JP5750777B2 - Calixarene derivative, method for producing calixarene derivative, curing agent for epoxy resin, epoxy resin composition, and electronic component device - Google Patents

Description

  The present invention relates to a calixarene derivative, a production method thereof, an epoxy resin curing agent, an epoxy resin composition, and an electronic component device including an element sealed thereby.

  Conventionally, curable resins such as epoxy resins have been widely used in the fields of molding materials, laminates and adhesives, various electronic and electrical components, paints and ink materials. In particular, epoxy resin compositions are widely used as sealing materials in the field related to sealing technology for electronic component elements such as transistors and ICs. This is because epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

  On the other hand, in recent years, in the field of electronic components, speeding up and density increase have progressed, and accordingly, heat generation of electronic components has become remarkable. In addition, electronic components that operate at high temperatures are also increasing. For this reason, plastics used for electronic parts, particularly cured epoxy resins, are required to have high heat resistance and little change in physical properties compared to room temperature at high temperatures.

  In order to improve various properties of cured epoxy resins including heat resistance, methods using calixarenes as curing agents have been reported (see Patent Documents 1 to 5). According to these methods, it is possible to improve the glass transition temperature of the cured epoxy resin and to impart high heat resistance.

JP 2000-264953 A JP 2001-106868 A JP-A-2-123126 Japanese Patent Laid-Open No. 3-66724 JP-A-6-136341

  However, since the curing agent used in the above method has low solubility with the constituent components of the epoxy resin composition, the epoxy resin composition containing the curing agent is inferior in fluidity and difficult to mold, and has a curing reaction. There is a problem that it does not proceed completely and sufficient performance is not exhibited.

  An object of the present invention is to provide a novel calixarene derivative that can be used as a curing agent for an epoxy resin that has good solubility when formed into an epoxy resin composition and can impart high heat resistance to a cured epoxy resin. Is to provide. Moreover, the other subject of this invention is providing the electronic component apparatus provided with the epoxy resin composition containing the said hardening | curing agent for epoxy resins, and the element sealed by it.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that a novel calixarene derivative formed by β-alkenyl etherification of part or all of the phenolic hydroxyl group of calixarene is an epoxy resin. The present invention has been found to be useful as a curing agent for the use and capable of achieving the intended problem.

  The present invention relates to the following.

The present invention relates to (1) a calixarene derivative represented by the following general formula (I-1).

(In the above formula, n ′ and n ″ are 0 to 4, n ′ + n ″ is 1 to 4, m is an average number of 2 to 20, m × n ″ ≧ 0, and m repetitions. For each, R ¹ , R ² , R ³ , n ′, n ″ may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , Selected from the group consisting of optionally substituted hydrocarbon thio groups having 1 to 18 carbon atoms, all of which may be the same or different. )

The present invention is also as described in (1) above, wherein (2) 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the following general formula (I-2) is β-alkenyl etherified. To calixarene derivatives of

(In the above formula, n is 1 to 4, m is an average of 2 to 20, and R ¹ , R ² , and n may be the same or different for each of m repetitions,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )
The present invention also provides (3) the calixarene according to (1) or (2) above, wherein the calixarene (b1) is a compound represented by the following general formula (I-3): Relates to derivatives.

(In the above formula, m is an average number of 2 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )

In addition, the present invention provides (4) any one of the above (1) to (3), wherein the calixarene (b1) is a compound represented by the following general formula (I-4): The calixarene derivative described in 1. above.

(In the above formula, m is an average number of 2 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )

Further, the present invention provides (5) at least one selected from the group of calixarenes (b1) represented by the above general formula (I-2) and β-alkenyl halide represented by the following general formula (I-5). It relates to a method for producing a calixarene derivative according to any one of (1) to (4) above, wherein two compounds are reacted.

(In the above formulae, each R ³ independently represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a C 1 to 18 carbon atom which may have a substituent. Selected from the group consisting of a hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, all of which may be the same or different, and X is selected from a halogen atom .)

