JP2008222732A - Phenolic resin composition, epoxy resin composition, their cured products, water-based coating, new phenolic resin, and new epoxy resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new phenolic resin or new epoxy resin capable of being self-dispersed in aqueous media without modifying phenolic hydroxyl groups in the phenolic resin or epoxy groups in the epoxy resin and without using a large amount of an emulsifier, and to provide a phenolic resin composition or epoxy resin composition which contains the new phenolic resin or new epoxy resin, is excellent in storage stability and gives cured coating films excellent in mechanical strengths. <P>SOLUTION: The phenolic resin represented by structural formula (P1) or its epoxidized product is dispersed in an aqueous medium. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous phenolic resin composition, an epoxy resin composition, a cured product thereof, a novel phenolic resin, and a novel epoxy resin that are excellent in storage stability and corrosion resistance / adhesion of a processed product to be obtained.

  Thermosetting resin composition mainly composed of phenolic resin or epoxy resin is excellent in mechanical strength, corrosion resistance, adhesion, etc. of the resulting cured product, so it can be used for paints, adhesives, laminates, electrical / electronic parts, etc. Widely used in various fields. These thermosetting resins generally have a low affinity for water, and are usually used in the form of a solid or diluted in an organic solvent. However, due to environmental problems in recent years, it has been desired to reduce the amount of organic solvent discharged from the composition while maintaining the characteristics inherent to phenolic resins or epoxy resins. Development of an aqueous resin composition in which a thermosetting resin is dispersed is underway.

  As a technique for dissolving or dispersing the thermosetting resin in such an aqueous medium, from the viewpoint of making the epoxy resin aqueous, for example, by reacting a bisphenol type epoxy resin with a polyoxyalkylamine, And those obtained by reacting an epoxy resin with an alkanolamine, introducing a carboxyl group into the side chain, and neutralizing with an amine (see Patent Document 2 below) For example).

  However, the aqueous resins using these epoxy resins as raw materials are those in which a hydrophilic group is introduced into the polymer structure by modifying with an epoxy group as an active site, and the epoxy group is modified by modification. In addition to the disappearance, it is difficult to cause a curing reaction even in combination with a curing agent for epoxy resin, and the properties such as mechanical strength, corrosion resistance and the like inherently possessed by the cured epoxy resin are not expressed. When a general-purpose curing agent for epoxy resin was dispersed, a stable aqueous paint could not be obtained.

  On the other hand, in order to make the epoxy resin itself an aqueous dispersion without adding any modification to the epoxy group in the epoxy resin, a large amount of an emulsifier is required, which lowers the height and adhesion of the cured coating film. Met. Further, when the amount of the emulsifier was reduced with emphasis on the physical properties of the cured product, the storage stability of the emulsion itself was significantly impaired.

  On the other hand, in the field of phenolic resins, in order to introduce a hydrophilic group into the phenolic resin, it is necessary to modify the phenolic hydroxyl group in the phenolic resin, and to emulsify for the purpose of making it aqueous. Needed to use a large amount of emulsifier, protective colloid, etc., and had the same problems as those of the aqueous epoxy resin.

JP-A-10-183055 (pages 3-4) JP 2000-053745 A (pages 3 to 4)

  Therefore, the problem to be solved by the present invention is that the phenolic hydroxyl group in the phenolic resin or the epoxy group in the epoxy resin is not modified in any way, and it is self-reacting in an aqueous medium without using a large amount of emulsifier. Disclosed is a novel phenolic resin or epoxy resin that can be dispersed, and a phenolic resin composition or epoxy resin composition that contains this and has excellent storage stability and excellent mechanical strength of the cured coating film. is there.

  As a result of intensive studies to solve the above problems, the present inventors have introduced a specific partial structure into the molecular structure of the phenolic resin or epoxy resin, so that the phenolic resin or epoxy resin has its functional group. It has been found that a self-dispersing aqueous dispersion can be obtained without any loss, and that its storage stability is remarkably improved, and the present invention has been completed.

  That is, the present invention is a phenolic resin having a phenoxy structure in the main skeleton, wherein the phenoxy structure is represented by the following structural formula (1):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、ｎは繰り返し単位の平均値で１〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は直接結合を表す。）
で表される化学構造を有するフェノール系樹脂（Ａ）、及び、硬化剤（Ｂ）を必須成分とすることを特徴とするフェノール系樹脂組成物に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural moiety having a hydroxyl group further to the aliphatic hydrocarbon group, or a direct bond)
It is related with the phenol-type resin composition characterized by making the phenol-type resin (A) which has chemical structure represented by this, and a hardening | curing agent (B) into an essential component.

  The present invention further relates to a cured product obtained by curing the phenolic resin composition.

  The present invention further relates to an aqueous paint comprising a phenolic resin composition containing an aqueous medium (C) in addition to the phenolic resin (A) and the curing agent (B).

  The present invention further relates to a phenolic resin having a phenoxy structure in the main skeleton, wherein the phenoxy structure is represented by the following structural formula (1):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、ｎは繰り返し単位の平均値で１〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は直接結合を表す。）
で表される化学構造を有するフェノール系樹脂（Ａ）及び水性媒体（Ｃ）を必須成分とすることを特徴とするフェノール系樹脂組成物に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural moiety having a hydroxyl group further to the aliphatic hydrocarbon group, or a direct bond)
It is related with the phenol-type resin composition characterized by making the phenol-type resin (A) and aqueous medium (C) which have a chemical structure represented by these into an essential component.

  The present invention further provides an epoxy resin having a phenoxy structure in the main skeleton, wherein the phenoxy structure is represented by the following structural formula (1):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、ｎは繰り返し単位の平均値で１〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は直接結合を表す。）
で表される化学構造を有するエポキシ樹脂（Ａ’）、及び、硬化剤（Ｂ’）を必須成分とすることを特徴とするエポキシ樹脂組成物に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural moiety having a hydroxyl group further to the aliphatic hydrocarbon group, or a direct bond)
It is related with the epoxy resin composition characterized by making the epoxy resin (A ') and the hardening | curing agent (B') which have a chemical structure represented by these into an essential component.

  The present invention further relates to a cured product obtained by curing the epoxy resin composition.

  The present invention further relates to an aqueous paint comprising an epoxy resin composition containing an aqueous medium (C) in addition to the epoxy resin (A ′) and the curing agent (B ′).

  The present invention further provides an epoxy resin having a phenoxy structure in the main skeleton, wherein the phenoxy structure is represented by the following structural formula (1):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、ｎは繰り返し単位の平均値で１〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は、直接結合を表す。）
で表される化学構造を有するエポキシ樹脂（Ａ’）及び水性媒体（Ｃ）を必須成分とすることを特徴とするエポキシ樹脂組成物に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural part having a hydroxyl group on the aliphatic hydrocarbon group, or a direct bond)
It is related with the epoxy resin composition characterized by making the epoxy resin (A ') and the aqueous medium (C) which have a chemical structure represented by these into an essential component.

  The present invention further includes the following structural formula (3):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は同一でも異なっても良い、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、Ｒは水素原子又はメチル基であり、ｎは繰り返し単位の平均値で１〜５０であり、ｐは繰り返し数の平均値であって０〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は直接結合を表す。）
で表される分子構造を有することを特徴とする新規フェノール系樹脂に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms, R is a hydrogen atom or a methyl group, n is an average value of repeating units of 1 to 50, and p is an average of the number of repeating units. X ¹ is an aliphatic hydrocarbon group in which a plurality of alkylene groups having 1 to 4 carbon atoms are knotted by a carbonyl group or a carbonyloxy group, and the aliphatic hydrocarbon group. It represents a structural moiety having a hydroxyl group or a direct bond.)
It has the molecular structure represented by these.

  The present invention further includes the following structural formula (5):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は同一でも異なっても良い、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基又は水素原子であり、Ｒは水素原子又はメチル基であり、ｎは繰り返し単位の平均値で１〜５０であり、ｐは繰り返し数の平均値であって０〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は直接結合を表す。）
で表される分子構造を有することを特徴とする新規エポキシ樹脂に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, R is a hydrogen atom or methyl group, n is an average value of repeating units of 1 to 50, and p is a repeating group. X ¹ is an aliphatic hydrocarbon group in which a plurality of alkylene groups having 1 to 4 carbon atoms are knotted by a carbonyl group or a carbonyloxy group, the aliphatic hydrocarbon It represents a structural part having a hydroxyl group in the group or a direct bond.)
It has the molecular structure represented by these.

According to the present invention, a phenolic hydroxyl group in a phenolic resin or a novel phenolic compound that is self-dispersible in an aqueous medium without any modification of the epoxy group in the epoxy resin and without using a large amount of an emulsifier. It is possible to provide a resin or a novel epoxy resin, and a phenol-based resin composition or an epoxy resin composition that contains this resin and has excellent storage stability and excellent mechanical strength of the cured coating film.
Accordingly, the phenolic resin composition and the epoxy resin composition of the present invention can be suitably used for paints, adhesives, fiber sizing agents, concrete primers, and the like.

Hereinafter, the present invention will be described in detail.
The phenolic resin (A) used in the phenolic resin composition of the present invention is a phenolic resin having a phenoxy structure in the main skeleton, and the phenoxy structure is represented by the following structural formula (1).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、ｎは繰り返し単位の平均値で１〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は、直接結合を表す。）
で表される化学構造を有することを特徴としている。

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural part having a hydroxyl group on the aliphatic hydrocarbon group, or a direct bond)
It has the chemical structure represented by these.

