JP2016190985A - Thermosetting resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin excellent in storage stability, producibility, conductivity and adhesion; and to provide a conductive paste composition.SOLUTION: There is provided a thermosetting resin shown by formula (I) [R-Rare each specific group; L is an alkylene group or a dialkylene ether group; X and Y are each structure in which an epoxy group of a compound having each independently one H or epoxy group is added in the ring-opened state to a phenolic hydroxyl group; nand nare each integer of 0-2; m is 0 or 1; (i) when m is 0, N is an integer of 2-20, (ii) when m is 1, N is an integer of 1-10].SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin excellent in storage stability, production efficiency, conductivity and adhesion, and a conductive paste composition containing the thermosetting resin.

  Conventionally, a conductive paste containing a binder resin and a conductive substance has been used as a material for a transparent conductive film or a transparent conductive ink. Some conductive pastes include acrylic resins, polyester resins, phenol resins, vinyl chloride vinyl acetate resins, epoxy resins, urethane resins, and the like as binder resins.

For example, Patent Document 1 proposes a conductive paste in which an epoxy resin is cured using a curing agent of a nitrogen-containing compound and solder particles are contained as metal particles. The conductive paste has excellent resistance under high temperature, high humidity and pressurized environment, but it is considered that there is room for improvement in conductivity and storage stability.
Patent Document 2 proposes a conductive paste containing a composite resin composed of an epoxy-modified polyester resin and a phenol resin. The conductive paste has an excellent balance of storage stability, conductivity and adhesion to copper foil, but it needs to be cured at a high temperature in order to obtain sufficient conductivity. There seems to be room. Also, there is room for further improvement in conductivity.

  Therefore, development of a resin excellent in all of storage stability, production efficiency, conductivity and adhesion, and a conductive paste containing the resin has been demanded.

JP 2013-25375 A JP 2003-68141 A

  An object of this invention is to provide the thermosetting resin excellent in storage stability, manufacturing efficiency, electroconductivity, and adhesiveness, and the electrically conductive paste composition containing this thermosetting resin.

  As a result of intensive studies, the present inventors have reduced adhesion to metals by adding a compound having one epoxy group to a phenol resole resin having a hydroxymethyl group that contributes to curing shrinkage. Thus, the present inventors have found that a conductive paste having excellent storage stability, production efficiency and conductivity can be provided, and the present invention has been completed.

［式中、
Ｒ_１はアルキレン基または単結合を示し、
Ｒ_２およびＲ_３は同じであっても異なっていてもよく、水素原子、炭素数１〜１０個のアルキル基又はアルコキシ基であり、
Ｌはアルキレン基またはジアルキレンエーテル基であり、
Ｘは水素原子であるか、または、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、
Ｙは水素原子であるか、または、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、
ｎ_１およびｎ_２は同じであっても異なっていてもよく、０〜２の整数であり、
ｍは０または１であり、
（ｉ）ｍが０の場合、Ｎは２〜２０の整数であり、
（ｉｉ）ｍが１の場合、Ｎは１〜１０の整数である］
で表される熱硬化性樹脂であって、
（ｉ）ｍが０の場合、Ｎ個のＸ基のうち一部の基は、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、その他のＸ基は水素原子であり、ｎ_１は１または２であり、
（ｉｉ）ｍが１の場合、Ｎ個のＸ基およびＮ個のＹ基のうち一部の基は、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、その他のＸ基およびＹ基は水素原子であり、ｎ_１およびｎ_２は同時に０にならない、熱硬化性樹脂、
（２）（ｉ）ｍが０の場合、Ｎ個のＸ基のうち５〜８０％の基が、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、その他のＸ基は水素原子であり、
（ｉｉ）ｍが１の場合、Ｎ個のＸ基およびＮ個のＹ基のうち５〜８０％の基が、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、その他のＸ基およびＹ基は水素原子である、前記（１）に載の熱硬化性樹脂、
（３）（ｉ）ｍが０の場合、Ｎ個のＸ基のうち１５〜５０％の基が、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、その他のＸ基は水素原子であり、
（ｉｉ）ｍが１の場合、Ｎ個のＸ基およびＮ個のＹ基のうち１５〜５０％の基が、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、その他のＸ基およびＹ基は水素原子である、前記（１）または（２）に記載の熱硬化性樹脂。
（４）前記エポキシ基を１つ有する化合物は下記式：

［式中、Ｒ_４は、炭素数１〜１５個の直鎖又は分岐の炭化水素基または置換もしくは非置換のアリール基である］
で表される化合物から選択される１または複数の化合物である、前記（１）〜（３）のいずれか１項に記載の熱硬化性樹脂、
（５）前記エポキシ基を１つ有する化合物は下記式：

で表される化合物であるか、或いは、下記式：

［式中、Ｒ_５は、炭素数１〜１５個の直鎖又は分岐の炭化水素基である］
で表される化合物から選択される１または複数の化合物である、請求項１〜４のいずれか１、前記（１）〜（４）のいずれか１項に記載の熱硬化性樹脂、
（６）Ｘ基およびＹ基は下記式：

［式中、Ｒ_４は、炭素数１〜１５個の直鎖又は分岐の炭化水素基または置換もしくは非置換のアリール基である］
で表される基から選択される１または複数の基である、前記（１）〜（５）のいずれか１項に記載の熱硬化性樹脂、
（７）Ｘ基およびＹ基は下記式：

で表される基であるか、或いは、下記式：

［式中、Ｒ_５は、炭素数１〜１５個の直鎖又は分岐の炭化水素基である］
で表される基から選択される１または複数の基である、前記（１）〜（６）のいずれか１項に記載の熱硬化性樹脂、
（８）前記熱硬化性樹脂が、下記式：