（上記式中、Ｒ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基、置換基を有していてもよい炭素数１〜１８の炭化水素オキシ基、置換基を有していてもよい炭素数１〜１８の炭化水素チオ基、及びハロゲン原子からなる群より選ばれ、全てが同一でも異なっていてもよく、
Ｒ^３は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基、置換基を有していてもよい炭素数１〜１８の炭化水素オキシ基、置換基を有していてもよい炭素数１〜１８の炭化水素チオ基からなる群より選ばれ、全てが同一でも異なっていてもよく、ｐは、平均で２未満の数である。） The present invention is characterized in that (6) a resorcinol derivative represented by the following general formula (I-7) is reacted with at least one compound selected from the group of aldehyde compounds, ketone compounds, and their multimers. The method for producing a calixarene derivative according to any one of (1) to (4) above.

(In the above formula, each R ² independently represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or an optionally substituted carbon group having 1 to 18 carbon atoms. Are selected from the group consisting of a hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, all may be the same or different, and p is an average number of less than 2. )

  The present invention also relates to (7) a curing agent for epoxy resins, characterized by using the calixarene derivative according to any one of (1) to (5) above.

  Moreover, this invention relates to the epoxy resin composition characterized by including the epoxy resin and the hardening | curing agent for epoxy resins as described in said (7).

  The present invention also relates to (9) an electronic component device comprising an element sealed with the epoxy resin composition described in (8) above.

  According to the present invention, a novel calixarene derivative is provided as a curing agent for an epoxy resin that has good solubility when formed into an epoxy resin composition and can impart high heat resistance to the cured epoxy resin. Can do. Moreover, according to this invention, the electronic component apparatus provided with the epoxy resin composition containing the said hardening | curing agent for epoxy resins, and the element sealed by it can be provided.

2 is a ¹ H-NMR chart of calixarene derivative 1 synthesized in Example 1. FIG. 2 is an IR chart of calixarene derivative 1 synthesized in Example 1. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 2 synthesized in Example 2. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 3 synthesized in Example 3. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 4 synthesized in Example 4. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 5 synthesized in Example 5. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 6 synthesized in Example 6. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 7 synthesized in Example 7. FIG. 6 is a GPC chart of calixarene derivative 7 synthesized in Example 7. 2 is a ¹ H-NMR chart of calixarene derivative 8 synthesized in Example 8. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 9 synthesized in Example 9. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 10 synthesized in Example 10. FIG. 2 is a ¹ H-NMR chart of calixarene derivative 11 synthesized in Example 11. FIG. It is a figure which shows the dynamic viscoelastic behavior of 175 degreeC and a 6-hour postcure in an Example and a comparative example. It is a figure which shows the dynamic viscoelastic behavior of 250 degreeC and the postcure after 6 hours in an Example and a comparative example. It is a figure which shows the dynamic viscoelastic behavior of 250 degreeC and the postcure after 6 hours in an Example and a comparative example.

  Hereinafter, the present invention will be described in detail.

<Calixarene derivative>
The calixarene derivative of the present invention is represented by the following general formula (I-1).

(In the above formula, n ′ and n ″ are 0 to 4, n ′ + n ″ is 1 to 4, m is an average number of 2 to 20, m × n ″ ≧ 1, and m repetitions. For each, R ¹ , R ² , R ³ , n ′, n ″ may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , Selected from the group consisting of optionally substituted hydrocarbon thio groups having 1 to 18 carbon atoms, all of which may be the same or different. )
Note that the “optionally substituted hydrocarbon group having 1 to 18 carbon atoms” here may be any hydrocarbon group having 1 to 18 carbon atoms in the main skeleton, and these hydrocarbons have. A part of hydrogen atoms may be substituted with other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups and the like.

  Similarly, the “hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent” may be any hydrocarbon oxy group having 1 to 18 carbon atoms in the main skeleton. Some of the hydrogen atoms may be substituted with other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, etc. The “hydrocarbon thio group having 1 to 18 carbon atoms that may be present” may be any hydrocarbon thio group having 1 to 18 carbon atoms in the main skeleton, and a part of the hydrogen atoms that these hydrocarbons have. It may be substituted by other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups and the like.