  In the present invention, since such a partial chemical structure is included in the molecular structure as a phenoxy structure, excellent self-dispersibility can be expressed without using an emulsifier, a dispersant, and a protective colloid. In addition, the balance between the hydrophilicity and hydrophobicity of the phenolic resin (A) can be adjusted by adjusting the length of the alkylene oxide moiety in the structural formula (1), that is, the value of n.

The phenolic resin (A) is represented by the following structural formula (2) as X ¹ in the structural formula (1).

（式中、Ｘ^２は単結合又は炭素原子数１〜４のアルキレン基であり、Ｒは水素原子又はメチル基である。）で表される化学構造部位を有するものがフェノール系樹脂（Ａ）の水性媒体中での自己分散性がより良好となり貯蔵安定性が良好となる他、塗料に用いた際の効果塗膜の機械的強度が良好となる点から好ましい。

(Wherein, X ² is a single bond or an alkylene group having 1 to 4 carbon atoms, and R is a hydrogen atom or a methyl group). In addition to better self-dispersibility in an aqueous medium and better storage stability, it is preferable from the viewpoint that the mechanical strength of the effect coating film when used in a paint is good.

Further, the phenolic resin (A) is more specifically,
1) Structural formula (3)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は同一でも異なっても良い、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、Ｒは水素原子又はメチル基であり、ｎは繰り返し単位の平均値で１〜５０であり、ｐは繰り返し数の平均値であって０〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は直接結合を表す。）
で表される分子構造を有するフェノール系樹脂（ａ）、

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms, R is a hydrogen atom or a methyl group, n is an average value of repeating units of 1 to 50, and p is an average of the number of repeating units. X ¹ is an aliphatic hydrocarbon group in which a plurality of alkylene groups having 1 to 4 carbon atoms are knotted by a carbonyl group or a carbonyloxy group, and the aliphatic hydrocarbon group. It represents a structural moiety having a hydroxyl group or a direct bond.)
A phenolic resin (a) having a molecular structure represented by:

2) a phenolic resin (b) having a structure obtained by reacting the phenolic resin (a) with a bifunctional epoxy resin;
3) A phenolic resin (c) obtained by reacting the phenolic resin (a), a bifunctional phenol, and a bifunctional epoxy resin,
The above phenol-type resin (a), (b), (c) is mentioned.

  Specific examples of the bifunctional phenol used in the production of the phenolic resin (b) include dihydric phenols such as hydroquinone, resorcinol and catechol, bisphenols such as bisphenol A and bisphenol F, and 1,6-dihydroxy. Examples include naphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene, and 4,4′-dihydroxybiphenyl.

  Moreover, as for the bifunctional epoxy resin used for manufacture of a phenol-type resin (b), the diglycidyl ether of the said bivalent phenol, bisphenols, dihydroxynaphthalene, and 4,4'-dihydroxybiphenyl is mentioned.

  The phenolic resin (A) described above is a phenolic resin from the viewpoints of excellent storage stability when it is an aqueous dispersion among the above (a) to (c) and excellent mechanical strength of a cured coating film. A resin (a) is preferred.

Here, in the structural formula (3), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, as described above, Specific examples of the alkyl group having 1 to 4 atoms include a hydrogen atom, ethylene, propylene, methylene, n-butyl, t-butyl group, and the like. Among these, a hydrogen atom or a methyl group is preferable from the viewpoint of excellent mechanical strength of the cured coating film, and a hydrogen atom is particularly preferable.

In the structural formula (3), as described above, R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group having 1 to 4 carbon atoms is Specific examples include a hydrogen atom or ethylene, propylene, methylene, n-butyl, t-butyl group, and the like.

Further, in the structural formula (3), X ¹ is, X ¹ is an aliphatic alkylene group is nodules with a carbonyl group or a carbonyloxy group of the plurality of 1 to 4 carbon atoms hydrocarbon group, the aliphatic hydrocarbon This represents a structural moiety further having a hydroxyl group in the group or a direct bond. Specifically, as described above, the following structural formula (2)

（構造式（２）中、Ｘ^２は単結合又は炭素原子数１〜４のアルキレン基であり、Ｒは水素原子又はメチル基である。）で表される構造部位が好ましい。

(In the structural formula (2), X ² is a single bond or an alkylene group having 1 to 4 carbon atoms, and R is a hydrogen atom or a methyl group).

Here, in the structural formula (2), the alkylene group having 1 to 4 carbon atoms in X ² includes a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, and a 2,2-propylidene group. 1,4-butylene group.

  In Structural Formula (3), Y is an alkyl group having 1 to 15 carbon atoms. Here, the alkyl group having 1 to 15 carbon atoms is methyl group, ethyl group, propyl group, i-propyl group, butyl group, t-butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, An undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and the like can be given.

  Moreover, in Structural formula (3), n is 1-50 by the average value of a repeating unit. As described above, the phenolic resin (a) represented by the structural formula (3) can exhibit excellent self-dispersibility without using an emulsifier, a dispersant, and a protective colloid. In addition, the balance between the hydrophilicity and hydrophobicity of the phenolic resin (A) can be adjusted by adjusting the length of the alkylene oxide moiety in the structural formula (3), that is, the value of n. From such a viewpoint, the value of n is particularly preferably 10 to 45.

  Among the phenolic resins (a) detailed above, the following structural formula (4)

で表される構造を有するもの（以下、これを「フェノール系樹脂（ａ２）」と略記する。）が特に、工業的生産が容易である他、水性分散体として保存安定性に優れ、かつ、その硬化塗膜の強度が著しく良好となる点から好ましい。
上記構造式（４）中、Ｒ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は構造式（３）の場合と同義であるが、これらのなかでもＲ^１、Ｒ^２、Ｒ^３、Ｒ^４は特に硬化塗膜の機械的強度に優れる点から水素原子又はメチル基であることが好ましく、特に水素原子であることが好ましく、Ｒは水素原子であることが好ましい。更に、Ｘ^２は前記構造式（２）と同義であり、メチレン基、エチレン基、１，３−プロピレン基、１，２−プロピレン基、２，２−プロピリデン基、１，４−ブチレン基が挙げられるが、特にフェノール系樹脂（Ａ）の親水性と疎水性とのバランスに優れる点からメチレン基が好ましい。

In particular (hereinafter abbreviated as “phenolic resin (a2)”), in addition to easy industrial production, and excellent storage stability as an aqueous dispersion, and This is preferable because the strength of the cured coating film is remarkably good.
In the structural formula (4), R, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ have the same meaning as in the structural formula (3). Among these, R ¹ , R ² , R ³ , R ⁴ is preferably a hydrogen atom or a methyl group from the viewpoint of excellent mechanical strength of the cured coating film, particularly preferably a hydrogen atom, and R is preferably a hydrogen atom. Further, X ² has the same meaning as in the structural formula (2), and a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 2,2-propylidene group, and a 1,4-butylene group. In particular, a methylene group is preferable because the balance between the hydrophilicity and the hydrophobicity of the phenolic resin (A) is excellent.

  In the structural formula (4), p is an average value of the number of repetitions, and is 0 to 50. From the viewpoint of good dispersibility in the medium (C), p = 0, the following structural formula (4 ′)

であらわされる化合物（以下、これを「フェノール系樹脂（ａ３）」と略記する。）が好ましい。

(Hereinafter, this is abbreviated as “phenolic resin (a3)”).

  The phenolic resin (A) described in detail above has a hydroxyl equivalent weight of 150 to 3000 g / from the viewpoint of storage stability when it is made into an aqueous dispersion, and the corrosion resistance of a cured coating film as a water-based coating becomes good. eq. It is preferable that it is the range of these.

  Here, in the structural formula (4 ′), n is an average value of repeating units of 1 to 50, and as described above, it is particularly preferably 10 to 45 from the viewpoint of storage stability of the aqueous dispersion. In the phenolic resin (A), p is an average value of repeating units of 0 to 50, and is preferably 0 to 30 from the viewpoint of corrosion resistance.

  Specific examples of the method for producing the phenolic resin (A) include the following methods 1) to 3) for producing the phenolic resin (a).

  Method 1) Structural formula (i)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に水素原子又は炭素原子数１〜４のアルキル基である。）
で示されるモノフェノールと、下記構造式（ii）

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
And the following structural formula (ii)

（式中、Ｒ^５は、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、ｎは繰り返し単位の平均値で１〜５０であり、Ｘ^１は、炭素原子数１〜４のアルキレン基を表す。）で示されるカルボニル化合物とを酸触媒下に反応させる方法。
方法２）前記方法１）で得られたフェノール系樹脂とエピハロヒドリン類とを前者／後者のモル比が１／０．５〜１／０．９となる割合で反応させる方法。
方法３）下記構造式（iii）

(In the formula, R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁶ is an alkylene group having 2 to 5 carbon atoms, and Y is an alkyl group having 1 to 15 carbon atoms. Yes, n is an average value of repeating units of 1 to 50, and X ¹ represents an alkylene group having 1 to 4 carbon atoms.) A method of reacting with a carbonyl compound represented by an acid catalyst.
Method 2) A method in which the phenolic resin obtained in the above method 1) is reacted with epihalohydrins at a ratio of the former / the latter molar ratio of 1 / 0.5 to 1 / 0.9.
Method 3) Structural formula (iii)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＸは前記と同じである。）
で表されるカルボキシル基含有ビスフェノール類（iii）とポリアルキレングリコール鎖を有するモノグリシジルエーテル（iv）とを反応させる方法。
方法４）前記方法３）で得られたフェノール系樹脂とエピハロヒドリン類とを前者／後者のモル比が１／０．５〜１／０．９となる割合で反応させる方法。

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are the same as above).
And a monoglycidyl ether (iv) having a polyalkylene glycol chain is reacted with a carboxyl group-containing bisphenol represented by formula (iii).
Method 4) A method in which the phenolic resin obtained in the above method 3) and the epihalohydrin are reacted at a ratio of the former / the latter molar ratio of 1 / 0.5 to 1 / 0.9.