で表される、前記（１）〜（７）のいずれか１項に記載の熱硬化性樹脂、
（９）前記（１）〜（８）のいずれか１項に記載の熱硬化性樹脂と導電性物質とを含む導電性ペースト組成物、
（１０）（Ｉ）下記式：

［式中、
Ｒ_１はアルキレン基を示し、
Ｒ_２およびＲ_３は同じであっても異なっていてもよく、炭素数１〜１０個のアルキル基又はアルコキシ基であり、
ｎ_１およびｎ_２は同じであっても異なっていてもよく、０〜２の整数であり、
ｍは０または１である］
で表される繰り返し単位をＮ個、アルデヒドによって重合して、フェノールレゾール化合物を得る工程と、
（ＩＩ）前記工程（Ｉ）で得られた前記フェノールレゾール化合物と、エポキシ基を１つ有する化合物とを反応させることを含む、熱硬化性樹脂の製造方法、
（１１）前記繰り返し単位が、下記式：

で表される、前記（１０）に記載の製造方法、
（１２）前記（１０）または（１１）に記載の製造方法によって製造された熱硬化性樹脂
を、提供するものである。 That is, the present invention
(1) The following formula:

[Where:
R ₁ represents an alkylene group or a single bond,
R ₂ and R ₃ may be the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group,
L is an alkylene group or a dialkylene ether group,
X is a hydrogen atom or has a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group,
Y is a hydrogen atom or has a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group,
n ₁ and n ₂ may be the same or different and are integers from 0 to 2,
m is 0 or 1,
(I) When m is 0, N is an integer of 2 to 20,
(Ii) When m is 1, N is an integer of 1 to 10]
A thermosetting resin represented by
(I) When m is 0, some of the N X groups have a structure in which the epoxy group of the compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group; X group of is a hydrogen atom, n ₁ is 1 or 2,
(Ii) When m is 1, some of the N X groups and the N Y groups are ring-opened and added to the phenolic hydroxyl group of the compound having one epoxy group. A thermosetting resin having a structure, wherein the other X group and Y group are hydrogen atoms, and n ₁ and n ₂ are not simultaneously 0,
(2) (i) When m is 0, a structure in which 5 to 80% of N X groups are ring-opened and added to a phenolic hydroxyl group of a compound having one epoxy group And the other X group is a hydrogen atom,
(Ii) When m is 1, 5 to 80% of N X groups and N Y groups are ring-opened with respect to the phenolic hydroxyl group of the epoxy group of the compound having one epoxy group. The thermosetting resin according to (1), which has an added structure, and the other X group and Y group are hydrogen atoms,
(3) When m is 0, 15 to 50% of N X groups have a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group And the other X group is a hydrogen atom,
(Ii) When m is 1, 15 to 50% of N X groups and N Y groups are ring-opened with respect to the phenolic hydroxyl group of the epoxy group of the compound having one epoxy group. The thermosetting resin according to (1) or (2), wherein the thermosetting resin has an added structure and the other X and Y groups are hydrogen atoms.
(4) The compound having one epoxy group has the following formula:

[Wherein R ₄ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms or a substituted or unsubstituted aryl group]
The thermosetting resin according to any one of (1) to (3), which is one or more compounds selected from the compounds represented by:
(5) The compound having one epoxy group has the following formula:

Or a compound represented by the following formula:

[Wherein R ₅ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms]
The thermosetting resin according to any one of claims 1 to 4 and (1) to (4), wherein the thermosetting resin is one or a plurality of compounds selected from the compounds represented by:
(6) X group and Y group are represented by the following formula:

[Wherein R ₄ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms or a substituted or unsubstituted aryl group]
The thermosetting resin according to any one of (1) to (5), which is one or a plurality of groups selected from the group represented by:
(7) X group and Y group are represented by the following formula:

Or a group represented by the following formula:

[Wherein R ₅ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms]
The thermosetting resin according to any one of (1) to (6), which is one or a plurality of groups selected from the group represented by:
(8) The thermosetting resin has the following formula:

The thermosetting resin according to any one of (1) to (7), represented by:
(9) A conductive paste composition comprising the thermosetting resin according to any one of (1) to (8) and a conductive substance,
(10) (I) The following formula:

[Where:
R ₁ represents an alkylene group,
R ₂ and R ₃ may be the same or different, and are an alkyl group or alkoxy group having 1 to 10 carbon atoms,
n ₁ and n ₂ may be the same or different and are integers from 0 to 2,
m is 0 or 1]
A step of polymerizing N repeating units represented by aldehyde with an aldehyde to obtain a phenol resole compound;
(II) A method for producing a thermosetting resin, comprising reacting the phenol resole compound obtained in the step (I) with a compound having one epoxy group,
(11) The repeating unit has the following formula:

The production method according to (10), represented by:
(12) A thermosetting resin produced by the production method described in (10) or (11) is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin excellent in storage stability, manufacturing efficiency, electroconductivity, and adhesiveness, and the electrically conductive paste composition containing this thermosetting resin can be provided.

FIG. 1 is a graph showing a plot of changes in adhesion against the addition rate of a compound having one epoxy group with respect to the phenolic hydroxyl group of a base resole resin.