From the viewpoint of solubility, the calixarene derivative is preferably formed by β-alkenyl etherification of 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the following general formula (I-2). More preferably, 10 to 50% is β-alkenyl etherified.

(In the above formula, n is 1 to 4, m is an average of 2 to 20, and R ¹ , R ² , and n may be the same or different for each of m repetitions,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )
The calixarene (b1) is not particularly limited as long as it is a compound represented by the general formula (I-2), but is a compound represented by the following general formula (I-3) from the viewpoint of high heat resistance. The compound represented by the following general formula (I-4) is more preferable.

(In the above formula, m is an average number of 2 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )

(In the above formula, m is an average number of 2 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )
In the above general formulas (I-1) to (I-3), R ¹ is selected from the group consisting of a divalent organic group having 0 to 18 carbon atoms, such as an oxygen atom, a sulfur atom, or a sulfoxide group. , A sulfonyl group, and a divalent hydrocarbon group having 1 to 18 carbon atoms which may have a substituent.

  In this case, the “divalent hydrocarbon group having 1 to 18 carbon atoms which may have a substituent” may be any hydrocarbon group having a main skeleton of 1 to 18 carbon atoms. A part of hydrogen atoms of the hydrocarbon may be substituted with other atoms (for example, halogen etc.) or substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups.

Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms that may have the above substituent as R ¹ include, for example, an aliphatic hydrocarbon group such as a methylene group, an ethylene group, and a propylene group; An alicyclic hydrocarbon group such as a xylene group or a cyclopentylene group; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen, or the like is substituted on the aliphatic hydrocarbon group or the alicyclic hydrocarbon group; Aromatic hydrocarbon groups such as phenylene group, naphthylene group, anthracenylene group, etc .; those aromatic hydrocarbon groups substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens, etc. Is mentioned.

Among the divalent organic groups having 0 to 18 carbon atoms as R ¹ , an aliphatic hydrocarbon which may have a sulfur atom and a substituent from the viewpoint of ease of synthesis and synthesis yield. Group is preferable, and a methylene group which may have a substituent is more preferable. Examples of the methylene group which may have a substituent include, for example, a methylmethylene group, an ethylmethylene group, an isopropylmethylene group, a phenylmethylene group, a hydroxyphenylmethylene group, a cyclohexylmethylene group, a dimethylmethylene group, and a methyldiisopropylmethylene. Group, methylphenylmethylene group, cyclohexylmethylene group, cyclopentylmethylene group and the like. Among these, a methylmethylene group is preferable.

In the general formulas (I-1) to (I-3), each R ² independently represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a substituent. It is selected from the group consisting of a hydrocarbon oxy group having 1 to 18 carbon atoms which may have, a hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom.

As the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ² , an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, alicyclic Hydrocarbon group, aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group , Aliphatic hydrocarbon groups such as decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, Substituted with mercapto group, imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

Examples of the hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent as R ² include an aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent, and an aliphatic group. Cyclic hydrocarbonoxy group, aromatic hydrocarbonoxy group, etc., for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group , Aliphatic hydrocarbon oxy groups such as hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, allyloxy group, vinyloxy group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon oxy groups such as cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclopentenyloxy group, cyclohexenyloxy group;
These alicyclic hydrocarbon oxy groups include an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, methacryloyl Substituted with a group, mercapto group, imino group, ureido group, isocyanate group, etc .;
Aromatic hydrocarbon oxy groups such as phenoxy group, tolyloxy group, dimethylphenoxy group, ethylphenoxy group, butylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, ethoxyphenoxy group, butoxyphenoxy group, tert-butoxyphenoxy group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

