 10, R12 represents an alkylene group having a carbon number of 1 to 10, and R13 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 10 or the following In the structure represented by the formula (12), R14 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a structure represented by the following formula (13):

[化15]

In the above formula (12), R15 represents an alkylene group having a carbon number of 1 to 10;

[Chemistry 16]

In the above formula (13), R16 represents an alkylene group having a carbon number of 1 to 10.

When the carbon number of the above alkylene group in the above formulas (11) to (13) exceeds 10, the curing rate of the curable composition may decrease. In addition, when the carbon number of the alkyl group in the above formula (11) exceeds 10, the curing rate of the curable composition may decrease. When the alkylene group in the above formulas (11) to (13) and the carbon number of the above alkyl group are small, the curing rate of the curable composition becomes high.

R11 in the above formula (11) is preferably an alkylene group having a carbon number of 1 to 6, more preferably an alkylene group having a carbon number of 1 to 5, particularly preferably a carbon number of 1 to 3. The alkyl group, and more preferably the methylene group or the ethyl group, is particularly preferably a methylene group. R12 in the above formula (11) is preferably an alkylene group having a carbon number of 1 to 6, more preferably an alkylene group having a carbon number of 1 to 5, particularly preferably a carbon number of 1 to 3. The alkyl group, and more preferably the methylene group or the ethyl group, is particularly preferably a methylene group. Further, the above alkylene group may be an alkylene group having a linear structure or an alkylene group having a branched structure. Further, the above R11 and the above R12 may be the same or different.

R13 in the above formula (11) is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a structure represented by the above formula (12), more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. The structure represented by the above formula (12) is particularly preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a structure represented by the above formula (12), and further preferably a hydrogen atom, a methyl group or a The structure represented by the above formula (12) is particularly preferably a hydrogen atom, a methyl group or a structure represented by the above formula (12). R14 in the above formula (11) is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a structure represented by the above formula (13), more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. The structure represented by the above formula (13) is particularly preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a structure represented by the above formula (13), and further preferably a hydrogen atom, a methyl group or a The structure represented by the above formula (13) is particularly preferably a hydrogen atom, a methyl group or a structure represented by the above formula (13). Further, the alkyl group may be an alkyl group having a linear structure or an alkyl group having a branched structure. Further, the above R13 and the above R14 may be the same or different.

R15 in the above formula (12) is preferably an alkylene group having a carbon number of 1 to 6, more preferably an alkylene group having a carbon number of 1 to 5, particularly preferably a carbon number of 1 to 3. The alkyl group, and more preferably the methylene group or the ethyl group, is particularly preferably a methylene group. R16 in the above formula (13) is preferably an alkylene group having a carbon number of 1 to 6, more preferably an alkylene group having a carbon number of 1 to 5, particularly preferably a carbon number of 1 to 3. The alkyl group, and more preferably the methylene group or the ethyl group, is particularly preferably a methylene group. Further, the above alkylene group may be an alkylene group having a linear structure or an alkylene group having a branched structure.

The epoxy compound having the structure represented by the above formula (11) is characterized by having an unsaturated double bond and at least two epoxy groups. By using the above epoxy component B, the curable composition can be rapidly cured at a low temperature. Further, when the epoxy component B and the conductive particles are added to the curable composition, and the composition containing the epoxy component B and the conductive particles is used for connection between electrodes of a circuit board or an electronic component, The electrodes can be connected efficiently.

Examples of the epoxy compound having the structure represented by the above formula (11) include, in the above formula (11), R11 is a methylene group, R12 is a methylene group, R13 is a hydrogen atom, and R14 is a hydrogen atom. In the above formula (11), R11 is a methylene group, R12 is a methylene group, R13 is a structure represented by the following formula (14), and R14 is a hydrogen atom; and the above formula ( In the above), an epoxy compound in which R11 is a methylene group, R12 is a methylene group, and R13 and R14 are each a structure represented by the following formula (14):

[化17]

Since the curable composition can be hardened more rapidly at a low temperature, R13 and R14 in the above formula (11) are preferably a hydrogen atom. That is, the epoxy compound having the structure represented by the above formula (11) is preferably an epoxy compound having a structure represented by the following formula (11A):

[化18]

In the above formula (11A), R11 represents an alkylene group having a carbon number of 1 to 10, and R12 represents an alkylene group having a carbon number of 1 to 10.

Further, since the curable composition can be hardened more rapidly at a low temperature, it is more preferable that R11 in the above formula (11) is a methylene group, R12 is a methylene group, R13 is a hydrogen atom, and R14 is a hydrogen atom. An epoxy compound represented by the following formula (11B):

[Chemistry 19]

The epoxy compound having the structure represented by the above formula (11) is a monomer. In the present invention, a monomer having an epoxy compound having a structure represented by the above formula (11) or a monomer having the epoxy compound may be used in combination with at least two of the above formula (11). A polymer formed by bonding an epoxy compound having a structure. In particular, the epoxy component B is preferably a monomer having an epoxy compound having a structure represented by the above formula (11), a polymer obtained by bonding 2 to 10 epoxy compounds, or the single More preferably, the mixture of the body and the polymer is a monomer of the above epoxy compound, a polymer obtained by bonding two or three of the epoxy compounds, or a monomer and the polymer. A mixture, especially preferably a mixture of the monomer and the polymer. When a polymer composed of more than 10 epoxy compounds having a structure represented by the above formula (11) is used, the viscosity of the curable composition may become too high. In addition, when a monomer having an epoxy compound having a structure represented by the above formula (11) is used, a polymer obtained by bonding two or three of the above monomers as a by-product may be contained, or Two or more of the above monomers are bonded by the storage conditions.