［式中、
Ｒ_１はアルキレン基または単結合を示し、
Ｒ_２およびＲ_３は同じであっても異なっていてもよく、水素原子、炭素数１〜１０個のアルキル基又はアルコキシ基であり、
Ｌはアルキレン基またはジアルキレンエーテル基であり、
Ｘは水素原子であるか、または、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、
Ｙは水素原子であるか、または、エポキシ基を１つ有する化合物の該エポキシ基がフェノール性水酸基に対して開環付加した構造を有し、
ｎ_１およびｎ_２は同じであっても異なっていてもよく、０〜２の整数であり、
ｍは０または１であり、
（ｉ）ｍが０の場合、Ｎは２〜２０の整数であり、
（ｉｉ）ｍが１の場合、Ｎは１〜１０の整数である］
で表される。 Hereinafter, the present invention will be described in more detail.
The thermosetting resin of the present invention has a structure in which a compound having one epoxy group is randomly added to the main structure obtained by polymerization of N repeating units (monomers).
That is, the thermosetting resin of the present invention has the following formula:

[Where:
R ₁ represents an alkylene group or a single bond,
R ₂ and R ₃ may be the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group,
L is an alkylene group or a dialkylene ether group,
X is a hydrogen atom or has a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group,
Y is a hydrogen atom or has a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group,
n ₁ and n ₂ may be the same or different and are integers from 0 to 2,
m is 0 or 1,
(I) When m is 0, N is an integer of 2 to 20,
(Ii) When m is 1, N is an integer of 1 to 10]
It is represented by

  Here, a total of N structural units are connected to each other via L groups, and (N-1) L groups are included in the thermosetting resin. The L group is an alkylene group or a dialkylene ether group, preferably an alkylene group or dialkylene ether group having 1 to 15 carbon atoms, more preferably an alkylene group or dialkylene ether group having 1 to 7 carbon atoms. It is.

［式中、
Ｒ_１はアルキレン基または単結合を示し、
Ｒ_２およびＲ_３は同じであっても異なっていてもよく、水素原子、炭素数１〜１０個のアルキル基又はアルコキシ基であり、
ｎ_１およびｎ_２は同じであっても異なっていてもよく、０〜２の整数であり、
ｍは０または１である］
で表される。
該構造単位において、Ｒ_２基およびＲ_３基は、Ｒ_１基に対して、例えばオルト位、メタ位、パラ位に位置する。また、ＯＸ基およびＯＹ基は、Ｒ_１基に対して、例えばオルト位、メタ位、パラ位に位置することができ、好ましくはオルト位およびパラ位に位置する。 Each structural unit of the thermosetting resin has the following formula:

[Where:
R ₁ represents an alkylene group or a single bond,
R ₂ and R ₃ may be the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group,
n ₁ and n ₂ may be the same or different and are integers from 0 to 2,
m is 0 or 1]
It is represented by
In the structural unit, the R ₂ group and the R ₃ group are located, for example, in the ortho position, the meta position, and the para position with respect to the R ₁ group. Further, the OX group and the OY group can be located, for example, in the ortho position, the meta position, and the para position with respect to the R ₁ group, and are preferably located in the ortho position and the para position.

In the structural unit, each arylene group has up to two —CH ₂ OH groups.
If n ₁ or _{n 2} is 1, i.e., when the phenyl group having one _-CH 2 OH group, _-CH 2 OH group, located in an ortho position, the para position relative to the OX group and OY group It is preferable to do.
When n ₁ or n ₂ is 2, that is, when the phenyl group has _two —CH ₂ OH groups, the two —CH ₂ OH groups are ortho- and para-positions with respect to the OX group and the OY group. It is preferable to be located at.
Note that the structural unit has at least one —CH ₂ OH group. More specifically, when m is 0, n ₁ is 1 or 2, and when m is 1, n ₁ and n ₂ are not 0 simultaneously.

In the above formula (I), (i) when m is 0, N is an integer of 2-20. Some of the N X groups have a structure in which the epoxy group of the compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group, and the other X groups are hydrogen atoms. is there. That is, when the structural unit is a mononuclear body, the number of structural units contained in the thermosetting resin is 2 to 20, and some of the 2 to 20 X groups are epoxy groups. This means that the epoxy group of a compound having one group has a structure in which ring-opening addition is performed on a phenolic hydroxyl group, and the other X groups are hydrogen atoms.
Here, the X group is a residue of a compound having one of the epoxy groups ring-opened and added to the phenolic hydroxyl group contained in the structural unit.

In the above formula (I), (ii) when m is 1, N is an integer of 1 to 10. Some of the N X groups and the N Y groups have a structure in which the epoxy group of the compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group, X group and Y group are hydrogen atoms. That is, when the structural unit is a binuclear body, the number of structural units contained in the thermosetting resin is 1 to 10, among 1 to 10 X groups and 1 to 10 Y groups. A part of the group has a structure in which the epoxy group of the compound having one epoxy group is subjected to ring-opening addition to the phenolic hydroxyl group, and the other X group and Y group are hydrogen atoms. means.
Here, the X group and the Y group are residues of a compound having one epoxy group that has undergone ring-opening addition to a phenolic hydroxyl group contained in the structural unit.
“Some groups out of N X groups and N Y groups have a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group” Only one X group in one structural unit may have a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group, and only the Y group has the structure. It means that both the X group and the Y group may have this structure, or that neither the X group nor the Y group need have such a structure.
And the pattern which has the said structure may differ among N structural units, respectively. For example, in a certain structural unit, the X group and the Y group have the above ring-opening addition structure, and in the other structural unit, the X group and the Y group are hydrogen atoms, or either the X group or the Y group May have the above ring-opened structure. That is, the number of the compounds having one epoxy with respect to the phenolic hydroxyl group may be different between the structural units.