Examples of the hydrocarbon thio group having 1 to 18 carbon atoms that may have a substituent as R ² include an aliphatic hydrocarbon thio group having 1 to 18 carbon atoms that may have a substituent, and an aliphatic group. Cyclic hydrocarbon thio group, aromatic hydrocarbon thio group, etc., for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, Aliphatic hydrocarbon thio groups such as hexylthio group, octylthio group, decylthio group, dodecylthio group, allylthio group, vinylthio group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon thio groups such as cyclopentylthio group, cyclohexylthio group, cycloheptylthio group, cyclopentenylthio group, cyclohexenylthio group;
These alicyclic hydrocarbon thio groups, groups containing an epoxy group such as an alkyl group, alkoxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group, etc., methacryloyl Substituted with a group, mercapto group, imino group, ureido group, isocyanate group, etc .;
Phenylthio group, tolylthio group, dimethylphenylthio group, ethylphenylthio group, butylphenylthio group, tert-butylphenylthio group, methoxyphenylthio group, ethoxyphenylthio group, butoxyphenylthio group, tert-butoxyphenylthio group, etc. An aromatic hydrocarbon thio group of
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

Examples of the halogen atom as R ² include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Among these, R ² is preferably a hydrogen atom from the viewpoint of high heat resistance.

In the general formula (I-1), R ³ is a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or an optionally substituted group having 1 to 18 carbon atoms. It is selected from the group consisting of a hydrocarbon oxy group and an optionally substituted hydrocarbon thio group having 1 to 18 carbon atoms.

As the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ³ , an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent or an alicyclic group Hydrocarbon group, aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group , Aliphatic hydrocarbon groups such as decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, glycidyloxy groups, epoxycyclohexyl groups, groups containing epoxy groups such as epoxy groups, methacryloyl groups, mercapto groups, Substituted by imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
These alicyclic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a glycidyloxy group, an epoxy cyclohexyl group, an epoxy group or other group containing an epoxy group, a methacryloyl group, a mercapto group. , Imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
They further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, a ureido group, And the like substituted with an isocyanate group.

Examples of the hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent as R ³ include an aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent, and an aliphatic group. Cyclic hydrocarbonoxy group, aromatic hydrocarbonoxy group, etc., for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group , Aliphatic hydrocarbon oxy groups such as hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, allyloxy group, vinyloxy group;
These aliphatic hydrocarbon oxy groups include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, glycidyloxy groups, epoxycyclohexyl groups, epoxy group-containing groups such as methacryloyl groups, mercapto groups. Substituted with an imino group, a ureido group, an isocyanate group, etc .; an alicyclic hydrocarbonoxy group such as a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclopentenyloxy group, a cyclohexenyloxy group;
These alicyclic hydrocarbon oxy groups include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, glycidyloxy groups, epoxycyclohexyl groups, epoxy groups and other groups containing methacryloyl groups, mercapto groups. Substituted by a group, imino group, ureido group, isocyanate group, etc .;
Aromatic hydrocarbon oxy groups such as phenoxy group, tolyloxy group, dimethylphenoxy group, ethylphenoxy group, butylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, ethoxyphenoxy group, butoxyphenoxy group, tert-butoxyphenoxy group;
They further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, a ureido group, And the like substituted with an isocyanate group.

As the hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent as R ³ , an aliphatic hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, an aliphatic group Cyclic hydrocarbon thio group, aromatic hydrocarbon thio group, etc., for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, Aliphatic hydrocarbon thio groups such as hexylthio group, octylthio group, decylthio group, dodecylthio group, allylthio group, vinylthio group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group, a methacryloyl group, a mercapto group , Imino group, ureido group, isocyanate group and the like substituted;
Cyclopentylthio group, cyclohexylthio group, cycloheptylthio group, cyclopentenylthio group, cyclohexenylthio group, and other alicyclic hydrocarbon thio groups; these alicyclic hydrocarbon thio groups include alkyl groups, alkoxy groups, aryl groups, An aryloxy group, a hydroxyl group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, a group containing an epoxy group such as an epoxy group, a methacryloyl group, a mercapto group, an imino group, a ureido group, or an isocyanate group;
Phenylthio group, tolylthio group, dimethylphenylthio group, ethylphenylthio group, butylphenylthio group, tert-butylphenylthio group, methoxyphenylthio group, ethoxyphenylthio group, butoxyphenylthio group, tert-butoxyphenylthio group, etc. An aromatic hydrocarbon thio group of
They further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, a ureido group, And the like substituted with an isocyanate group.