In 100% by weight of the curable composition of the present invention, the content of the epoxy component B is preferably in the range of 10 to 50% by weight. When the content of the epoxy component B is too small, the curing rate at a low temperature may not be sufficiently increased. When the content of the epoxy component B is too large, the content of the curing agent is relatively small, and the component A, the epoxy component B, and the like may not be sufficiently cured.

The content of the epoxy component B in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is preferably in the range of 1 to 50% by weight. When the content of the above epoxy component B is in this preferred range, the curable composition can be hardened more rapidly at a low temperature. A more preferred lower limit of the content of the epoxy component B in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is 3% by weight, particularly preferably a lower limit of 5% by weight, and more preferably The upper limit is 40% by weight, and particularly preferably the upper limit is 30% by weight.

The curable composition of the present invention may further contain the above-mentioned component A and other epoxy components other than the epoxy component B (hereinafter also referred to as epoxy component C).

The component having at least one of an epoxy group and a thiopyranyl group is preferably an epoxy compound C3 containing a hetero ring having a nitrogen atom as the epoxy component C. By using the epoxy compound C3, the heat resistance of the cured product of the curable composition can be further improved. Moreover, since the heat resistance of the cured product can be further improved, the nitrogen atom-containing heterocyclic ring is preferably three skeleton.

Further, the component having at least one of an epoxy group and a thiopyran group may include the epoxy resin C1 other than the epoxy compound C3 as the epoxy component C. Further, the component having at least one of an epoxy group and a thiopyranyl group may further include the epoxy compound C3 other than the epoxy compound C3 and the epoxy resin C1.

The curable composition of the present invention preferably contains the above epoxy compound C2 or the above epoxy compound C3, more preferably contains the above epoxy compound C2, and particularly preferably contains the above epoxy compound C2 and the above epoxy compound. C3.

The composition containing the above epoxy component B has a relatively low viscosity. By using the epoxy component B and the epoxy compound C2 in combination, the viscosity of the curable composition can be improved. Moreover, by using the epoxy component B and the epoxy compound C3 in combination, the curing rate of the curable composition can be further increased, or the heat resistance of the cured product of the curable composition can be improved. In particular, by using the epoxy component B, the epoxy compound C2, and the epoxy compound C3 in combination, the curing rate of the curable composition can be increased, and the heat resistance of the cured product of the curable composition can be improved, and the coating can be easily applied. A curable composition.

In addition, the term "epoxy resin" generally means a polymer or prepolymer having a low molecular weight of two or more epoxy groups and having a molecular weight of 10,000 or less, or by the polymer or prepolymerization. A curable resin produced by ring-opening reaction of an epoxy group of a substance. The curable resin may be a thermosetting resin or a photocurable resin.

Specific examples of the epoxy resin C1 include a bisphenol epoxy resin, a novolac epoxy resin, and an epoxy resin having a naphthalene structure.

For example, ADEKA RESIN EP-3300S and ADEKA RESIN EP-3300E (all of which are manufactured by ADEKA Co., Ltd.) are mentioned as a commercial item of the said epoxy compound C2. The curable composition preferably contains at least one of ADEKA RESIN EP-3300S and ADEKA RESIN EP-3300E, more preferably ADEKA RESIN EP-3300S. By using these preferred commercial products, the viscosity of the curable composition can be effectively improved.

Further, the epoxy compound C2 is preferably an epoxy compound having an aromatic ring. The above component having at least one of an epoxy group and a thiopyranyl group preferably contains an epoxy compound having an aromatic ring. By using an epoxy compound having an aromatic ring, the curing speed of the curable composition can be accelerated, and the curable composition can be easily applied.

The above aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring, more preferably a benzene ring or a naphthalene ring. At this time, the curable composition can be applied more easily.

The epoxy compound having an aromatic ring may, for example, be resorcinol diglycidyl ether or 1,6-naphthalene diglycidyl ether, and particularly preferably resorcinol diglycidyl ether. By using resorcinol diglycidyl ether, the hardening rate of the curable composition can be accelerated, and the curable composition can be easily applied.

Since the hardening speed of the curable composition can be further accelerated, the above has three The skeleton epoxy compound C3 preferably has at least two epoxy groups, more preferably three epoxy groups.

The epoxy compound C3 is preferably an epoxy compound represented by the following formula (16) or the following formula (17). By using these preferred epoxy compounds, the curing rate of the curable composition can be accelerated, and the heat resistance of the cured product of the curable composition can be further improved:

[Chemistry 20]

In the above formula (16), R21 to R23 each represent an alkylene group having a carbon number of 1 to 5, Z represents an epoxy group or a hydroxymethyl group; and R21 to R23 may be the same or different;

[Chem. 21]

In the above formula (17), R24 to R26 represent an alkylene group having a carbon number of 1 to 5, respectively, p, q and r represent an integer of 1 to 5, respectively, and R27 to R29 represent a stretching of 1 to 5, respectively. alkyl. R24~R26 can be the same or different. p, q, and r may be the same or different. R27~R29 can be the same or different.

When the carbon number of R21 to R23 in the above formula (16) exceeds 5, the curing rate of the curable composition may be slow. When the carbon number of R21 to R23 is small, the curing rate of the curable composition becomes fast. R21 to R23 in the above formula (16) are each preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group or an ethylidene group, and particularly preferably a methylene group.