［式中、Ｒ_４は、炭素数１〜１５個の直鎖又は分岐の飽和若しくは不飽和炭化水素基または置換もしくは非置換のアリール基である］
で表される化合物から選択される１または複数の化合物である。 The compound having one epoxy group has the following formula:

[Wherein R ₄ represents a linear or branched saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms or a substituted or unsubstituted aryl group]
Or one or more compounds selected from the compounds represented by:

［式中、Ｒ_４は、炭素数１〜１５個の直鎖又は分岐の飽和若しくは不飽和炭化水素基または置換もしくは非置換のアリール基である］
で表される基から選択される１または複数の基である。
Ｘ基とＹ基とは、同じでも異なっていてもよい。また、Ｘ基およびＹ基が、上記より選択される複数の基である場合、Ｘ基の構造は各構造単位間で同じであってもそれぞれ異なっていてもよく、Ｙ基の構造も各構造単位間で同じであってもそれぞれ異なっていてもよい。 That is, the X group and the Y group have the following formula:

[Wherein R ₄ represents a linear or branched saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms or a substituted or unsubstituted aryl group]
Or a group selected from the group represented by:
X group and Y group may be the same or different. Further, when the X group and the Y group are a plurality of groups selected from the above, the structure of the X group may be the same or different between the structural units, and the structure of the Y group is also the structure of each structure. The units may be the same or different.

  The compound having one epoxy group may be a synthetic product or a commercial product. In the case of a commercial item, what is marketed as a reactive diluent can be used. Examples of the compound having one epoxy group include ADEKA glycilol ED-502, ADEKA glycilol ED-509E, ADEKA glycilol ED-509S, and ADEKA glycilol ED-529 manufactured by ADEKA; YED111N and YED111AN manufactured by Mitsubishi Chemical. YED122 and YED188; Nippon Kayaku BROC, BR-250H; NOF's Epiol (registered trademark) B, Epiol (registered trademark) EH-N, Epiol (registered trademark) A, Epiol (registered trademark) P, Epiol (registered trademark) SB, Epiol (registered trademark) TB and Epiol (registered trademark) OH; and Denasel EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX- from Nagase ChemteX 146 and Denacol EX-192, and the like.

  As described above, the thermosetting resin of the present invention has a structure in which a compound having only one epoxy group is added to a part of a phenolic hydroxyl group in a structural unit, thereby reducing adhesion to a metal. Therefore, a conductive paste having excellent conductivity can be provided. This is because the hydroxyl group produced by the ring-opening addition of epoxy has a higher degree of spatial freedom than the phenolic hydroxyl group, can be flexibly bonded to the metal surface, and can provide a strong adhesion to the metal. This is probably because of this.

In addition, since the thermosetting resin of the present invention has a hydroxymethyl group that contributes to curing shrinkage, volume shrinkage occurs due to dehydration condensation of the hydroxymethyl group, and the density of the conductive material can be increased. A conductive paste composition having sufficiently high conductivity can be provided.
Furthermore, since the thermosetting resin of the present invention is prepared by reacting an epoxy with a phenol resol compound in advance, it is not necessary to mix in use, and the operation is simple. And a high curing temperature is not required. Therefore, it is excellent also in manufacturing efficiency.

  Furthermore, the thermosetting resin of the present invention has excellent storage stability by adding a compound having only one epoxy group. For example, when a compound containing a plurality of epoxy groups is added to a phenolic resole resin, an increase in molecular weight and a broad distribution of the high molecular weight region occur remarkably, thus providing excellent storage stability. difficult.

The weight average molecular weight of the thermosetting resin of this invention is 200-20000, for example, Preferably it is 500-10000. If the weight average molecular weight is too low, the viscosity becomes low and cannot be pasted. If it is too high, the viscosity may increase during the storage period or gelation may occur.
Here, for example, the weight average molecular weight is a numerical value measured by using gel permeation chromatography HLC-8220 GPC manufactured by Tosoh Corporation and converted to polystyrene standards.

In a preferred embodiment of the thermosetting resin of the present invention,
(I) When m is 0, 5 to 80% of N X groups have a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group And the other X groups are hydrogen atoms,
(Ii) When m is 1, 5 to 80% of N X groups and N Y groups are ring-opened with respect to the phenolic hydroxyl group of the epoxy group of the compound having one epoxy group. It has an added structure, and the other X and Y groups are hydrogen atoms.

That is, when m is 0 (that is, when the structural unit is a mononuclear body) and N is 20, a total of 1 to 16 phenolic hydroxyl groups out of 20 phenolic hydroxyl groups. On the other hand, a compound having one epoxy is added, and it is preferable that 1 to 16 X groups out of 20 X groups have a structure in which a compound having one epoxy is ring-opened. .
When m is 1 (that is, when the structural unit is a binuclear body) and N is 10, 10 phenolic hydroxyl groups (bonded to the bonding position of the X group) and (Y Among 10 phenolic hydroxyl groups (bonded to the bonding position of the group), a compound having one epoxy is added to 1 to 16 phenolic hydroxyl groups in total, and among 20 X groups and Y groups In addition, it is preferable that a total of 1 to 16 X groups and / or Y groups have a structure in which a compound having one epoxy is opened.
When the compound having one epoxy group is added to the phenolic hydroxyl group at the above ratio, a sufficient and appropriate thermosetting resin having adhesion to a metal can be obtained. If the ratio is too low, it is difficult to obtain adhesion to the metal. On the other hand, if the ratio is too high, the amount of the compound having one epoxy group is used even though the adhesion is saturated. This increases the manufacturing cost.