  Among the above methods 1) to 4), the above methods 3) and methods are easy because industrial production is easy, storage stability as an aqueous dispersion is excellent, and the strength of the cured coating film is remarkably good. 4) is preferred, and method 3) is particularly preferred.

  Examples of the acid catalyst used in Method 1 include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Of Lewis acids.

  The carboxyl group-containing bisphenols (iii) used in the above method 3) have a substituent at the ortho position of, for example, orthocresol, 2,6-xylenol, orthobutylphenol in the presence of no catalyst or catalyst. By reaction of a compound containing a carboxyl group and a carbonyl group independent of this in one molecule such as 2-oxopropanoic acid, 3-oxobutanoic acid, 3-acetylpropionic acid, and glyoxylic acid. Can be obtained. Various catalysts can be used as the catalyst. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, and trifluoride. Examples include Lewis acids such as boron, anhydrous aluminum chloride, and zinc chloride. Examples of the basic catalyst include alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Although the usage-amount of these catalysts is not specifically limited, It is preferable to use 0.1-30 mass% with respect to the phenols which may have a substituent in the ortho position used as a raw material. The form of the catalyst is not particularly limited, and may be an aqueous solution or a solid.

  The reaction can be performed in the absence of a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, and the like. These may be used alone or in combination of two or more. As the usage-amount of an organic solvent, it is 50-300 mass% normally with respect to the total mass of the raw material to be used, Preferably it is 100-250 mass%. The reaction temperature is usually 40 to 180 ° C., and the reaction time is usually 1 to 10 hours. Further, it is preferable to distill off the water produced during the reaction by using a fractionating tube or the like outside the system in order to carry out the reaction quickly.

  Moreover, when the coloring of carboxyl group-containing bisphenols (iii) obtained by the reaction is large, an antioxidant or a reducing agent may be added in order to suppress it. Although it does not specifically limit as said antioxidant, For example, hindered phenol type compounds, such as a 2, 6- dialkyl phenol derivative, a bivalent sulfur type compound, a phosphite type compound containing a trivalent phosphorus atom, etc. Can be mentioned. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

  After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. There are no particular restrictions on the method of neutralization treatment or water washing treatment. For example, when an acidic catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, aniline, When a neutral catalyst is used, acidic substances such as hydrochloric acid, sodium hydrogen phosphate, and oxalic acid can be used as a neutralizing agent.

  After neutralization or washing with water, the carboxyl group-containing bisphenol (iii) can be obtained by distilling off the solvent and unreacted substances under heating under reduced pressure.

Among the carboxyl group-containing bisphenols (iii) thus obtained, the resulting phenolic resin (a2) or (a3) is excellent in water solubility and excellent in storage stability when used as an aqueous phenolic resin composition. In view of the excellent corrosion resistance and mechanical strength of the obtained compound, R ¹ , R ² , R ³ and R ^{4 in the} general formula (iii) are hydrogen atoms and R ⁵ is a methyl group. In addition, X in the general formula (iii) is preferably an ethylene chain, and most preferably diphenolic acid. In addition, since diphenolic acid is commercially available from Otsuka Chemical Co., Ltd., the commercially available product can be used as it is.

  Next, the monoglycidyl ether (iv) having a polyalkylene glycol chain used in the method 3) is, for example, the following structural formula (iv)

（Ｒ^６炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、Ｒは水素原子又はメチル基であり、ｎは繰り返し単位の平均値で１〜５０である）で表されるものが挙げられ、具体的には、ポリエチレングリコールモノメチルエーテルモノグリシジルエーエル、ポリプロピレングリコールモノメチルエーテルモノグリシジルエーエル、ポリテトラメチレングリコールモノエチルエーテルモノグリシジルエーエル、ポリヘキサメチレングリコールモノプロピルエーテルモノグリシジルエーエル、その他、前記構造式（iv）において、Ｒが水素原子、ｎが１５、Ｒ^６がエチレン、Ｙが炭素原子数１２のアルキル基である化合物（例えば、ナガセ化成工業株式会社製「デナコールＥＸ−１７１」エポキシ当量：９４３ｇ／ｅｑ）、Ｒが水素原子、ｎが４１、Ｒ^６がエチレン、Ｙが炭素原子数１２のアルキル基である化合物（例えば、ナガセ化成工業株式会社製「デナコールＦＣＡ−０５０」エポキシ当量：１４４２ｇ／ｅｑ）が挙げられる。

(R ⁶ is an alkylene group having 2 to 5 carbon atoms, Y is an alkyl group having 1 to 15 carbon atoms, R is a hydrogen atom or a methyl group, and n is an average value of repeating units of 1 to 50. Specific examples include polyethylene glycol monomethyl ether monoglycidyl aer, polypropylene glycol monomethyl ether monoglycidyl aer, polytetramethylene glycol monoethyl ether monoglycidyl aer, polyhexamethylene glycol monopropyl Ether monoglycidyl ether, and other compounds in the structural formula (iv) wherein R is a hydrogen atom, n is 15, R ⁶ is ethylene, and Y is an alkyl group having 12 carbon atoms (for example, manufactured by Nagase Chemical Industries, Ltd.) “Denacol EX-171” epoxy equivalent: 943 g / eq), a compound in which R is a hydrogen atom, n is 41, R ⁶ is ethylene, and Y is an alkyl group having 12 carbon atoms (for example, “Denacol FCA-050” manufactured by Nagase Chemical Industries, Ltd., epoxy equivalent: 1442 g) / Eq).

  Among these, polyethylene glycol monomethyl ether monoglycidyl air and polypropylene glycol monomethyl ether monoglycidyl air are preferable from the viewpoint of good balance of storage stability, coating film performance, and curability of the aqueous dispersion.

From the viewpoint of easy availability, in the structural formula (iv), a compound in which R is a hydrogen atom, n is 15, R ⁶ is ethylene, and Y is an alkyl group having 12 carbon atoms (for example, Nagase Kasei Kogyo Co., Ltd.) “Denacol EX-171” epoxy equivalent manufactured by the company: 943 g / eq), R is a hydrogen atom, n is 41, R ⁶ is ethylene, and Y is an alkyl group having 12 carbon atoms (for example, Nagase Chemical Industries, Ltd.) “Denacol FCA-050” epoxy equivalent: 1442 g / eq) is preferable.

  The specific method of reacting the carboxyl group-containing bisphenol (iii) with the monoglycidyl ether (iv) having a polyalkylene glycol chain is the same as the carboxyl group and monoglycidyl ether (iv) in the carboxyl group-containing bisphenol (iii). The glycidyl group is preferably reacted with the glycidyl group in the catalyst, and the reaction can be carried out in the absence of a catalyst or in the presence of a catalyst, but it is preferable to use a catalyst as appropriate from the viewpoint that the reaction proceeds rapidly. Examples of the catalyst that can be used here include alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, Metal alcoholates such as butoxy lithium and sodium methoxy, Lewis acids such as lithium chloride and aluminum chloride, and mixtures of Lewis acids and Lewis bases such as triphenylphosphine oxide, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, etc. Of chloride, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium, chloride, bromide, iodide, acetate 3 such as quaternary ammonium salts such as triethylamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene-7, 1,4-diazabicyclo [2.2.2] octane Examples include primary amines, imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole. Two or more of these may be used in combination. As a usage-amount of a catalyst, it is normally used in 5 ppm (mass basis)-2 mass% with respect to the total mass with the said monoglycidyl ether (iv), Preferably it is 20 ppm (mass basis)-0.5. % By mass. The form of these catalysts is not particularly limited, and the catalyst may be diluted with an appropriate solvent, used in the form of an aqueous solution, or used in a solid form.

  The reaction temperature for carrying out the reaction is preferably in the range of 100 to 150 ° C. from the viewpoint of an appropriate reaction rate and suppression of side reactions.

  The reaction can be performed in the absence of a solvent or in the presence of a solvent. As the solvent, the carboxyl group-containing bisphenol (iii) and the monoglycidyl ether (iv) are uniformly dissolved, and the carboxyl group-containing bisphenol (iii), monoglycidyl ether (iv) and a reaction product It is not particularly limited as long as it is inert with respect to the phenolic resin (a3). For example, water, methanol, ethanol, isopropanol, n-butanol, isobutanol and other alcohols, toluene, xylene, Hydrocarbons such as cyclohexane and decalin, ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, esters such as ethoxyethyl propionate, 3-methoxybutyl acetate, methoxypropyl acetate, cellosolve acetate, methyl cellosolve , Ethyl cellosolve , Cellosolves such as propyl cellosolve, butyl cellosolve, isobutyl cellosolve, tert-butyl cellosolve, glymes such as monoglyme, diglyme, triglyme, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether And aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide, and the like, and propylene glycol mono-tert-butyl ether. These can be used either as a single solvent or as a mixed solvent of two or more. Among these, since the reaction product solution obtained can be used as it is as the aqueous epoxy resin composition of the present invention, water alone, alcohols, cellosolves, glymes, aprotic polar solvents, Or it is preferable to use each mixed solvent.