Z in the above formula (16) is preferably an epoxy group. At this time, the curing speed of the curable composition can be accelerated, and the heat resistance of the cured product of the curable composition can be further improved.

When the carbon number of R24 to R26 in the above formula (17) exceeds 5, the curing rate of the curable composition may be slow. When the carbon number of R24 to R26 is small, the curing rate of the curable composition becomes faster. R24 to R26 in the above formula (17) are each preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and particularly preferably an ethyl group.

Further, when p, q and r in the above formula (17) exceed 5, the curing rate of the curable composition may be slow. When p, q and r are small, the curing rate of the curable composition becomes fast. The p, q and r in the above formula (17) are preferably an integer of 1 to 3, more preferably 1 or 2, particularly preferably 1.

When the carbon number of R27 to R29 in the above formula (17) exceeds 5, the curing rate of the curable composition may be slow. When the carbon number of R27 to R29 is small, the curing rate of the curable composition becomes faster. R27 to R29 in the above formula (17) are each preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group or an ethylidene group, and particularly preferably a methylene group.

The epoxy compound C3 is more preferably an epoxy compound represented by the above formula (16). By using the epoxy compound represented by the above formula (16), the curing rate of the curable composition can be accelerated, and the heat resistance of the cured product of the curable composition can be further improved.

The above epoxy compound C3 is preferably trihydroxyethyl isocyanurate triglycidyl ether or triglycidyl isocyanurate, more preferably triglycidyl isocyanurate. In other words, the epoxy compound C3 is preferably an epoxy compound represented by the following formula (16A) or the following formula (17A), more preferably an epoxy compound represented by the following formula (16A). By using these preferred epoxy compounds, the hardening rate of the curable composition can be further increased:

[化22]

[化23]

The content of the epoxy component C in the 100% by weight of the curable composition is preferably in the range of 0.1 to 45% by weight.

The content of the epoxy compound C2 in the 100% by weight of the curable composition is preferably in the range of 20 to 40% by weight. By setting the content of the above epoxy compound C2 within this preferred range, the viscosity of the curable composition can be more effectively improved.

The content of the epoxy compound C2 in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is preferably in the range of 5 to 95% by weight. Further, it is preferred that the epoxy compound C2 is an epoxy compound having an aromatic ring, and the content of the compound having an aromatic ring in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is 5 Within the range of ~95% by weight. By setting the content of the epoxy compound C2 or the epoxy compound having an aromatic ring in the preferred range, the viscosity of the curable composition can be more effectively improved. A lower limit of the content of the epoxy compound C2 or the epoxy compound having an aromatic ring in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is 15% by weight, and particularly preferably, the lower limit is 35. The weight %, and more preferably, the upper limit is 75% by weight, and particularly preferably the upper limit is 60% by weight.

In 100% by weight of the curable composition, the content of the epoxy compound C3 is preferably in the range of 0.1 to 5% by weight, and the content of the epoxy compound C3 is further increased by the content of the epoxy compound C3. The hardening rate of the curable composition.

Further, the content of the epoxy compound C3 in 100% by weight of the component having at least one of the epoxy group and the thiopyranyl group is preferably in the range of 0.1 to 10% by weight. Further, it is preferred that the epoxy compound C3 is an epoxy compound having a hetero ring containing a nitrogen atom, and the above-mentioned one having at least one of an epoxy group and a thiopyranyl group having a nitrogen atom is contained in 100% by weight. The content of the heterocyclic epoxy compound is in the range of 0.1 to 10% by weight. By setting the content of the epoxy compound C3 or the epoxy compound having a hetero ring containing a nitrogen atom in the preferred range, the curing rate of the curable composition can be accelerated, and the cured product of the curable composition can be further improved. Heat resistance.

The viscosity (25 ° C) of the curable composition is preferably in the range of 20,000 to 100,000 mPa ‧ s.

Further, the chloride ion concentration of the curable composition is preferably 500 ppm or less. When the chlorine ion concentration is too high, the curing rate of the curable composition may be slow. Further, the chloride ion concentration can be measured, for example, by ICP (Inductively Coupled Plasma) luminescence analysis.

The above curing agent is not particularly limited. Examples of the curing agent include an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, and an acid anhydride. Among them, an imidazole curing agent, a polythiol curing agent or an amine curing agent is preferred because the curable composition can be cured more rapidly at a low temperature. Further, since the storage stability can be improved when the component having at least one of the epoxy group and the thiopyranyl group is mixed with the above-mentioned curing agent, a latent curing agent is preferred. The latent hardener is preferably a latent imidazole hardener, a latent polythiol hardener or a latent amine hardener. These hardeners may be used alone or in combination of two or more. Further, the curing agent may be coated with a polymer material such as a polyurethane resin or a polyester resin.

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 group. -2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-all three Or 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-all three Isocyanuric acid adducts, etc.

The polythiol curing agent is not particularly limited, and examples thereof include trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate or dipentaerythritol hexa-3-mercaptopropionate. Wait.

The amine curing agent is not particularly limited, and examples thereof include hexamethylenediamine, octanediamine, decanediamine, and 3,9-bis(3-aminopropyl)2,4,8,10-tetraspiro[ 5.5] undecane, bis(4-aminocyclohexyl)methane, m-phenylenediamine or diaminodiphenylphosphonium.