Furthermore, in a more preferred embodiment of the thermosetting resin of the present invention,
(I) When m is 0, 15 to 50% of N X groups have a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group And the other X groups are hydrogen atoms,
(Ii) When m is 1, 15 to 50% of N X groups and N Y groups are ring-opened with respect to the phenolic hydroxyl group of the epoxy group of the compound having one epoxy group. It has an added structure, and the other X and Y groups are hydrogen atoms.
When the compound having one epoxy group is added to the phenolic hydroxyl group at the above ratio, the balance between the adhesiveness of the obtained thermosetting resin and the production cost can be improved.

で表される化合物であるか、或いは、下記式：

［式中、Ｒ_５は、炭素数１〜１５個の直鎖又は分岐の炭化水素基である］
で表される化合物から選択される１または複数の化合物である。 The compound having one epoxy group is preferably represented by the following formula:

Or a compound represented by the following formula:

[Wherein R ₅ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms]
Or one or more compounds selected from the compounds represented by:

で表される基であるか、或いは、下記式：

［式中、Ｒ_５は、炭素数１〜１５個の直鎖又は分岐の炭化水素基である］
で表される基から選択される１または複数の基である。 That is, the X group and the Y group are preferably represented by the following formula:

Or a group represented by the following formula:

[Wherein R ₅ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms]
Or a group selected from the group represented by:

で表される化合物と、下記式：

で表される化合物との混合物であることが好ましい。 When the compound having one epoxy group is a plurality of compounds, the compound having one epoxy group has the following formula:

And a compound represented by the following formula:

It is preferable that it is a mixture with the compound represented by these.

で表される基、および下記式：

で表される基が混在している。
エポキシ基を１つ有する化合物が上記２つの化合物の混合物である市販品としては、ＡＤＥＫＡ社製のＥＤ−５０２が挙げられる。 In this case, in the thermosetting resin of the present invention, as the X group and the Y group, the following formula:

And a group represented by the following formula:

The group represented by is mixed.
As a commercial product in which the compound having one epoxy group is a mixture of the above two compounds, ED-502 manufactured by ADEKA can be mentioned.

で表される。 The thermosetting resin of the present invention preferably has the following formula:

It is represented by

で表される構造単位がＮ個、互いにＬ基を介して連結された構造を有する。 That is, the thermosetting resin preferably has the following formula:

N has a structure in which N structural units are connected to each other via an L group.

［式中、
Ｒ_１はアルキレン基を示し、
Ｒ_２およびＲ_３は同じであっても異なっていてもよく、炭素数１〜１０個のアルキル基又はアルコキシ基であり、
ｎ_１およびｎ_２は同じであっても異なっていてもよく、０〜２の整数であり、
ｍは０または１である］
で表される繰り返し単位（即ち、モノマー）をＮ個、アルデヒドによって重合して、フェノールレゾール化合物を得る。 The thermosetting resin of the present invention can be synthesized, for example, according to a production method including the following steps.
<Process (I)>
In this process, the following formula:

[Where:
R ₁ represents an alkylene group,
R ₂ and R ₃ may be the same or different, and are an alkyl group or alkoxy group having 1 to 10 carbon atoms,
n ₁ and n ₂ may be the same or different and are integers from 0 to 2,
m is 0 or 1]
Is polymerized with N aldehydes to obtain a phenol resole compound.

As the repeating unit, for example, a compound in which the hydrogen atom of phenol, cresol, bisphenol A, bisphenol F, biphenol, allylphenol, tert-butylphenol, octylphenol or phenylphenol is substituted with n —CH ₂ OH groups is used. be able to.

で表される。
また、最も好ましい繰り返し単位は、ビスフェノールＡおよびビスフェノールＦの水素原子がｎ個の−ＣＨ_２ＯＨ基で置換された化合物である。これらは、製造時に、作業環境に影響を及ぼすモノマーガスを発生させない点で有利である。 The repeating unit is preferably a compound in which hydrogen atoms of phenol, cresol, bisphenol A and bisphenol F are substituted with n —CH ₂ OH groups, each represented by the following formula:

It is represented by
The most preferred repeating unit is a compound in which the hydrogen atoms of bisphenol A and bisphenol F are substituted with n —CH ₂ OH groups. These are advantageous in that no monomer gas that affects the working environment is generated during production.

Examples of the aldehyde used in the step (I) include formaldehyde, an aqueous solution thereof, paraformaldehyde, benzaldehyde and acetylaldehyde, and preferably formaldehyde, an aqueous solution thereof and paraformaldehyde.
Step (I) is performed, for example, at a temperature of 40 to 120 ° C. and a reaction time of 1 to 10 hours, preferably at a temperature of 60 to 100 ° C. and a reaction time of 1 to 5 hours.

  The weight average molecular weight of the phenol resole compound synthesized in the step (I) is, for example, 200 to 20000, preferably 500 to 10,000. If the weight average molecular weight is too low, the viscosity is low and cannot be pasted. If it is too high, the viscosity may increase during the storage period, or gelation may occur.

<Process (II)>
In this step, the phenol resole compound obtained in the step (I) is reacted with a compound having one epoxy group.
The structure of the compound having one epoxy group is as described above.

  In the step (II), the reaction is performed at a temperature of 40 to 120 ° C., for example. Preferably, the reaction is performed at a temperature of 60 to 100 ° C. The reaction is preferably performed, for example, for 0.5 to 10 hours, preferably 0.5 to 5 hours.

If necessary, a neutralization reaction step may be performed with an acid, for example, an organic acid such as acetic acid or oxalic acid, or an inorganic acid such as hydrochloric acid or sulfuric acid, followed by a step of removing the neutralized salt by washing with water or the like.
After step (II), for example, a solvent can be appropriately substituted at a temperature of 30 to 120 ° C. under a vacuum of 400 to 10 torr to prepare a thermosetting resin.