Among these, R ³ is preferably a hydrogen atom from the viewpoint of high heat resistance.

  In the general formulas (I-1) to (I-3), m is not particularly limited as long as m is a number of 2 to 20 on average, but from the viewpoint of high heat resistance, 3 to 10 It is preferably 3, more preferably 3-5, and still more preferably 4.

The calixarene derivative of the present invention is a compound represented by the above general formula (I-1), and 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the above general formula (I-2) A β-alkenyl etherified compound is preferred. Here, the phenolic hydroxyl group to be β-alkenyl etherified includes a phenolic hydroxyl group as R ² in addition to the hydroxyl group bonded to the benzene ring of the general formula (I-2). It is preferable that 5 to 100% of the total is β-alkenyl etherified. If the proportion of the β-alkenyl etherified phenolic hydroxyl group is less than 5%, the solubility with the constituent components of the epoxy resin composition may be inferior. The ratio of the β-alkenyl etherified phenolic hydroxyl group is more preferably 10 to 60%. From the viewpoint of solubility with the constituent components of the epoxy resin composition, it is more preferably 10% or more, and from the viewpoint of high heat resistance, it is more preferably 60% or less.

A method for confirming what percentage of the phenolic hydroxyl group of the calixarene (b1) represented by the general formula (I-2) is β-alkenyl etherified can be confirmed by, for example, ¹ H-NMR. . Specifically, it can be confirmed how much the phenolic hydroxyl group of the raw material calixarene (b1) disappeared when the calixarene derivative was used.

<Manufacturing method>
The method for producing the calixarene derivative of the present invention is not particularly limited, but the phenolic hydroxyl group of the calixarene (b1) represented by the general formula (I-2) is represented by the following general formula (I- The method of making the at least 1 compound chosen from the group of the allyl halide shown by 5) react is mentioned. In order to obtain a calixarene derivative in which 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) is β-alkenyl etherified, the amount of allyl halide used is controlled, or the reaction is stopped halfway. There is a way.

(In the above formulae, each R ³ independently represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a C 1 to 18 carbon atom which may have a substituent. Selected from the group consisting of a hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, all of which may be the same or different, and X is selected from a halogen atom .)
In the above general formula (I-5), each R ³ may independently have a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a substituent. It is selected from the group consisting of a hydrocarbon oxy group having 1 to 18 carbon atoms and a hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent. Incidentally, ^{R 3} of the above general formula (I-5) is may be the same as those with ^{R 3} in the above general formula (I-1). Specifically, it is as follows.

As C1-C18 hydrocarbon group which may have a substituent as R < ³ > of the said general formula (I-5), C1-C18 which may have a substituent An aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group , Aliphatic hydrocarbon groups such as pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, glycidyloxy groups, epoxycyclohexyl groups, groups containing epoxy groups such as epoxy groups, methacryloyl groups, mercapto groups, Substituted by imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
These alicyclic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a glycidyloxy group, an epoxy cyclohexyl group, an epoxy group or other group containing an epoxy group, a methacryloyl group, a mercapto group. , Imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
They further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, a ureido group, And the like substituted with an isocyanate group.

As C1-C18 hydrocarbon oxy group which may have a substituent as R < ³ > of the said general formula (I-5), C1-C18 which may have a substituent An aliphatic hydrocarbonoxy group, an alicyclic hydrocarbonoxy group, an aromatic hydrocarbonoxy group, etc., for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group Aliphatic hydrocarbon oxy groups such as tert-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, allyloxy group, vinyloxy group;
These aliphatic hydrocarbon oxy groups include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, glycidyloxy groups, epoxycyclohexyl groups, epoxy group-containing groups such as methacryloyl groups, mercapto groups. , Imino group, ureido group, isocyanate group and the like substituted;
Cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclopentenyloxy group, cyclohexenyloxy group and other alicyclic hydrocarbon oxy groups; these alicyclic hydrocarbon oxy groups include alkyl groups, alkoxy groups, aryl groups, An aryloxy group, a hydroxyl group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, a group containing an epoxy group such as an epoxy group, a methacryloyl group, a mercapto group, an imino group, a ureido group, or an isocyanate group;
Aromatic hydrocarbon oxy groups such as phenoxy group, tolyloxy group, dimethylphenoxy group, ethylphenoxy group, butylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, ethoxyphenoxy group, butoxyphenoxy group, tert-butoxyphenoxy group; They further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, a ureido group, And the like substituted with an isocyanate group.