The content of the above curing agent is not particularly limited. It is preferred that the content of the curing agent is in the range of 1 to 40 parts by weight based on 100 parts by weight of the total of the components having at least one of the epoxy group and the thiopyranyl group. When the content of the above curing agent is less than 1 part by weight, the curable composition may not be sufficiently cured. When the content of the curing agent exceeds 40 parts by weight, the heat resistance of the cured product of the curable composition may be lowered. In addition, the "100 parts by weight of the total amount of the component having at least one of the epoxy group and the thiopyranyl group" means 100 parts by weight of the above component A when the epoxy component other than the component A is not contained. When the epoxy component other than the above component A is contained, it means 100 weight part of the total of the said component A and other epoxy components.

Further, when the curing agent is an imidazole curing agent or a phenol curing agent, it is preferably an imidazole hardener or 100 parts by weight based on 100 parts by weight of the total of the components having at least one of an epoxy group and a thiopyranyl group. The content of the phenol hardener is in the range of 1 to 15 parts by weight. Further, when the curing agent is an amine curing agent, a polythiol curing agent or an acid anhydride, it is preferably an amine with respect to 100 parts by weight of the total of the components having at least one of an epoxy group and a thiopyranyl group. The content of the hardener, the polythiol hardener or the acid anhydride is in the range of 15 to 40 parts by weight.

The curable composition of the present invention may further contain a solvent. For example, when the component A is in a solid state, when the component A in the solid state is added to the solvent, the component A is dissolved in the solvent, so that the dispersibility of the component A in the curable composition can be improved. Examples of the solvent include ethyl acetate, methyl cellulose, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran or diethyl ether.

The curable composition of the present invention may further contain a polymerizable compound in order to adjust the viscosity of the composition or to prevent wet diffusion of the applied composition. The polymerizable compound is not particularly limited. The polymerizable compound may, for example, be a crosslinkable compound or a non-crosslinkable compound. The polymerizable compound may be used alone or in combination of two or more.

The crosslinkable compound is not particularly limited. Specific examples of the crosslinkable compound include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-fluorene. Alcohol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di Methyl) acrylate, glycerol methacrylate acrylate, pentaerythritol tri(meth) acrylate, trimethylolpropane trimethacrylate, allyl (meth) acrylate, (meth) acrylate Vinyl ester, divinylbenzene, polyester (meth) acrylate, or (meth) acrylate urethane or the like.

The above non-crosslinkable compound is not particularly limited. Specific examples of the non-crosslinkable compound include ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. Isobutyl methacrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid-2- Ethylhexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, ( Dodecyl (meth)acrylate, tridecyl (meth)acrylate, or tetradecyl (meth)acrylate, and the like.

The content of the above polymerizable compound is not particularly limited. It is preferred that the content of the polymerizable compound is in the range of 10 to 60 parts by weight based on 100 parts by weight of the total of the components having at least one of the epoxy group and the thiopyranyl group. When the content of the above polymerizable compound is less than 10 parts by weight, the heat resistance of the cured product of the curable composition may be lowered. When the content of the above polymerizable compound exceeds 60 parts by weight, the viscosity of the curable composition may become too high.

Since the adhesion of the cured product of the curable composition to the adherend can be enhanced, the curable composition of the present invention preferably contains an adhesion regulator. The above-mentioned adhesion regulator is preferably a decane coupling agent.

The above decane coupling agent is not particularly limited. As the above decane coupling agent, for example, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl A Dimethoxyoxane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxy Decane, 3-aminopropyldimethylethoxydecane, 3-aminopropylmethyldiethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxylate Base decane, vinyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl trichloro decane, 3-mercaptopropyl trimethoxy decane, 3-mercaptopropyl methyl Dimethoxydecane, 3-chloropropyltrimethoxydecane, 3-chloropropyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxy Propyltriethoxydecane, ethyltrimethoxydecane, propyltrimethoxydecane, propyltriethoxydecane,dodecyltriethoxydecane,hexyltrimethoxydecane, tert-butyl Isobutyl diethoxy decane, methyl phenyl diethoxy decane, 3-condensation Glycidoxypropyltriethoxydecane or methylphenyldimethoxydecane. The decane coupling agent may be used alone or in combination of two or more.

The content of the above decane coupling agent is not particularly limited. It is preferred that the content of the above decane coupling agent is in the range of 4 to 20 parts by weight based on 100 parts by weight of the total of the components having at least one of the epoxy group and the thiopyranyl group. When the content of the above decane coupling agent is less than 4 parts by weight, the adhesion of the cured product of the curable composition to the adherend may decrease. When the content of the above decane coupling agent exceeds 20 parts by weight, the curable composition may hardly be cured.

The curable composition of the present invention preferably contains inorganic particles. By using the above inorganic particles, the latent heat expansion of the cured product of the curable composition can be suppressed. The inorganic particles are not particularly limited. Examples of the inorganic particles include cerium oxide, aluminum nitride, and aluminum oxide. The inorganic particles may be used alone or in combination of two or more.

The content of the above inorganic particles is not particularly limited. It is preferred that the content of the inorganic particles is in the range of 3 to 900 parts by weight based on 100 parts by weight of the total of the components having at least one of the epoxy group and the thiopyranyl group. When the content of the inorganic particles is less than 3 parts by weight, the latent heat expansion of the cured product of the curable composition may not be inhibited. When the content of the inorganic particles exceeds 900 parts by weight, the inorganic particles may not be sufficiently dispersed in the curable composition.

The curable composition of the present invention may also contain a polymerization initiator which generates a reactive species by light irradiation or heating. The curing rate of the curable composition can be further increased by using the above polymerization initiator.