The 2nd side surface of this invention is related with the electrically conductive paste composition containing the said thermosetting resin and an electroconductive substance.
Examples of the conductive substance include silver particles, nickel particles, titanium oxide particles, tin oxide particles, phosphorus-containing tin oxide particles, antimony-containing tin oxide particles, indium oxide particles, tin-containing indium oxide particles and other metal particles, carbon black, graphite Etc. These may be used alone or in combination of two or more. In particular, when the conductive paste is required to be transparent, metal particles such as tin oxide particles, phosphorus-containing tin oxide particles, antimony-containing tin oxide particles, indium oxide particles, and tin-containing indium oxide particles are preferably used.

When the conductive paste composition contains a conductive substance, the conductive paste composition is prepared by kneading a thermosetting resin and a conductive substance.
For example, the conductive paste composition is cured, for example, at a temperature range of 80 to 250 ° C., preferably 100 to 200 ° C., for example, for 1 to 4 hours, preferably 1 to 3 hours.

  As described above, since the thermosetting resin of the present invention has sufficient adhesion and is excellent in conductivity, the conductive paste composition of the present invention including the thermosetting resin is similarly applied to metal. It has sufficient adhesion and is excellent in conductivity. And since the electrically conductive paste composition of this invention has the said outstanding property, it is applicable to the various uses. For example, the conductive paste composition of the present invention is used as an electrode, for example, a transparent substrate, a touch panel electrode, a flat panel display display electrode, a thin film solar cell electrode, an organic EL lighting electrode, and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited at all by these Examples.

<Preparation of base resole resin>
(1) Preparation of Base Resol Resin 1 A glass reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer and a condenser tube was charged with 400 g of phenol, 300 g of 50% formaldehyde aqueous solution and 40 g of 10% sodium hydroxide aqueous solution, and 70 ° C. The temperature was raised to. After maintaining at 70 ° C. for 4 hours, the base resol resin 1 was obtained by cooling.

(2) Preparation of base resol resin 2 A glass reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer, and a cooling tube was charged with 300 g of bisphenol A, 160 g of 50% formaldehyde aqueous solution and 30 g of 10% sodium hydroxide aqueous solution. Was kept at 30 ° C. for 3 hours, and the temperature was raised to 80 ° C. After maintaining at 80 ° C. for 4 hours, the base resol resin 2 was obtained by cooling.

(3) Preparation of Base Resol Resin 3 Into a 1 L glass reaction vessel equipped with a thermometer, a stirrer and a cooling tube, 400 g of paracresol, 250 g of 50% formaldehyde aqueous solution and 40 g of 10% sodium hydroxide aqueous solution were charged. The temperature was raised to ° C. After maintaining at 80 ° C. for 4 hours, the base resol resin 3 was obtained by cooling.

(4) Preparation of Base Resol Resin 4 A 1 L glass reaction vessel equipped with a thermometer, a stirrer and a cooling tube was charged with 300 g of bisphenol F, 180 g of 50% formaldehyde aqueous solution and 30 g of 10% sodium hydroxide aqueous solution, and 80 ° C. The temperature was raised to. After maintaining at 80 ° C. for 4 hours, the base resol resin 4 was obtained by cooling.

<Addition of epoxy compound>
(1) Example 1
The base resol resin 1 obtained above was charged with 150 g of ED-529 (ADEKA reactive diluent) as an epoxy, heated to 80 ° C., held at 80 ° C. for 1 hour, and neutralized with 90% acetic acid. The neutralized salt was removed by washing with water. 300 g of methyl carbitol was added, and the solvent was replaced by raising the temperature to 100 ° C. under a vacuum of 50 Torr to obtain a resol resin 1 (thermosetting resin 1) to which epoxy was added.

(2) Example 2
Resole resin 2 (thermosetting resin 2) to which epoxy was added was obtained in the same manner as in Example 1 except that the amount of ED-529 charged was 300 g.

(3) Example 3
The base resol resin 1 obtained above was charged with 280 g of ED-502 (ADEKA reactive diluent) as an epoxy, heated to 80 ° C., held at 80 ° C. for 1 hour, and neutralized with 90% acetic acid. Went. Washing with water was carried out to remove the neutralized salt, and the resin layer and the water-washing water layer were allowed to stand overnight to separate them. Thereafter, 300 g of methyl carbitol was added, and the solvent was replaced by raising the temperature to 100 ° C. under a vacuum of 50 Torr to obtain a resol resin 3 (thermosetting resin 3) to which epoxy was added.

(4) Example 4
The base resol resin 2 obtained above was charged with 110 g of ED-509S (reactive diluent made by ADEKA) as an epoxy, heated to 80 ° C., held at 80 ° C. for 1 hour, and neutralized with 90% acetic acid. The neutralized salt was removed by washing with water. 300 g of methyl carbitol was added, and the solvent was replaced by raising the temperature to 100 ° C. under a vacuum of 50 Torr to obtain a resol resin 4 (thermosetting resin 4) to which epoxy was added.

(5) Example 5
Resole resin 5 (thermosetting resin 5) to which epoxy was added was obtained in the same manner as in Example 4 except that the amount of ED-509S charged was 220 g.

(6) Example 6
The base resol resin 3 obtained above was charged with 130 g of ED-529 (ADEKA reactive diluent) as an epoxy, heated to 80 ° C., held at 80 ° C. for 1 hour, and neutralized with 90% acetic acid. The neutralized salt was removed by washing with water. 300 g of methyl carbitol was added, and the solvent was replaced by raising the temperature to 100 ° C. under a vacuum of 50 Torr to obtain a resol resin 6 (thermosetting resin 6) to which epoxy was added.