As C1-C18 hydrocarbon thio group which may have a substituent as R < ³ > of the said general formula (I-5), C1-C18 which may have a substituent An aliphatic hydrocarbon thio group, an alicyclic hydrocarbon thio group, an aromatic hydrocarbon thio group, and the like, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group , An aliphatic hydrocarbon thio group such as tert-butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, allylthio group, vinylthio group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group, a methacryloyl group, a mercapto group , Imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon thio groups such as cyclopentylthio group, cyclohexylthio group, cycloheptylthio group, cyclopentenylthio group, cyclohexenylthio group;
These alicyclic hydrocarbon thio groups include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, glycidyloxy groups, epoxycyclohexyl groups, epoxy group-containing groups, methacryloyl groups, mercapto groups, etc. Substituted by a group, an imino group, a ureido group, an isocyanate group, etc .;
Phenylthio group, tolylthio group, dimethylphenylthio group, ethylphenylthio group, butylphenylthio group, tert-butylphenylthio group, methoxyphenylthio group, ethoxyphenylthio group, butoxyphenylthio group, tert-butoxyphenylthio group, etc. An aromatic hydrocarbon thio group of
They further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, a mercapto group, an imino group, a ureido group, And the like substituted with an isocyanate group.

Among these, as R ^{3 in the} general formula (I-5), a hydrogen atom is preferable from the viewpoint of high heat resistance.

  Moreover, as X of the said general formula (I-5), halogen atoms, such as a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, are illustrated, and a bromine atom is preferable from a reactive viewpoint.

When the calixarene (b1) represented by the general formula (I-2) is reacted with at least one compound selected from the group of allyl halides represented by the general formula (I-5), a solvent is used. You can also. The solvent that can be used is not particularly limited. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, water , Methanol, ethanol, isopropanol and the like.
The reaction conditions are not particularly limited as long as the reaction proceeds and the product can be obtained. For example, the reaction is performed at room temperature to 200 ° C., and if necessary after the reaction, a by-product, Examples thereof include a method of removing the solvent after removing unnecessary components, a method of distilling off the solvent, a method of filtering the solid precipitated by cooling, a method of filtering the solid deposited by pouring into a poor solvent, and the like.
Moreover, you may use the compound which accelerates | stimulates the reaction of the phenolic hydroxyl group of calixarene (b1) and the at least 1 compound chosen from the compound group shown by general formula (I-5) as needed. . The compound that accelerates the reaction that can be used is not particularly limited as long as the reaction is promoted, but is described below as an inorganic acid, organic acid, inorganic base, organic base, onium salt, and curing accelerator. And known compounds that promote the reaction between a hydroxyl group and a hydrocarbon halide. Among them, ammonium salts are preferable.

The calixarene (b1) can be produced by a known method. For _{example, R1 = CH (CH 3)} ( when described under the name of group: methylmethylene), ^{R 2} = calixarene of hydrogen, the formula is m = 4 (I-3) (b-1) is It can be obtained by reacting resorcinol with paraaldehyde in a solvent at 30 to 200 ° C. in the presence of an acid catalyst such as concentrated hydrochloric acid.