The polymerization initiator is not particularly limited. Examples of the polymerization initiator include an acetophenone polymerization initiator, a ketal polymerization initiator, a halogenated ketone, a decylphosphine oxide, or a mercaptophosphonate. The acetophenone polymerization initiator is not particularly limited. Specific examples of the acetophenone polymerization initiator include 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone and 2-hydroxy-2-methyl-1. -Phenylpropan-1-one, methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-cyclohexylacetophenone Wait. Further, the ketal polymerization initiator is not particularly limited. Specific examples of the ketal polymerization initiator include benzoin dimethyl ketal and the like. The polymerization initiator may be used alone or in combination of two or more.

The content of the above polymerization initiator is not particularly limited. It is preferred that the content of the polymerization initiator is in the range of 2 to 10 parts by weight based on 100 parts by weight of the total of the components having at least one of the epoxy group and the thiopyranyl group. When the content of the polymerization initiator is less than 2 parts by weight, the effect of adding a polymerization initiator may not be sufficiently obtained. When the content of the polymerization initiator is more than 10 parts by weight, the adhesion of the cured product of the curable composition to the adherend may be lowered.

The method for producing the curable composition of the present invention is not particularly limited. Specific examples of the method for producing the curable composition include a method of preparing at least one of the epoxy group and the thiopyranyl group, the curing agent, and other components added as needed, and Mix thoroughly using a planetary mixer or the like.

The curable composition of the present invention can be used as a one-component adhesive for subsequent bonding of a liquid crystal panel or a semiconductor wafer or the like. The curable composition of the present invention may be a paste-like adhesive or a film-like adhesive.

The method of processing the curable composition of the present invention into a film-like adhesive is not particularly limited. For example, a method of applying the curable composition of the present invention to a substrate such as release paper to form a film-like adhesive agent; or adding a solvent to the curable composition of the present invention and applying it to a release paper The method of processing the film into a film-like adhesive or the like by volatilizing the solvent at a temperature lower than the activation temperature of the curing agent, and the like.

Examples of the method for curing the curable composition of the present invention include a method of heating a curable composition, a method of irradiating light to a curable composition, and then heating the curable composition; and a curable composition; A method of irradiating light and heating the curable composition at the same time.

The heating temperature at which the curable composition of the present invention is cured is preferably in the range of 160 to 250 ° C, more preferably in the range of 160 to 200 ° C. Since the curable composition of the present invention can be hardened at a low temperature, the energy required for heating can be reduced.

In the case of the prior curable composition, if the heating temperature is 200 ° C or lower, the curing time becomes long. For example, if the heating temperature is 200 ° C, the curing time is longer than 10 seconds. On the other hand, in the curable composition of the present invention, even if the heating temperature is 200 ° C or lower, the curing can be performed in a short time. For example, if the heating temperature is 200 ° C, the curing time may be as long as 10 seconds. . In the present specification, the term "low temperature" means a temperature of 200 ° C or lower.

Further, as a method of curing the curable composition of the present invention, when a method of irradiating light to the curable composition and then heating the curable composition is used, it can be used in a shorter period of time than the method of heating only The hardenable composition is hardened internally.

The light source used when the curable composition of the present invention is irradiated with light is not particularly limited. Examples of the light source include a light source having a sufficient light emission distribution at a wavelength of 420 nm or less. Further, specific examples of the light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, or a metal halide lamp. Among them, a chemical lamp is preferred. The chemical lamp can efficiently emit light in the active wavelength region of the polymerization initiator, and the amount of luminescence in the light absorption wavelength region of the components other than the polymerization initiator in the composition is small. Further, by using a chemical lamp, light can be efficiently obtained to reach the polymerization initiator present inside the composition.

For example, when a cleavage type polymerization initiator having an acetophenone group is contained, the light irradiation intensity in a wavelength region of 365 nm to 420 nm is preferably 0.1 to 100 mW/cm ² .

(transverse conductive material)

The anisotropic conductive material can be obtained by including the conductive particles in the curable composition of the present invention.

The conductive particles are electrically connected to each other between the electrically connected portions, for example, between the electrodes of the circuit board and the electrodes of the electronic component. The conductive particles are not particularly limited as long as they are at least conductive particles on the outer surface. Examples of the conductive particles include conductive particles in which a surface of an organic particle, an inorganic particle, an organic-inorganic hybrid particle, or a metal particle is coated with a metal layer, or a metal particle substantially composed only of a metal. . The metal layer is not particularly limited. Examples of the metal layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, and a metal layer containing tin.

The content of the above conductive particles is not particularly limited. It is preferred that the content of the conductive particles is in the range of 0.5 to 5 parts by weight based on 100 parts by weight of the total of the components having at least one of the epoxy group and the thiopyranyl group. When the content of the conductive particles is less than 0.5 parts by weight, the electrodes may not be reliably electrically connected to each other. When the content of the conductive particles exceeds 5 parts by weight, a short circuit may occur between adjacent electrodes which should not be turned on.

When the anisotropic conductive material is in a liquid or paste form, the viscosity (25 ° C) of the anisotropic conductive material is preferably in the range of 20,000 to 100,000 mPa ‧ s. When the viscosity is too low, the conductive particles may settle in the anisotropic conductive material. When the viscosity is too high, the conductive particles may not be sufficiently dispersed in the anisotropic conductive material.

Further, the chloride ion concentration of the anisotropic conductive material is preferably 500 ppm or less. When the chlorine ion concentration is too high, the curing rate of the curable composition contained in the anisotropic conductive material may be slow.