  The reaction ratio of the carboxyl group-containing bisphenol (iii) and the monoglycidyl ether (iv) is not particularly limited, but the carboxyl group equivalent in the carboxyl group-containing bisphenol (iii) and the monoglycidyl ether (iv) When the ratio (iii) / (iv) to the epoxy equivalent of is small, the carboxyl group remains, and the carboxyl group reacts with the epihalohydrin during the reaction of the resulting phenolic resin (a3) with the epihalohydrin. Therefore, it becomes easy to finally form a fragile branched structure. Further, when the ratio is large, the amount of unreacted monoglycidyl ether (iv) increases, and the phenolic resin (a3) in the phenolic resin (a3) reacts with the obtained phenolic resin (a3) and epihalohydrins, which will be described later. A side reaction occurs between the phenolic hydroxyl group and the monoglycidyl ether (iv). As a result, a monofunctional epoxy resin in which one end of the molecule is an epoxy group and one is a polyalkylene glycol chain structure, or both ends are poly A non-functional resin having an alkylene bricol chain structure is generated, and a non-responsible one that does not contribute to the three-dimensional cross-linking easily reacts with the curing agent (B ′) described later. Therefore, the value of the ratio (iii) / (iv) is preferably 0.8 or more and 2 or less, particularly preferably 1 or more and 1.5 or less.

  Even if the phenol resin (A) thus obtained is used as it is, removal of the solvent, removal of unreacted monoglycidyl ether (iv), by-products (polymerized product, etc.), etc., as necessary. These purification steps may be performed.

  Moreover, when the coloring of the obtained phenol-type resin (A) is large, in order to suppress it, you may add antioxidant and a reducing agent. Although it does not specifically limit as antioxidant, For example, a hindered phenol type compound, such as a 2, 6- dialkylphenol derivative, a bivalent sulfur type compound, a phosphite type compound containing a trivalent phosphorus atom, etc. are mentioned. Can do. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

  The phenolic resin (A) is also useful as a raw material for the epoxy resin (A ′), which is the main component of the epoxy resin composition of the present invention described later (a raw material for reaction with epihalohydrins and an extender for general-purpose epoxy resins). It is.

  Next, the curing agent (B) that can be used in the phenolic resin composition of the present invention is an amino resin such as hexamethylenetetramine and aqueous melamine, an isocyanate compound such as methylene diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate, and the isocyanate compound. And water-based isocyanate compounds, epoxy resins and the like.

  Here, when the epoxy resin is used as the curing agent (B), examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and resorcin type epoxy resin. , Hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, liquid epoxy resin such as tetramethylbiphenyl type epoxy resin, brominated epoxy resin such as brominated phenol novolac type epoxy resin, solid bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, DISIC Pentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic carbonization Examples include a hydrogen formaldehyde resin-modified phenolic resin type epoxy resin, a biphenyl-modified novolac type epoxy resin, and the like.

  Moreover, when using an epoxy resin as a hardening | curing agent (B), further, in the range used as less than 70 mass% with respect to the synthetic | combination mass with the said phenol-type resin (A), Preferably it is less than 60 mass%. An epoxy resin curing agent may be used in combination. Here, the epoxy resin curing agent that can be used in combination is not particularly limited, and various types can be used. For example, amine compounds, acid anhydride compounds, amide compounds, phenol resins (A) Examples include other phenol compounds.

  Examples of the amine compounds include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, metaxylylenediamine, diaminodiphenylmethane, and phenylenediamine. Polyamide resins synthesized from aromatic polyamines, alicyclic polyamines such as 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, etc., dimers of dicyandiamide, linolenic acid and ethylenediamine Can be mentioned.

  Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, And methyl hexahydrophthalic anhydride.

  Other phenolic compounds of the phenolic resin (A) include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenolic resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, Trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin, aminotriazine-modified phenol resin, and modified products thereof Can be mentioned. Examples of the latent catalyst include imidazole, BF3-amine complex, and guanidine derivatives.

  Further, these amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like curing agents may be used alone or in combination of two or more. In addition, it is preferable to use the said acid anhydride type compound or amine-type compound in uses, such as an underfill material, and general paint uses. Also, amine-based compounds are preferred for applications such as adhesives. Furthermore, amine compounds, particularly dicyandiamide, are preferable from the viewpoint of workability and curability for flexil wiring board applications. Moreover, in the semiconductor sealing material use, a solid type phenolic compound is preferable from the point of the heat resistance of hardened | cured material.

  In the phenolic resin composition of the present invention, the blending ratio of the phenolic resin (A) and the curing agent (B) may be appropriately selected as a blending ratio at which the phenolic resin (A) is cured well. Although not limited, when using an epoxy resin as a hardening | curing agent (B), the phenolic hydroxyl group in a phenol-type resin (A) is 0.7 with respect to the total 1 equivalent of the epoxy group of an epoxy resin. It is preferable from the point that the mechanical property etc. of the hardened | cured material obtained that it is a ratio used as -1.5 equivalent become favorable.

  Next, the epoxy resin composition of the present invention is an epoxy resin having a phenoxy structure in the main skeleton, and the phenoxy structure is represented by the following structural formula (1).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基であり、ｎは繰り返し単位の平均値で１〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は、直接結合を表す。）
で表される化学構造を有するエポキシ樹脂（Ａ’）、及び、硬化剤（Ｂ’）を必須成分とすることを特徴とするものである。

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural part having a hydroxyl group on the aliphatic hydrocarbon group, or a direct bond)
An epoxy resin (A ′) having a chemical structure represented by formula (B) and a curing agent (B ′) are essential components.

  As in the case of the phenol resin (A), the epoxy resin (A ′) can exhibit excellent self-dispersibility without using an emulsifier, a dispersant, and a protective colloid. In addition, the balance between the hydrophilicity and hydrophobicity of the epoxy resin (A ′) can be adjusted by adjusting the length of the alkylene oxide moiety in the structural formula (1), that is, the value of n.

The epoxy resin (A ′) is represented by the following structural formula (2) as X ¹ in the structural formula (1).

（式中、Ｘ^２は単結合又は炭素原子数１〜４のアルキレン基であり、Ｒは水素原子又はメチル基である。）で表される化学構造部位を有するものがエポキシ樹脂（Ａ’）の水性媒体中での自己分散性がより良好となり貯蔵安定性が良好となる他、塗料に用いた際の効果塗膜の機械的強度が良好となる点から好ましい。

(Wherein X ² is a single bond or an alkylene group having 1 to 4 carbon atoms, and R is a hydrogen atom or a methyl group). In addition to better self-dispersibility in an aqueous medium and better storage stability, it is preferable from the viewpoint that the mechanical strength of the effect coating film when used in a paint is good.

  From this point of view, the epoxy resin (A ′) has an epoxy equivalent of 200 to 3100 g / eq. This range is particularly preferred from the viewpoint of excellent balance between the hydrophilicity and hydrophobicity of the epoxy resin (A ′).

The epoxy resin (A ′) is more specifically,
1) Structural formula (5)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は同一でも異なっても良い、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^６は炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基又は水素原子であり、Ｒは水素原子又はメチル基であり、ｎは繰り返し単位の平均値で１〜５０であり、ｐは繰り返し数の平均値であって０〜５０であり、Ｘ^１は、複数の炭素原子数１〜４のアルキレン基がカルボニル基若しくはカルボニルオキシ基で結節された脂肪族炭化水素基、該脂肪族炭化水素基に更に水酸基を有する構造部位、又は、直接結合を表す。）
で表される分子構造を有するエポキシ樹脂（ａ’）、

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, R is a hydrogen atom or methyl group, n is an average value of repeating units of 1 to 50, and p is a repeating group. X ¹ is an aliphatic hydrocarbon group in which a plurality of alkylene groups having 1 to 4 carbon atoms are knotted by a carbonyl group or a carbonyloxy group, the aliphatic hydrocarbon This represents a structural moiety having a hydroxyl group in the group or a direct bond.)
An epoxy resin (a ′) having a molecular structure represented by:

2) An epoxy resin (b ') obtained by further reacting the epoxy resin (a') with a bifunctional phenol,

3) An epoxy resin (c ′) obtained by reacting the phenolic resin (A) with a bifunctional epoxy resin, and

4) An epoxy resin (d ′) obtained by reacting the phenolic resin (A), a bifunctional phenol, and a bifunctional epoxy resin,
The above epoxy resins (a ′), (b ′), (c ′), and (d ′) are mentioned.

  Here, the bifunctional phenols used in the production of the epoxy resins (b ′) and (d ′) are specifically dihydric phenols such as hydroquinone, resorcinol and catechol, and bisphenols such as bisphenol A and bisphenol F. , Dihydroxynaphthalene such as 1,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl and the like.

  In addition, the bifunctional epoxy resin used in the production of the epoxy resins (b ′) to (d ′) includes diglycidyl ether of the dihydric phenol, bisphenols, dihydroxynaphthalene, and 4,4′-dihydroxybiphenyl. Can be mentioned.

  Among these, in the present invention, the epoxy resin (a ′) is particularly preferable from the viewpoint of the storage stability of the aqueous dispersion, and the (b ′) from the viewpoint that the corrosion resistance of the cured coating film is good as an aqueous paint. ) To (d ′) are preferably epoxy resins having a high molecular weight, and the epoxy resin (a) is particularly preferable because the aqueous dispersion has a good balance of storage stability, coating film performance, and curability. ') Is preferred.