(7) Example 7
Resole resin 7 (thermosetting resin 7) to which epoxy was added was obtained in the same manner as in Example 6 except that the amount of ED-529 charged was 260 g.

(8) Example 8
The base resole resin 4 obtained above was charged with 110 g of ED-529 (ADEKA reactive diluent) as an epoxy, heated to 80 ° C., held at 80 ° C. for 1 hour, and neutralized with 90% acetic acid. The neutralized salt was removed by washing with water. 300 g of methyl carbitol was added, and the solvent was replaced by raising the temperature to 100 ° C. under a vacuum of 50 Torr to obtain a resol resin 8 (thermosetting resin 8) to which epoxy was added.

(9) Example 9
Resole resin 9 (thermosetting resin 9) to which epoxy was added was obtained in the same manner as in Example 8 except that the amount of ED-529 charged was 220 g.

(10) Comparative Example 1
The base resole resin 1 was neutralized with 90% acetic acid, and the neutralized salt was removed by washing with water. Thereafter, 300 g of methyl carbitol was added, and the solvent was replaced by raising the temperature to 100 ° C. under a vacuum of 50 Torr to obtain a comparative resole resin 1 (comparative thermosetting resin 1).

(11) Comparative Example 2
Base resol resin 1 is charged with 160 g of bisphenol A type epoxy resin EP-4100E (manufactured by ADEKA) containing two or more epoxy groups, heated to 80 ° C., held at 80 ° C. for 1 hour, 90% Neutralization was performed with acetic acid. Washing with water was carried out to remove the neutralized salt, and the resin layer and the water-washing water layer were allowed to stand overnight to separate them. Thereafter, 500 g of methyl carbitol was added, and the solvent was replaced by raising the temperature to 100 ° C. under a vacuum of 50 Torr to obtain a comparative resole resin 2 (comparative thermosetting resin 2).

(12) Comparative Example 3
The base resole resin 1 was neutralized with 90% acetic acid, and the neutralized salt was removed by washing with water. Thereafter, 300 g of methyl carbitol was added, and the solvent was replaced by raising the temperature to 100 ° C. under a vacuum of 50 Torr. Thereafter, 160 g of bisphenol A type epoxy resin EP-4100E (manufactured by ADEKA) and 3 g of 2-methylimidazole 2MZ-H (manufactured by Shikoku Kasei Co., Ltd.) as a curing catalyst were mixed, and comparative resole resin 3 (comparative thermosetting resin 3). ) Here, the base resole resin 1 and EP-4100E have not reacted, and the comparative resole resin 3 is a simple mixture of the base resole resin 1 and the epoxy group-containing compound.

(13) Comparative Example 4
A comparative resole resin 4 (comparative thermosetting resin 4) was obtained in the same manner as in Comparative Example 3 except that EP-4100E was 320 g and 2MZ-H was 6 g.

The following evaluation was performed about the resole resin 1-9 and the comparative resole resin 1-4 which were obtained as mentioned above and to which epoxy was added.
[Evaluation of manufacturing efficiency]
The manufacturing processes in the above-described Examples and Comparative Examples were evaluated as follows.
◎ ・ ・ ・ Each process proceeds without any waiting time,
○ ... Standing time is required in some steps (for example, dissolving step, reacting step), but the step proceeds.

[Evaluation of adhesion]
On a 25 μm-thick electrolytic copper foil (manufactured by Nikko Materials), a thermosetting resin is applied to a thickness of 50 μm, and is cured at 150 ° C. for 1 hour in a hot air dryer. Thereafter, the test piece is cut so as to have a width of 1 cm, the opposite surface of the resin-coated surface is bonded to a 3 mm thick aluminum plate with a double-sided tape, and the aluminum plate is set on a measuring jig. Next, the tip of the thermosetting resin is peeled off from the copper foil, the peeled resin is sandwiched between measurement jigs, and the resin is peeled off perpendicular to the copper foil. The load at this time was measured as 90 ° peel strength. The measurement used an SV-5 type push-pull stand and GT-40 type jig manufactured by Imada Manufacturing Co., Ltd. The jig speed was 5 mm / min, and the value of the measured adhesion load was read to evaluate adhesion.

[Evaluation of conductivity]
Commercially available silver powder (spherical, average particle size 50 μm, manufactured by Kanto Chemical Co.) 90 was mixed with the obtained thermosetting resin (solid content) 10 in a weight ratio to prepare a conductive paste composition. Using this paste, a line having a width of 5 mm and a length of 10 cm was drawn on the PET film, and a curing treatment was performed at 150 ° C. for 1 hour with a hot air drier. The specific resistance value of the line was measured by a four-terminal method using a milliohm high tester (No. 3540, manufactured by Hioki Electric Co., Ltd.). Based on the read resistance value, the conductivity was evaluated as follows.
○ ・ ・ ・ When the specific resistance value is less than 5 × 10 ⁻⁵ Ω · cm,
×: When the specific resistance value is 5 × 10 ⁻⁵ Ω · cm or more.

[Evaluation of monomer gas generation]
Each of the prepared resins was weighed on an aluminum petri dish having a diameter of 5 cm and placed on a 150 ° C. heat plate. The gas generated at this time was adsorbed on 400 g of pure water in the suction bottle at 2 L / min for 30 minutes using a suction pump. This pure water is supplied with JIS K 0102 No. The amount of the monomer adsorbed purely was measured in a test according to 28 and 29. The presence or absence of monomer gas generation was evaluated as follows.
Yes ... Monomer gas generation confirmed
No ... Generation of monomer gas was not confirmed.