The anisotropic conductive material of the present invention can be used as an anisotropic conductive paste, an anisotropic conductive ink, an anisotropic conductive adhesive, an anisotropic conductive film, or an anisotropic conductive sheet. When the anisotropic conductive material containing the conductive particles of the present invention is used as a film-like adhesive such as an anisotropic conductive film or an anisotropic conductive sheet, it may be laminated on the film-like adhesive containing the conductive particles. A film-like adhesive that does not contain conductive particles.

(connection structure)

The connection structure member can be joined by using the curable composition of the present invention or the anisotropic conductive material of the present invention, whereby a connection structure can be obtained. The connection target member is preferably at least one of an electronic component and a circuit board.

Preferably, the connection structure includes a first connection target member, a second connection target member, and a connection portion that connects the first and second connection target members, and the connection portion is made of the anisotropic conductive material of the present invention or The curable composition of the present invention is formed. The connecting portion is a cured layer formed by curing the anisotropic conductive material of the present invention or the curable composition of the present invention.

It is preferable that the connection structure includes a first connection target member, a second connection target member, and a connection portion that electrically connects the first and second connection target members. The connecting portion is formed of the anisotropic conductive material of the present invention. Further, the joint portion is a cured layer formed by curing the anisotropic conductive material of the present invention.

The first and second connection target members may be the first and second electrical connection target members that are electrically connected. Examples of the first and second electrical connection target members include various electrical connection target members that are electrically connected to each other. For example, one of the first and second electrical connection target members may be an electrode of a circuit board, and the other may be an electrode of an electronic component wafer such as an IC wafer. Further, the first and second electrical connection target members are not necessarily both electrodes.

Fig. 1 is a front cross-sectional view schematically showing a connection structure using an anisotropic conductive material containing a curable composition according to an embodiment of the present invention and conductive particles.

The connection structure 1 shown in FIG. 1 includes a first connection target member 2, a second connection target member 3, and a connection portion 4 that electrically connects the first and second connection object members 2 and 3. The connecting portion 4 is a cured layer, and is formed by using an anisotropic conductive paste containing a plurality of conductive particles 5 as an anisotropic conductive material.

A plurality of electrodes 2b are provided on the upper surface 2a of the first connection member 2. A plurality of electrodes 3b are provided on the lower surface 3a of the second connection member 3. The second connection member 3 is laminated on the upper surface 2a of the first connection member 2 by interposing the cured layer 4 formed of the anisotropic conductive paste containing the conductive particles 1. The electrode 2b and the electrode 3b are electrically connected by the conductive particles 5.

Specific examples of the connection structure include a connection structure in which an electronic component wafer such as a semiconductor wafer, a capacitor wafer, or a diode wafer is mounted on a circuit board and electrically connected to electrodes on the circuit board. Examples of the circuit board include various printed circuit boards such as a flexible printed circuit board, and various circuit boards such as a glass substrate or a substrate on which a metal foil is laminated.

The method for producing the joined structure of the present invention is not particularly limited. For example, the above-described anisotropic conductive material is disposed between the first connection target member such as an electronic component or a circuit board, and the second connection member such as an electronic component or a circuit board, and the laminated body is obtained. Then, the laminated body is heated and pressurized, and the like.

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

In order to obtain an anisotropic conductive paste, the following materials were prepared.

(1) Ingredient A

As the component A, various compounds in which R1, R2, R3, X1 and X2 are groups shown in the following Tables 1 to 15 are prepared. Further, in Tables 1 to 15, when R1 has the structure represented by the formula (2A), it is referred to as "formula (2A)" in the column of R1, and further represents R4 and X3 in the formula (2A). Further, in the preparation, the component A is a mixture of a monomer and a polymer of the above compound.

(2) Epoxy component B

As the epoxy component B, various compounds in which R11, R12, R13 and R14 are groups shown in the following Tables 1 to 15 are prepared. Further, in the preparation, the epoxy component B is a mixture of a monomer and a polymer of the above compound.

(3) Epoxy component C

Epoxy resin C1: bisphenol A epoxy resin

Epoxy compound C2-1: ADEKA RESIN EP-3300S (made by ADEKA)

Epoxidized content C2-2: resorcinol diglycidyl ether

Epoxy compound C3-1: triglycidyl isocyanurate (epoxy compound represented by the above formula (16A))

Epoxy compound C3-2: trihydroxyethyl isocyanurate triglycidyl ether (epoxy compound represented by the above formula (17A))

(4) Solvent

Ethyl acetate

(5) Hardener

1,2-dimethylimidazole

Imidazole hardener (amine adduct type hardener, "Ajicure PN-23J" manufactured by Ajinomoto Fine-Techno Co., Ltd.)

Amine hardener (ethylenediamine)

Polythiol hardener ("TMMP: Trimethylolpropane tri-3-mercaptopropionate" manufactured by SC Organic Chemical Co., Ltd.)

Phenol curing agent (Sumilite-PR-HF-3 manufactured by Sumitomo Bakelite)

Anhydride ("YH-307" manufactured by Nippon Epoxy Co., Ltd.)

(Example 1)

As the component A, an epoxy compound represented by the above formula (1B) is prepared. In the compound represented by the above formula (1B), R2 in the above formula (1A) is a methylene group, R3 is a methylene group, X1 is an oxygen atom, X2 is an oxygen atom, and R1 is represented by the above formula (2A). The compound of the above formula (2A) wherein R4 is a methylene group and X3 is an oxygen atom.