  In the epoxy resin (a ′), in the structural formula (5), n is an average value of repeating units of 1 to 50, and is particularly preferably 10 to 45 from the viewpoint of storage stability of the aqueous dispersion. preferable.

  Among the epoxy resins (a ′) detailed above, in particular, the following structural formula (6)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ_６炭素原子数２〜５のアルキレン基であり、Ｙは炭素原子数１〜１５のアルキル基又は水素原子であり、Ｒは水素原子又はメチル基であり、Ｘ^２は単結合又は炭素原子数１〜４のアルキレン基であり、ｎは繰り返し単位の平均値で１〜５０であり、ｐは繰り返し数の平均値であって０〜５０である。）
で表される構造を有するものが特に工業的生産が容易である他、水性分散体として保存安定性に優れ、かつ、その硬化塗膜の強度が著しく良好となる点から好ましい。

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₆ is an alkylene having 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, R is a hydrogen atom or methyl group, X ² is a single bond or an alkylene group having 1 to 4 carbon atoms, n Is an average value of the repeating units and is 1 to 50, and p is an average value of the number of repetitions and is 0 to 50.)
In particular, those having a structure represented by the formula (1) are preferred because industrial production is easy, the aqueous dispersion is excellent in storage stability, and the strength of the cured coating film is remarkably good.

In the structural formula (6), R, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ have the same meaning as in the structural formula (5). Among these, R ¹ , R ² , R ³ , R ⁴ is preferably a hydrogen atom or a methyl group from the viewpoint of excellent mechanical strength of the cured coating film, particularly preferably a hydrogen atom, and R is preferably a hydrogen atom. Further, X ² has the same meaning as in the structural formula (2), and a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 2,2-propylidene group, and a 1,4-butylene group. In particular, a methylene group is preferable from the viewpoint of excellent balance between hydrophilicity and hydrophobicity of the epoxy resin (a ′).

  In the structural formula (6), n is an average value of repeating units of 1 to 50, and is preferably 10 to 45 from the viewpoint of storage stability of the aqueous dispersion. p is an average of 0 to 50 repeating units, and preferably 0 to 0.4 from the viewpoint of good dispersibility in an aqueous medium.

  Specifically, in the method for producing the epoxy resin (a ′), the phenol resin (a) or (a ′) is reacted with epihalohydrins such as epichlorohydrin, epibromohydrin, β-methylepichlorohydrin. A method is mentioned.

  More specifically, the method specifically adds 0.3 to 20 mol of an epihalohydrin to 1 mol of the phenolic hydroxyl group of the phenol resin (a) or (a ′). At a temperature of 20 to 120 ° C., 0.9 to 2.0 mol of a basic catalyst is added all at once or gradually added to 1 mol of the phenolic hydroxyl group of the phenol resin (a) or (a ′). The method of making it react for 0.5 to 10 hours is mentioned. The added amount of epihalohydrins increases the excess of epihalohydrins, and the resulting epoxy resin becomes closer to the theoretical structure, and suppresses the formation of secondary hydroxyl groups caused by the reaction between unreacted phenolic hydroxyl groups and epoxy groups. can do. From this viewpoint, the range of 2.5 to 20 equivalents is preferable. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. It is also possible to use a method in which the water is removed and the epihalohydrins are continuously returned to the reaction mixture.

  When industrial production is performed, the first batch of epoxy resin production uses all of the prepared epihalohydrins, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount that disappears. At this time, epihalohydrins to be used are not particularly limited, and examples thereof include epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferable because it is easily available. The basic catalyst is not particularly limited, and examples thereof include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these alkali metal hydroxides may be used in the form of an aqueous solution of about 10 to 55% by mass or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples thereof include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After washing the reaction product of these glycidylation reactions, unreacted epihalohydrins and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain a high-purity epoxy resin (a ′).

  The epoxy resin composition of the present invention may be used in combination with other epoxy resins as long as the effects of the present invention are not impaired. When other epoxy resins are used in combination, the proportion of the epoxy resin (A ′) in the entire epoxy resin component is preferably in the range of 30% by mass or more, particularly in the range of 40% by mass or more.

  Examples of other epoxy resins that can be used in combination with the epoxy resin (A ′) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, and phenol novolac type epoxy resins. , Cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, Naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic tree Type epoxy resin, biphenyl-modified novolak type epoxy resins are not limited thereto. Moreover, these epoxy resins may be used independently and may mix 2 or more types. When these other epoxy resins are used in combination, surfactants and film-forming aids (organic solvents) that are essentially unnecessary in the present invention may be used in combination with water to make them water-based in advance and used as an aqueous dispersion. Good.

  Next, the curing agent (B ′) used in the epoxy resin composition of the present invention is, for example, an amine curing agent, a phenol novolak resin, a cresol novolak resin, a polycarboxylic acid, a polycarboxylic acid anhydride, or an imidazole such as phenylimidazole. , Dicyandiamides, dihydrazines such as adipic acid dihydrazide, and the like.

  Among these, an amine curing agent composed of a compound having two or more amino groups is preferred, and the structure is not particularly limited as long as it is a compound having two or more primary to tertiary amino groups, From the viewpoint of good compatibility with water, those based on aliphatic polyfunctional amines are more preferred, for example, pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine, diethylenetriamine, metaxylenediamine, Polyamide obtained by polycondensation of a part of the amino group of the aliphatic polyfunctional amines such as isophoronediamine, norbornenediamine, 1,3-bisaminomethylcyclohexane, N-aminoethylpiperazine and the like with an aliphatic dicarboxylic acid Examples include polyamines and modified products thereof.

  Examples of the aliphatic dicarboxylic acid include dimer acid composed of tall oil fatty acid, linolenic acid, linoleic acid, and the like.

  Examples of the modified product include the polyfunctional amines or the polyamide polyamines from the viewpoints of compatibility with the epoxy resin (A ′) and good dryness, chemical resistance, and corrosion resistance of the coating film. Adducts of dihydric or higher phenols and compounds derived from epichlorohydrin and / or Mannich modified polyamines of the polyfunctional amines, or the polyamide polyamines, compounds derived from phenols and formaldehyde Is particularly preferred.

  When the amine curing agent is used, it can be used as it is, or after neutralizing the amine with acid and adding water to form an aqueous solution, or an aqueous dispersion. These curing agents can be used alone or in combination of two or more.

  As the curing agent (B ′) in the aqueous epoxy resin composition of the present invention, the compounding amount in the case of using an amine curing agent is not particularly limited, but the impact resistance of the obtained workpiece, From the viewpoint of excellent corrosion resistance and the like, the molar ratio (epoxy group / active hydrogen group) of the total amount of epoxy groups in the aqueous epoxy resin composition containing the epoxy resin (A ′) to the active hydrogen groups in the amine curing agent is 100. / 60 to 100/120 is preferable.

  Further, as the curing agent (B ′), a compound capable of curing reaction with a hydroxyl group in the epoxy resin (A ′) can be used. As such a compound, it is preferable to use an amino resin, an isocyanate compound, or a phenol resin from the viewpoint of industrial availability.

  Examples of the amino resins include melamine resins derived from melamine and aldehyde compounds, guanamine resins derived from aldehyde compounds such as benzoguanamine and acetoguanamine, and urea resins derived from aldehyde compounds such as urea and thiourea. Can be mentioned.

  Further, as the amino resin, those in which amino components such as melamine and urea are co-condensed, and those in which methylol groups in the resin are substituted with alcohols such as methanol, propanol, isopropanol, butanol and isobutanol may be used. it can.

  As the use ratio of the amino resin, the solid content in the amino resin is 1 to 40 parts by mass with respect to 100 parts by mass of the total epoxy resin solid content including the epoxy resin (A ′) in the epoxy resin composition of the present invention. It is preferable that the ratio be 2 to 30 parts by mass.

  Although it does not specifically limit as said isocyanate compound, For example, aromatic isocyanates, such as phenylene diisocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate, metaxylylene diisocyanate, as diisocyanate, for example. Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated metaxylylene diisocyanate, norbornene Alicyclic diisocyanates such as diisocyanates S and the like, and solvent-free, can be used those which are diluted in a solvent.

  Examples of the polyisocyanate other than the diisocyanate include polymethylene polyphenyl isocyanate, dimethyltriphenylmethane tetraisocyanate, triphenylmethane triisocyanate, and tris (isocyanatophenyl) -triphosphate.

  Furthermore, as the isocyanate compound, it is also possible to use those subjected to various modification reactions for the purpose of reducing the vapor pressure, adjusting the viscosity, the number of functional groups, the reactivity, and imparting special physical properties using the above isocyanate. it can. Examples of these are urethane prepolymers that are reaction products with alcohols, allophanate-modified isocyanates obtained by addition reaction of isocyanate groups, biuret-modified isocyanates, uretdione-modified isocyanates, isocyanurate-modified isocyanates, Examples thereof include a carbodiimide-modified product, an uretonimine-modified product, an acylurea diisocyanate product, and the like utilizing an isocyanate group condensation reaction.

  Examples of the urethane prepolymers include diols composed of dimers of unsaturated alcohols such as ethylene glycol, polyethylene glycol, polypropylene glycol, and oleyl alcohol, trimethylolpropane, glycerin, 1,2,6-hexanetriol, Examples thereof include compounds having an isocyanate group at the terminal, obtained by reacting a polyol such as polyester polyol with the isocyanate compound.