[Evaluation of storage stability]
The viscosity of the produced thermosetting resin was measured, then stored at 25 ° C. for one month, and the viscosity after one month was measured. All of these viscosities were measured using an E-type viscometer manufactured by Tokimec Co., Ltd. Based on the measured viscosity, the storage stability of the thermosetting resin was evaluated as follows.
○ ・ ・ ・ Viscosity after one month is less than twice the initial viscosity,
X: The viscosity after one month is more than twice the initial viscosity.
The above evaluation results are shown in Table 1.

From Table 1, the resin of Comparative Example 1 containing only the base resol resin does not have sufficient adhesion, and the resins of Comparative Examples 3 and 4 that do not react the epoxy group-containing compound with the base resol resin are conductive and storage stable. It was shown to be inferior. Furthermore, it was shown that sufficient storage stability cannot be obtained with the resin of Comparative Example 2 in which the epoxy group-containing compound to be reacted with the base resol resin contains two epoxy groups.
On the other hand, all of the thermosetting resins (Examples 1 to 9) of the present invention obtained by reacting an epoxy group-containing compound having one epoxy group with a base resol resin reduce the adhesion to metal. In other words, it was shown to have excellent storage stability, production efficiency and conductivity. Further, in Examples 4 and 5 and Examples 8 and 9, it was shown that the thermosetting resin having the above excellent properties can be obtained without generating a monomer gas and affecting the working environment.

<Relationship between addition rate and adhesion of compounds having one epoxy group>
FIG. 1 shows a plot of changes in adhesion versus the addition rate of a compound having one epoxy group with respect to the phenolic hydroxyl group of the base resole resin.
Here, the thermosetting resin was produced by changing the addition rate of the epoxy-containing compound in Example 8 within a range of 0 to 100%, and the adhesion of the thermosetting resin obtained at each addition rate was measured. .

  From FIG. 1, when the addition ratio of the compound having only one epoxy group to the phenol resol compound is 80% or less, the adhesion can be improved by increasing the compound having only one epoxy group. At higher addition rates, adhesion was saturated and no improvement was seen.

Claims (12)

Following formula:

[Where:
R ₁ represents an alkylene group or a single bond,
R ₂ and R ₃ may be the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group,
L is an alkylene group or a dialkylene ether group,
X is a hydrogen atom or has a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group,
Y is a hydrogen atom or has a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group,
n ₁ and n ₂ may be the same or different and are integers from 0 to 2,
m is 0 or 1,
(I) When m is 0, N is an integer of 2 to 20,
(Ii) When m is 1, N is an integer of 1 to 10]
A thermosetting resin represented by
(I) When m is 0, some of the N X groups have a structure in which the epoxy group of the compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group; X group of is a hydrogen atom, n ₁ is 1 or 2,
(Ii) When m is 1, some of the N X groups and the N Y groups are ring-opened and added to the phenolic hydroxyl group of the compound having one epoxy group. has the structure, other X and Y groups are hydrogen atom, n ₁ and n ₂ does not become 0 at the same time, a thermosetting resin. (I) When m is 0, 5 to 80% of N X groups have a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group And the other X groups are hydrogen atoms,
(Ii) When m is 1, 5 to 80% of N X groups and N Y groups are ring-opened with respect to the phenolic hydroxyl group of the epoxy group of the compound having one epoxy group. The thermosetting resin according to claim 1, which has an added structure, and the other X group and Y group are hydrogen atoms. (I) When m is 0, 15 to 50% of N X groups have a structure in which the epoxy group of a compound having one epoxy group is subjected to ring-opening addition to a phenolic hydroxyl group And the other X groups are hydrogen atoms,
(Ii) When m is 1, 15 to 50% of N X groups and N Y groups are ring-opened with respect to the phenolic hydroxyl group of the epoxy group of the compound having one epoxy group. The thermosetting resin according to claim 1, wherein the thermosetting resin has an added structure, and the other X group and Y group are hydrogen atoms. The compound having one epoxy group has the following formula:

[Wherein R ₄ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms or a substituted or unsubstituted aryl group]
The thermosetting resin according to any one of claims 1 to 3, which is one or a plurality of compounds selected from the compounds represented by: The compound having one epoxy group has the following formula:

Or a compound represented by the following formula:

[Wherein R ₅ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms]
The thermosetting resin according to any one of claims 1 to 4, which is one or a plurality of compounds selected from compounds represented by: X group and Y group have the following formula:

[Wherein R ₄ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms or a substituted or unsubstituted aryl group]
The thermosetting resin according to claim 1, which is one or a plurality of groups selected from the group represented by: X group and Y group have the following formula:

Or a group represented by the following formula:

[Wherein R ₅ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms]
The thermosetting resin according to any one of claims 1 to 6, which is one or a plurality of groups selected from the group represented by: Following formula:

The thermosetting resin of any one of Claims 1-7 represented by these.   A conductive paste composition comprising the thermosetting resin according to claim 1 and a conductive substance. (I) The following formula:

[Where:
R ₁ represents an alkylene group,
R ₂ and R ₃ may be the same or different, and are an alkyl group or alkoxy group having 1 to 10 carbon atoms,
n ₁ and n ₂ may be the same or different and are integers from 0 to 2,
m is 0 or 1]
A step of polymerizing N repeating units represented by aldehyde with an aldehyde to obtain a phenol resole compound;
(II) A method for producing a thermosetting resin, comprising reacting the phenol resole compound obtained in the step (I) with a compound having one epoxy group. The repeating unit has the following formula:

The manufacturing method of Claim 10 represented by these.   The thermosetting resin manufactured by the manufacturing method of Claim 10 or 11.

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