100 parts by weight of a mixture of 100 parts by weight of an epoxy compound represented by the above formula (1B) and 20 parts by weight of ethyl acetate, and 7 parts by weight of cerium oxide particles having an average particle diameter of 0.02 μm, as the component A, 40% by weight of an imidazole hardener (amine adduct type hardener, "Ajicure PN-23J" manufactured by Ajinomoto Fine-Techno Co., Ltd.), 3-glycidoxypropyltriethoxydecane as a decane coupling agent 4.5 parts by weight and 2 parts by weight of the conductive particles having an average particle diameter of 3 μm were blended to obtain a composition. Further, the conductive particles to be used are conductive particles having a metal layer formed on the surface of the divinylbenzene resin particles and having a nickel plating layer and having a gold plating layer formed on the surface of the nickel plating layer.

The obtained composition was stirred at 2000 rpm for 8 minutes using a planetary mixer, and filtered using a nylon filter paper (pore size: 10 μm) to prepare an anisotropic conductive paste as an anisotropic conductive material.

(Example 2)

In place of 120 parts by weight of a mixture containing 100 parts by weight of the epoxy compound represented by the above formula (1B) and 20 parts by weight of ethyl acetate, 50 parts by weight of the epoxy compound represented by the above formula (1B) as the above component A is used. An anisotropic conductive paste was obtained in the same manner as in Example 1 except that 50 parts by weight of the epoxy compound represented by the above formula (11B) was used as the epoxy component B.

(Example 3)

In place of 120 parts by weight of a mixture containing 100 parts by weight of the epoxy compound represented by the above formula (1B) and 20 parts by weight of ethyl acetate, 30 parts by weight of the epoxy compound represented by the above formula (1B) as the above component A is used. 40 parts by weight of the epoxy compound represented by the above formula (11B) and 30 parts by weight of ADEKA RESIN EP-3300S (manufactured by Adeka Co., Ltd.) as the epoxy compound C2-1. An anisotropic conductive paste was obtained in the same manner as in Example 1.

(Example 4)

In place of 120 parts by weight of a mixture containing 100 parts by weight of the epoxy compound represented by the above formula (1B) and 20 parts by weight of ethyl acetate, 30 parts by weight of the epoxy compound represented by the above formula (1B) as the above component A is used. 40 parts by weight of the epoxy compound represented by the above formula (11B), 25 parts by weight of ADEKA RESIN EP-3300S (made by Adeka Co., Ltd.) as the epoxy compound C2-1, and the above-mentioned ring An anisotropic conductive paste was obtained in the same manner as in Example 1 except that 5 parts by weight of the epoxy compound represented by the above formula (16A) of the oxygen compound C3-1 was used.

(Comparative Example 1)

100 parts by weight of the bisphenol A type epoxy resin as the epoxy resin C1 and 5 parts by weight of 1,2-dimethylimidazole as a curing agent were blended, and stirred at 2000 rpm for 5 minutes using a planetary mixer to obtain a mixture. .

To the resulting mixture, 7 parts by weight of cerium oxide particles having an average particle diameter of 0.02 μm and 2 parts by weight of conductive particles having an average particle diameter of 3 μm were added to obtain a composition. Further, the conductive particles to be used are conductive particles having a metal layer formed on the surface of the divinylbenzene resin particles and having a nickel plating layer and a gold plating layer formed on the surface of the nickel plating layer.

The obtained curable composition was stirred at 2000 rpm for 8 minutes using a planetary mixer, and filtered through a nylon filter paper (pore size: 10 μm) to prepare an anisotropic conductive paste.

(Examples 5 to 84 and Comparative Examples 2 to 6)

An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the type and amount of the compounding component were changed as shown in the following Tables 2 to 15 (the compounding unit was a part by weight). Further, in the case of using ethyl acetate, ethyl acetate was used to dissolve the component A when the above component A was added.

(Evaluation)

A metal mold having a rectangular parallelepiped recess having a width of 0.3 cm, a length of 1 cm, and a depth of 7 cm was prepared. The resulting anisotropic conductive paste was filled into the concave portion of the above metal mold. The anisotropic conductive paste filled in the concave portion of the metal mold was heated at 100 ° C for 10 minutes, and then heated at 150 ° C for 30 minutes to prepare a cured product of the anisotropic conductive paste.

The coefficient of linear expansion of the obtained cured product was measured using a thermomechanical analyzer (manufactured by TA Instruments, model "TMA2940"). Further, the temperature was raised to 210 ° C at a temperature elevation rate of 5 ° C /min, and the coefficient of linear expansion was measured. In the above evaluation, the anisotropic conductive paste having a linear expansion coefficient of 65 ppm/° C. or less was evaluated as acceptable.

Further, using a differential scanning calorimeter (manufactured by TA Instruments, model "DSC2920"), the peak temperature of the anisotropic conductive paste obtained in the examples and the comparative examples was placed at a temperature rising rate of 10 ° C /min. The heat is measured. Further, in Tables 2 to 15 showing the evaluation results of Examples 5 to 84 and Comparative Examples 2 to 6, the evaluation was "◎" when the peak temperature was 125 ° C or lower, and the evaluation was performed when the peak temperature exceeded 125 ° C and was 135 ° C or lower. When it is "○", when the peak temperature exceeds 135 °C, it is evaluated as "△", and the result is shown.

The evaluation results of Examples 1 to 4 and Comparative Example 1 are shown in Table 1 below.