  These isocyanate compounds may be used alone or as a mixture of two or more.

  Although it does not restrict | limit especially as said isocyanate compound and a usage rate, From the point which is excellent in the said performance of the hardened | cured material obtained, the epoxy resin solid content total amount containing the epoxy resin (A ') in an aqueous epoxy resin composition It is preferable to use 1-30 mass parts of solid content in an isocyanate compound with respect to 100 mass parts, More preferably, it is 3-25 mass parts.

  The phenol resin is not particularly limited as long as it is a compound in which a phenol and an aldehyde compound are subjected to a condensation reaction in the presence of a catalyst, and can be used alone or in combination of two or more.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, nonylphenol, and xylenol. Monohydric phenols, bisphenols such as bisphenol A, bisphenol F, tetramethylbisphenol F, bisphenol AD, bisphenol Z, naphthalenediols such as 1,5-dioxynaphthalene, 1,6-dioxynaphthalene, biphenols, Examples thereof include tetramethylbiphenol, and these can be used alone or in combination of two or more.

  As the catalyst, a basic catalyst or an acid catalyst can be used. Examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, amines, ammonia and the like, and a resol-type condensate is obtained. Examples of the acid catalyst include hydrochloric acid, phosphoric acid, oxalic acid, and the like, and a novolac type condensate is obtained.

  The proportion of the phenol resin used is not particularly limited, but the solid content in the phenolic resin is 1 to 100 parts by mass of the total epoxy resin solid content including the epoxy resin (A) of the epoxy resin composition of the present invention. The ratio is preferably 40 parts by mass, particularly preferably 2 to 30 parts by mass.

  Moreover, the epoxy resin composition of the present invention can be used in combination with a curing accelerator as necessary. For example, 2,4,6-tri (dimethylaminomethyl) phenol, benzyldimethylamine, 1,8 -Tertiary amines such as diazabicyclo [5,4,0] undecene (DBU), imidazoles such as 2-methyl-4-ethylimidazole, phosphines such as triphenylphosphine, phenols such as phenol and cresol Is mentioned.

  A phenolic resin composition comprising the phenolic resin (A) and the curing agent (B) detailed above, or an epoxy resin composition comprising the epoxy resin (A ′) and the curing agent (B ′) as essential components. The product is preferably used as a water-soluble resin composition or an aqueous dispersion by further using an aqueous medium (C) in combination. In the present invention, an aqueous dispersion is particularly preferable from the viewpoint of excellent storage stability.

  The phenolic resin composition of the present invention comprises the phenolic resin (A) and the aqueous medium (C) in addition to those containing the phenolic resin (A) and the curing agent (B) as essential components. It may be an essential component. In this case, the phenolic resin composition forms an aqueous dispersion in which the phenolic resin (A) is dispersed in the aqueous medium (C). When this aqueous dispersion is applied to a paint application or an adhesive application, a necessary amount of the curing agent (B) can be blended in the dispersion and used for coating or the like.

  In the state of the aqueous dispersion containing the phenolic resin (A) and the aqueous medium (C) as essential components, the solid content concentration is preferably 10 to 70% by mass from the viewpoint of storage stability. The dispersed particle diameter of the phenolic resin (A) to be separated is preferably 10 nm to 10 μm on average.

  Similarly, the epoxy resin composition of the present invention includes the epoxy resin (A ′) and the curing agent (B ′) as essential components, the epoxy resin (A ′), and the aqueous medium (C). May be an essential component. In this case, the epoxy resin composition forms an aqueous dispersion in which the epoxy resin (A ′) is dispersed in the aqueous medium (C). When this aqueous dispersion is applied to paint applications or adhesive applications, a necessary amount of a curing agent (B ′) can be blended into the dispersion and used for coating or the like.

  In the state of the aqueous dispersion containing the epoxy resin (A ′) and the aqueous medium (C) as essential components, the solid content concentration is preferably 10 to 70% by mass from the viewpoint of storage stability. It is preferable that the dispersed particle diameter of the epoxy resin (A ′) is 10 nm to 10 μm on average.

  The aqueous medium (C) used here is not particularly limited, but deionized water is preferable. The aqueous medium (C) is added after the synthesis step of the phenolic resin (A) or after the synthesis, or at any step after the synthesis step of the epoxy resin (A ′) or after the synthesis, and uniformly mixed by stirring. A dispersion can be formed.

  In the phenolic resin composition or the epoxy resin composition of the present invention, a water-soluble organic solvent may be used as a hydrophilic auxiliary as necessary. Examples of the water-soluble organic solvent include lower alcohols such as methanol, ethanol and isopropanol, methyl solosolve, ethyl cellosolve, n-propyl cellosolve, isopropyl cellosolve, butyl cellosolve, isobutyl cellosolve, cellosolves such as tert-butyl cellosolve, Glymes such as monoglyme, diglyme and triglyme, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol mono n-butyl ether, polypropylene glycol monoisobutyl ether, polypropylene glycol mono-tert-butyl ether, etc. Among these, solubility in the epoxy resin (A) is good From a certain point, isopropanol, propyl cellosolve, butyl cellosolve, isobutyl Cellosolve, tert- butyl cellosolve, diglyme, it is preferable to use propylene glycol monomethyl ether.

  As described above, the phenolic resin composition or the epoxy resin composition of the present invention easily forms an aqueous dispersion without using any surfactant, and exhibits excellent stability. For the purpose of further improving the storage stability, a very small amount of a surfactant may be used as long as the physical properties of the cured film are not deteriorated.

  Examples of the surfactant used here include anionic surfactants such as fatty acid salts, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyalkylene ether phosphates, alkylbetaines, and alkylbenzyls. Zwitterionic surfactants such as ammonium salts and alkylammonium hydroxides, polyethylene glycol, polyoxyethylene sorbitan esters, polyoxyethylene alkylamines, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyalkylene polycyclic phenyl ethers, Nonionic surfactants such as polyoxyalkylene styrenated phenols may be mentioned. Among these, a nonionic surfactant is preferable and a polyoxyalkylene polycyclic phenyl ether is more preferable from the viewpoint of compatibility with an epoxy resin and non-reactivity with an epoxy group. The amount of these surfactants used is not particularly limited as long as an aqueous dispersion can be obtained, but is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of epoxy resins in the aqueous epoxy resin composition, and When used for water-based paint applications, etc., it is preferably 5 parts by mass or less, more preferably 2.5 parts by mass or less, from the viewpoint of good water resistance of the dried coating film.

  In addition, the phenolic resin composition or the epoxy resin composition of the present invention may be used in combination with other polyester-based aqueous resins, acrylic-based aqueous resins, and the like, as long as the characteristics of the present invention are not impaired. .

  Furthermore, the phenolic resin composition or the epoxy resin composition of the present invention includes a repellency inhibitor, an anti-sagging agent, a flow agent, an antifoaming agent, a curing accelerator, an ultraviolet absorber, a light stabilizer, and the like as necessary. Various additives may be blended.

  The use of the phenolic resin composition or the epoxy resin composition of the present invention can be suitably used as, for example, a paint, an adhesive, a fiber sizing agent, a concrete primer, etc., and particularly excellent in corrosion resistance and infinite dilution with water. It is preferable to use as a water-based paint.

  When the phenolic resin composition or epoxy resin composition of the present invention is used for coating applications, various fillers such as rust preventive pigments, colored pigments, extender pigments, various additives, etc. may be blended as necessary. preferable. Examples of the anticorrosion pigment include zinc powder, aluminum phosphomolybdate, zinc phosphate, aluminum phosphate, barium chromate, aluminum chromate, graphite and other scaly pigments, and the coloring pigment includes carbon black, oxidation pigment, etc. Examples thereof include titanium, zinc sulfide, and bengara. Examples of extender pigments include barium sulfate, calcium carbonate, talc, and kaolin. As a compounding quantity of these fillers, it is preferable from points, such as coating-film performance and coating workability, that it is 10-70 mass parts with respect to a total of 100 mass parts of an epoxy resin, water, and a hardening | curing agent.

  The coating method in the case of using the phenolic resin composition or the epoxy resin composition of the present invention for coating is not particularly limited, and roll coating, spraying, brush, spatula, bar coater, dip coating, electrodeposition coating method As the processing method, room temperature drying to heat curing can be performed. In the case of heating, a coating film can be obtained by reacting at 50 to 250 ° C., preferably 60 to 230 ° C., for 2 to 30 minutes, preferably 5 to 20 minutes.

  Moreover, when using the phenol-type resin composition or epoxy resin composition of this invention as an adhesive agent, it does not specifically limit, After apply | coating to a base material with a spray, a brush, and a spatula, match | combine the adhesive surface of a base material. The bonding part can form a strong adhesive layer by fixing the surrounding area or press-bonding. Steel plates, concrete, mortar, wood, resin sheets, resin films are suitable as the base material, and various surface treatments such as physical treatment such as polishing, electrical treatment such as corona treatment, and chemical treatment such as chemical conversion treatment are performed as necessary. More preferably, it is applied after application.

  In addition, when using the phenolic resin composition or epoxy resin composition of the present invention as a fiber sizing agent, for example, it is applied to a fiber immediately after spinning using a roller coater, wound as a fiber strand, and then dried. The method of performing is mentioned. The fiber to be used is not particularly limited. For example, inorganic fibers such as glass fiber, ceramic fiber, asbestos fiber, carbon fiber, and stainless steel fiber, natural fibers such as cotton and hemp, synthetic fibers such as polyester, polyamide, and urethane. Examples of the shape of the base material include short fibers, long fibers, yarns, mats, and sheets. The amount used as the fiber sizing agent is preferably 0.1 to 2% by mass as the resin solid content with respect to the fiber.

  Moreover, when using the phenol-type resin composition or epoxy resin composition of this invention as a concrete primer, it does not specifically limit, It can carry out with a roll, a spray, a brush, a spatula, and a scissors.

As a method for obtaining the cured product of the present invention, it is sufficient to comply with a general curing method of an epoxy resin composition, but the heating temperature and time differ depending on the kind of curing agent to be combined, and therefore the respective optimum temperature and time are set. It is preferable to select. In addition, a general method of the epoxy resin composition is used as the molding method and the like, and the conditions specific to the aqueous epoxy resin composition of the present invention are not particularly necessary.

Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, the part and% as described below are based on mass unless otherwise specified.
Example 1 Synthesis of Phenolic Resin (Ph-1) In a four-necked flask equipped with a thermometer, stirring device, dropping funnel, cooling pipe, nitrogen gas introduction pipe, and a separation cock at the bottom,
286 g of diphenolic acid (hydroxyl equivalent 143 g / eq, carboxyl equivalent 286 g / eq, manufactured by Otsuka Chemical Co., Ltd.) In the structural formula (iv), R is a hydrogen atom, n is 15, R ⁶ is ethylene, and Y is a carbon atom. A homogeneous solution was prepared by charging 1037 g of a compound having an alkyl group of 12 (“Denacol EX-171” epoxy equivalent: 943 g / eq) manufactured by Nagase Chemical Industries, Ltd.) and stirring with heating to 120 ° C. Thereafter, 13 g of a 4% by mass aqueous sodium hydroxide solution was added, and the mixture was further reacted at the same temperature for 8 hours. Thereafter, neutralized sodium phosphate was added to obtain 1320 g of a phenolic resin (hereinafter, this compound is abbreviated as “phenolic resin (Ph-1)”). This phenolic resin (Ph-1) was confirmed to contain a phenolic resin having a structure represented by the following structural formula (p1) from the NMR spectrum ( ¹³ C) of FIG.
The phenolic resin (Ph-1) had a hydroxyl equivalent of 615 g / eq.

Example 2 Synthesis of Epoxy Resin (Ep-1) 615 g of phenolic resin (Ph-1) obtained in Example 1 (hydroxyl equivalent 615 g / eq) on a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer .), 925 g (10 mol) of epichlorohydrin and 222 g of n-butanol were charged and dissolved. Thereafter, the temperature was raised to 65 ° C. while purging with nitrogen gas, and then the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under these conditions for 0.5 hour. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was conducted while returning the organic layer to the reaction system. Thereafter, the pressure was returned to normal pressure, and 240 g of water was charged and the produced salt was washed. After washing, unreacted epichlorohydrin was distilled off under reduced pressure. To the resulting crude epoxy resin, 1000 g of toluene was added and dissolved. Thereafter, a neutralized amount of sodium phosphate was added, and then the system was dehydrated by azeotropic distillation, followed by microfiltration, and then the solvent was distilled off under reduced pressure to obtain 685 g of a liquid epoxy resin (hereinafter referred to as this epoxy resin). Is abbreviated as “epoxy resin (Ep-1)”. This epoxy resin (Ep-1) was confirmed to contain an epoxy resin represented by the following structural formula (e1) from NMR spectrum ( ¹³ C). The epoxy equivalent of the obtained epoxy resin (Ep-1) was 755 g / eq. The viscosity was 1200 mm ² / s (25 ° C., Canon Fenske method), and p in the following structural formula calculated from the epoxy equivalent was 0.2. In addition, the value of n in the structural formula (e1) was 15. In the structural formula (e1), n and p represent the average of repeating units.

Example 3 Synthesis of Phenolic Resin (Ph-2) In Example 1, 1037 g of “Denacol EX-171” was converted into a hydrogen atom, n was 41, R ⁶ was ethylene, Y in the structural formula (iv) Is a compound having a carbon number of 12 (“Denacol FCA-050” epoxy equivalent: 1442 g / eq, manufactured by Nagase Chemical Industries, Ltd.) 1870 g of phenol-based resin 1540 g in the same manner as in Example 1. (Hereinafter, this phenolic resin is abbreviated as “phenolic resin (Ph-2).” The hydroxyl equivalent of this phenolic resin (Ph-2) was 1195 g / eq.

Example 4 Synthesis of Epoxy Resin (Ep-2) In Example 2, the raw material used was changed from 508 g of phenolic resin (Ph-1) to 1195 g of phenolic resin (Ph-2) (hydroxyl equivalent 1195 g / eq.). Except for the above, 1290 g of a liquid epoxy resin was obtained by the same operation as in Example 2 (hereinafter, this epoxy resin is abbreviated as “epoxy resin (Ep-2)”). The epoxy equivalent of this epoxy resin (Ep-2) is 1410 g / eq. The viscosity was 860 mm ² / s (25 ° C., Canon Fenske method), and p in the structural formula (e1) calculated from the epoxy equivalent was 0.2. Moreover, n in the structural formula (e1) was 41.

Example 5 Synthesis of Phenolic Resin (Ph-3) In Example 1, 1037 g of “Denacol EX-171” was obtained by combining R in the structural formula (iv) with a hydrogen atom, Y with 1 carbon atom, and R ⁶ with 1700 g of a phenolic resin was obtained in the same manner as in Example 1 except that ethylene and n were 41 polyethylene glycol monomethyl ether monoglycidyl ether (epoxy equivalent: 1288 g / eq, 1415 g). The resin is abbreviated as “phenolic resin (Ph-3).” The hydroxyl equivalent of this phenolic resin (Ph-3) was 1040 g / eq.

Example 6 Synthesis of Epoxy Resin (Ep-3) In Example 2, the raw material used was changed from phenolic resin (Ph-1) 508 g to phenolic resin (Ph-3) 1040 g (hydroxyl equivalent 1040 g / eq.). Except for the above, 1060 g of a liquid epoxy resin was obtained in the same manner as in Example 2 (hereinafter, this epoxy resin is abbreviated as “epoxy resin (Ep-3)”). The epoxy equivalent of this epoxy resin (Ep-3) is 1230 g / eq. The viscosity was 1100 mm ² / s (25 ° C., Canon Fenske method), and p in the structural formula (e1) calculated from the epoxy equivalent was 0.2. Moreover, n in the structural formula (e1) was 41.

Example 7 Synthesis of Epoxy Resin (Ep-4) A bisphenol A type liquid epoxy resin (Dainippon Ink Chemical Co., Ltd.) was placed in a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, a condenser tube, and a nitrogen gas inlet tube. “EPICLON 850-S” manufactured by Co., Ltd., 752 g of epoxy equivalent 188 g / eq), 690 g of phenolic resin (Ph-3) obtained in Example 5, and 228 g of bisphenol A (hydroxyl equivalent 114 g / eq) were charged up to 140 ° C. After heating for 30 minutes, 10 g of a 4 mass% aqueous sodium hydroxide solution was charged. Thereafter, the temperature was raised to 150 ° C. over 30 minutes, and the reaction was further continued at 150 ° C. for 8 hours. Thereafter, a neutralizing amount of sodium phosphate was added to obtain 1260 g of an epoxy resin (hereinafter, this epoxy resin is abbreviated as “epoxy resin (Ep-4)”). The epoxy equivalent of this epoxy resin (Ep-4) is 1280 g / eq. It was semisolid at 25 ° C.

Comparative Example 1 (Compound described in Patent Document 1)
EPICLON 1055 (Bisphenol A type solid epoxy resin, epoxy equivalent 475 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.) is attached to a four-necked flask equipped with a thermometer, stirring device, dropping funnel, cooling tube, and nitrogen gas introduction tube. ) 300 g and 135 g of butyl cellosolve were charged, heated to 100 ° C. and stirred and homogenized, then 4 g of monoethanolamine (alkanolamine, manufactured by Nippon Shokubai Co., Ltd.), Jeffamine M-1000 (polyoxyalkyleneamine compound, PT (Eye Japan Co., Ltd.) 101 g was charged in sequence while paying attention to heat generation, and the reaction was carried out at 130 ° C. until the solution viscosity was saturated to obtain an epoxy resin (A′-1). 360 g of ion exchange water was added to the epoxy resin (A′-1), and the mixture was stirred and homogenized to obtain an aqueous epoxy resin composition (E′-1) having a nonvolatile content of 45%.

Comparative Example 2 (Compound described in Patent Document 2)
EPICLON 2055 (Bisphenol A type solid epoxy resin, epoxy equivalent 625 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.) to a four-necked flask equipped with a thermometer, stirrer, dropping funnel, condenser and nitrogen gas inlet tube ) 300 g and diglyme 180 g were charged, heated to 70 ° C. and homogenized with stirring, 21 g of monoethanolamine was added, and the mixture was reacted at 100 ° C. for 7 hours. After cooling to 70 ° C., 59 g of succinic anhydride was added, the temperature was raised to 95 ° C. and reacted for 1 hour. Next, the reaction liquid was cooled to 60 ° C., 35 g of 29% ammonia water was added, and after stirring and homogenizing, 527 g of ion-exchanged water was added, and stirring and homogenizing were carried out to make an aqueous epoxy resin composition (E ′ -2) was obtained.