It is understood that the anisotropic conductive pastes of Examples 1 to 4 have a lower coefficient of linear expansion than the anisotropic conductive paste of Comparative Example 1, and therefore are not easily peeled off from the circuit board or the electronic component even if heated. Further, in the anisotropic conductive pastes of Examples 2 to 4, the peak temperature was lower and the amount of heat generation was higher than that of the anisotropic conductive pastes of Example 1 and Comparative Example 1, so that it was hardened relatively quickly.

The evaluation results of Examples 5 to 84 and Comparative Examples 2 to 6 are shown in Tables 2 to 15 below.

It is understood that the cured products of the anisotropic conductive pastes of Examples 5 to 84 have a low coefficient of linear expansion, and therefore are not easily peeled off from the circuit board or the electronic parts even when heated.

1. . . Connection structure

2. . . First connection object member

2a. . . Upper surface

2b. . . electrode

3. . . Second connection object member

3a. . . lower surface

3b. . . electrode

4. . . Connection

5. . . Conductive particles

Fig. 1 is a front cross-sectional view schematically showing a connection structure using an anisotropic conductive material containing a curable composition according to an embodiment of the present invention and conductive particles.

1. . . Connection structure

2. . . First connection object member

2a. . . Upper surface

2b. . . electrode

3. . . Second connection object member

3a. . . lower surface

3b. . . electrode

4. . . Connection

5. . . Conductive particles

Claims (14)

A curable composition containing a component having at least one of an epoxy group and a thiopyranyl group, and a curing agent, and the component having at least one of an epoxy group and a thiopyranyl group has the following formula (1) a monomer of a compound represented by the structure, a polymer obtained by bonding at least two of the compounds, or a mixture of the monomer and the polymer: [Chemical Formula 1] In the above formula (1), R1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a structure represented by the following formula (2), R2 represents an alkylene group having a carbon number of 1 to 5, and R3 represents a carbon number. It is an alkylene group of 1 to 5, X1 represents an oxygen atom or a sulfur atom, and X2 represents an oxygen atom or a sulfur atom: [Chemical 2] In the above formula (2), R4 represents an alkylene group having a carbon number of 1 to 5, and X3 represents an oxygen atom or a sulfur atom. The curable composition according to claim 1, wherein the monomer having a compound represented by the above formula (1) is at least 2 in 100% by weight of the component having at least one of an epoxy group and a thiopyranyl group. The polymer obtained by bonding the compound or the mixture of the monomer and the polymer is in the range of 5 to 100% by weight. The hardening composition of claim 1, wherein the component having at least one of an epoxy group and a thiopyranyl group further comprises a monomer having an epoxy compound having a structure represented by the following formula (11), and is at least 2 a polymer obtained by bonding the epoxy compound or a mixture of the monomer and the polymer: [Chemical 3] In the above formula (11), R11 represents an alkylene group having a carbon number of 1 to 10, R12 represents an alkylene group having a carbon number of 1 to 10, and R13 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 10 or the following In the structure represented by the formula (12), R14 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a structure represented by the following formula (13): [Chemical 4] In the above formula (12), R15 represents an alkylene group having a carbon number of 1 to 10; [Chemical 5] In the above formula (13), R16 represents an alkylene group having a carbon number of 1 to 10. The sclerosing composition of claim 3, wherein, in the above formula (11), R13 and R14 are a hydrogen atom. The sclerosing composition of claim 3, wherein the monomer having the structure represented by the above formula (11) is 100% by weight of the component having at least one of an epoxy group and a thiopyranyl group, The polymer obtained by bonding at least two of the epoxy compounds or the mixture of the monomer and the polymer is in a range of from 1 to 50% by weight. The curable composition of claim 1, wherein the component having at least one of an epoxy group and a thiopyranyl group further comprises an epoxy compound having a hetero ring containing a nitrogen atom. The sclerosing composition according to claim 6, wherein the epoxy compound having a hetero ring containing a nitrogen atom is an epoxy compound represented by the following formula (16) or an epoxy compound represented by the following formula (17) :[化6] In the above formula (16), R21 to R23 each represent an alkylene group having a carbon number of 1 to 5, and Z represents an epoxy group or a hydroxymethyl group; In the above formula (17), R24 to R26 each represent an alkylene group having a carbon number of 1 to 5; p, q and r each represent an integer of 1 to 5; and R27 to R29 represent an alkylene having a carbon number of 1 to 5, respectively. base. The sclerosing composition according to claim 7, wherein the epoxy compound having a hetero ring containing a nitrogen atom is triglycidyl isocyanurate or trishydroxyethyl triglycidyl triglycidyl ether. The hardening composition according to claim 6, wherein the epoxy compound having a nitrogen atom-containing heterocyclic ring is contained in an amount of 0.1 to 10% by weight based on 100% by weight of the component having at least one of an epoxy group and a thiopyranyl group. Within the range of %. The curable composition of claim 1, wherein the component having at least one of an epoxy group and a thiopyranyl group further comprises an epoxy compound having an aromatic ring. The sclerosing composition of claim 10, wherein the aromatic ring is a benzene ring, a naphthalene ring or an anthracene ring. An anisotropic conductive material comprising the curable composition of claim 1 and conductive particles. A connection structure including a first electrical connection target member, a second electrical connection target member, and a connection portion electrically connecting the first and second electrical connection target members, wherein the connection portion is requested by Item 12 is formed by an anisotropic conductive material. A connection structure including a first connection target member, a second connection target member, and a connection portion that connects the first and second connection target members, wherein the connection portion is made of the curable composition of claim 1 form.