Examples 8-12 and Comparative Examples 3-6
Four types of epoxy resins (Ep-1), (Ep-2), (Ep-3), (Ep-4), phenolic resin (Ph-1), and polyethylene glycol dimer synthesized as described above. Glycidyl ether (Ep-5, Nagase Kasei Kogyo “Denacol EX-861” epoxy equivalent 587 g / eq, average number of ethylene glycol repeats 22), bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd.) Each performance evaluation was performed by the following method using “EPICLON 1055”, epoxy equivalent 480 g / eq.).

[Water varnish stability]
An epoxy resin composition having a non-volatile content of 90% was obtained by adding each epoxy resin and propyl cellosolve and mixing the mixture according to Table 1 and homogenizing. Ion exchange water was added to this epoxy resin composition in accordance with the formulation shown in Table 1, and the mixture was stirred and homogenized to obtain an aqueous epoxy resin composition having a nonvolatile content of 45%. 90 g of this was weighed into a 100 ml mayonnaise bottle, stored in a dryer at 40 ° C., and the appearance after 3 months was visually observed.
○: Precipitation, no separation, ×: Separation or agglomeration confirmed

[Amine odor]
The mayonnaise bottle after 3 months of the stability test was opened, and a sensory test was conducted for amine odor.
○: No amine odor, ×: Amine odor present

Examples 13 to 16 and Comparative Examples 7 and 8
Next, using the obtained water-based epoxy resin composition to create a water-based paint at the blending ratio of Table 2, after applying by a bar coater on the cold-rolled steel plate surface-treated with # 400 sandpaper, The coating film physical properties were evaluated. In addition, the paint of Table 2 is PWC = 50%, and the physical property of a coating film is a test result after 60-micrometer film thickness and 25 degreeC x 7 day curing. Each test method and evaluation criteria are as follows.

Weight drop resistance: In accordance with JIS K-5600-5-3 (1999), a DuPont type was used with a striker of 1/2 inch and a load of 500 g.
◯: No crack or the like at 50 cm. X: Generation | occurrence | production of a crack etc. is recognized by 50 cm.

Adhesion test: According to JIS K-5600-5-6 (1999), cuts were made at intervals of 1 mm, and the state of the coating film was visually observed after peeling off after applying the tape.
○: No peeling. X: Peeling is seen.

表２中の略号は以下の通りである。
「８２９０Ｙ６０」：ジャパンエポキシレジン社製ポリアミン樹脂「エピキュア ８２９０Ｙ６０」活性水素当量（溶液値＝２７２ｇ／ｅｑ）、不揮発成分：６０％
「Ｋ−ホワイト」：テイカ株式会社製防錆顔料「Ｋ−ホワイト」
「ＣＲ−９７」：石原産業株式会社製酸化チタン「タイペークＣＲ−９７」
「ＳＮデフォーマー７７７」：サンノプコ株式会社製消泡剤
「ＢＹＫ−３４１」：ビックケミー社製添加剤

Abbreviations in Table 2 are as follows.
“8290Y60”: polyamine resin “Epicure 8290Y60” manufactured by Japan Epoxy Resin Co., Ltd., active hydrogen equivalent (solution value = 272 g / eq), nonvolatile component: 60%
“K-White”: Anti-corrosive pigment “K-White” manufactured by Teika Co., Ltd.
“CR-97”: Titanium oxide “Taipaque CR-97” manufactured by Ishihara Sangyo Co., Ltd.
“SN Deformer 777”: Defoamer manufactured by San Nopco Co., Ltd. “BYK-341”: Additive manufactured by Big Chemie

3 is a ¹³ C-NMR spectrum of the phenol resin obtained in Example 1. FIG. 3 is a ¹³ C-NMR spectrum of the epoxy resin obtained in Example 2.

Claims (20)

A phenolic resin having a phenoxy structure in the main skeleton, the phenoxy structure being represented by the following structural formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural moiety having a hydroxyl group further to the aliphatic hydrocarbon group, or a direct bond)
A phenolic resin composition comprising a phenolic resin (A) having a chemical structure represented by formula (B) and a curing agent (B) as essential components. The phenolic resin (A) is represented by the following structural formula (2) as X ¹ in the structural formula (1).

The compound according to claim 1, wherein X ² is a single bond or an alkylene group having 1 to 4 carbon atoms, and R is a hydrogen atom or a methyl group. A phenolic resin composition. The phenolic resin (A) has the following structural formula (3)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms, R is a hydrogen atom or a methyl group, n is an average value of repeating units of 1 to 50, and p is an average of the number of repeating units. X ¹ is an aliphatic hydrocarbon group in which a plurality of alkylene groups having 1 to 4 carbon atoms are knotted by a carbonyl group or a carbonyloxy group, and the aliphatic hydrocarbon group. It represents a structural moiety having a hydroxyl group or a direct bond.)
The phenolic resin composition according to claim 1, which has a molecular structure represented by: The phenolic resin (A) is represented by the following structural formula (4)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₆ having 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, R is a hydrogen atom or methyl group, X ² is a single bond or an alkylene group having 1 to 4 carbon atoms, n is an average value of the repeating units, and is 1 to 50, and p is an average value of the number of repetitions and is 0 to 50.)
The phenolic resin composition according to claim 3, which has a structure represented by: The phenolic resin (A) has a hydroxyl equivalent weight of 150 to 3000 g / eq. The phenolic resin composition according to claim 1, wherein the phenolic resin composition is in the range of The phenolic resin composition according to any one of claims 1 to 5, wherein the curing agent (B) is an epoxy resin. The phenolic resin composition according to any one of claims 1 to 6, further comprising an aqueous medium (C) in addition to the phenolic resin (A) and the curing agent (B). Hardened | cured material formed by hardening | curing the phenolic resin composition of any one of the said Claims 1-7. An aqueous paint comprising the phenolic resin composition according to claim 7. A phenolic resin having a phenoxy structure in the main skeleton, the phenoxy structure being represented by the following structural formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural moiety having a hydroxyl group further to the aliphatic hydrocarbon group, or a direct bond)
A phenolic resin composition comprising a phenolic resin (A) having a chemical structure represented by formula (A) and an aqueous medium (C) as essential components. An epoxy resin having a phenoxy structure in the main skeleton, wherein the phenoxy structure is represented by the following structural formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural part having a hydroxyl group on the aliphatic hydrocarbon group, or a direct bond)
An epoxy resin composition comprising an epoxy resin (A ′) having a chemical structure represented by formula (B) and a curing agent (B ′) as essential components. The epoxy resin (A ′) is represented by the following structural formula (5)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, R is a hydrogen atom or methyl group, n is an average value of repeating units of 1 to 50, and p is a repeating group. X ¹ is an aliphatic hydrocarbon group in which a plurality of alkylene groups having 1 to 4 carbon atoms are knotted by a carbonyl group or a carbonyloxy group, the aliphatic hydrocarbon It represents a structural part having a hydroxyl group in the group or a direct bond.)
The epoxy resin composition according to claim 11, which has a molecular structure represented by: The epoxy resin (A ′) is represented by the following structural formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₆ is an alkylene having 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, R is a hydrogen atom or methyl group, X ² is a single bond or an alkylene group having 1 to 4 carbon atoms, n Is an average value of the repeating units and is 1 to 50, and p is an average value of the number of repetitions and is 0 to 50.)
The epoxy resin composition according to claim 12, which has a structure represented by: The epoxy resin (A ′) has an epoxy equivalent of 200 to 3100 g / eq. The epoxy resin composition according to claim 11, 12 or 13. The epoxy resin composition according to any one of claims 11 to 14, further comprising an aqueous medium (C) in addition to the epoxy resin (A ') and the curing agent (B'). Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of the said Claims 11-15. An aqueous paint comprising the epoxy resin composition according to claim 15. An epoxy resin having a phenoxy structure in the main skeleton, wherein the phenoxy structure is represented by the following structural formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. An alkylene group, Y is an alkyl group having 1 to 15 carbon atoms, n is an average value of repeating units of 1 to 50, and X ¹ is a plurality of alkylene groups having 1 to 4 carbon atoms. An aliphatic hydrocarbon group linked by a group or a carbonyloxy group, a structural part having a hydroxyl group on the aliphatic hydrocarbon group, or a direct bond)
An epoxy resin composition comprising an epoxy resin (A ′) having a chemical structure represented by formula (A) and an aqueous medium (C) as essential components. The following structural formula (3)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms, R is a hydrogen atom or a methyl group, n is an average value of repeating units of 1 to 50, and p is an average of the number of repeating units. X ¹ is an aliphatic hydrocarbon group in which a plurality of alkylene groups having 1 to 4 carbon atoms are knotted by a carbonyl group or a carbonyloxy group, and the aliphatic hydrocarbon group. It represents a structural moiety having a hydroxyl group or a direct bond.)
A novel phenolic resin characterized by having a molecular structure represented by The following structural formula (5)

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ has 2 to 5 carbon atoms. Y is an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, R is a hydrogen atom or methyl group, n is an average value of repeating units of 1 to 50, and p is a repeating group. X ¹ is an aliphatic hydrocarbon group in which a plurality of alkylene groups having 1 to 4 carbon atoms are knotted by a carbonyl group or a carbonyloxy group, the aliphatic hydrocarbon It represents a structural part having a hydroxyl group in the group or a direct bond.)
A novel epoxy resin having a molecular structure represented by

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