（上記式中、Ｒ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基、置換基を有していてもよい炭素数１〜１８の炭化水素オキシ基、置換基を有していてもよい炭素数１〜１８の炭化水素チオ基、及びハロゲン原子からなる群より選ばれ、全てが同一でも異なっていてもよく、
Ｒ^３は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基、置換基を有していてもよい炭素数１〜１８の炭化水素オキシ基、置換基を有していてもよい炭素数１〜１８の炭化水素チオ基からなる群より選ばれ、全てが同一でも異なっていてもよく、ｐは、平均で２未満の数である。）
なお、ｐにおける「平均で２未満の数」とは、カリックスアレーン誘導体の製造方法のいて、原料となる上記一般式（Ｉ−７）で示されるレゾルシノール誘導体は、ｐに関して１種類である必要はなく、例えば、ｐ＝０〜２の範囲内であれば複数のレゾルシノール誘導体を混合して用いてもよいため、これらの混合物においてｐの平均が２未満となればよいことを示す。 Although it does not specifically limit as a manufacturing method of the calixarene derivative of this invention, As another example, the resorcinol derivative shown with the following general formula (I-7), an aldehyde compound, a ketone compound, and those The method of making it react with the at least 1 compound chosen from the group of a multimer is mentioned.

(In the above formula, each R ² independently represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or an optionally substituted carbon group having 1 to 18 carbon atoms. Are selected from the group consisting of a hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, all may be the same or different, and p is an average number of less than 2. )
The “number less than 2 on average” in p means that the resorcinol derivative represented by the above general formula (I-7) used as a raw material is one kind with respect to p in the method for producing calixarene derivatives. For example, a plurality of resorcinol derivatives may be mixed and used within the range of p = 0 to 2, so that the average of p in these mixtures should be less than 2.

In the formula (I-7), ^{R 2} is perforated above general formula (I-1) ~ may be of the same as ^{R 2} in (I-5), each independently, a hydrogen atom, a substituent C1-C18 hydrocarbon group which may have, C1-C18 hydrocarbon oxy group which may have a substituent, C1-C18 which may have a substituent It is selected from the group consisting of a hydrocarbon thio group and a halogen atom.

In the formula (I-7), ^{R 3} is the general formula (I-1), (I -5) in the well of the same as ^{R 3,} each independently, a hydrogen atom, have a substituent C1-C18 hydrocarbon group which may have, C1-C18 hydrocarbon oxy group which may have a substituent, C1-C18 which may have a substituent It is selected from the group consisting of hydrocarbon thio groups.

The hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ² and R ^{3 in the} general formula (I-7) may have 1 substituent. -18 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert group -Aliphatic hydrocarbon groups such as butyl, pentyl, hexyl, octyl, decyl, dodecyl, allyl and vinyl;
These aliphatic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, a methacryloyl group, Substituted with mercapto group, imino group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

The hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent as R ² and R ^{3 in the} general formula (I-7) may have a substituent. 1-18 aliphatic hydrocarbon oxy groups, alicyclic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, etc., for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec -Aliphatic hydrocarbon oxy groups such as butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, allyloxy group, vinyloxy group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon oxy groups such as cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclopentenyloxy group, cyclohexenyloxy group;
These alicyclic hydrocarbon oxy groups include an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, methacryloyl Substituted with a group, mercapto group, imino group, ureido group, isocyanate group, etc .;
Aromatic hydrocarbon oxy groups such as phenoxy group, tolyloxy group, dimethylphenoxy group, ethylphenoxy group, butylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, ethoxyphenoxy group, butoxyphenoxy group, tert-butoxyphenoxy group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

The hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent as R ² or R ^{3 in the} general formula (I-7) may have a substituent. 1-18 aliphatic hydrocarbon thio groups, alicyclic hydrocarbon thio groups, aromatic hydrocarbon thio groups, etc., for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, sec -Aliphatic hydrocarbon thio groups such as butylthio group, tert-butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, allylthio group, vinylthio group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
Cycloaliphatic hydrocarbon thio groups such as cyclopentylthio group, cyclohexylthio group, cycloheptylthio group, cyclopentenylthio group, cyclohexenylthio group;
These alicyclic hydrocarbon thio groups, groups containing an epoxy group such as an alkyl group, alkoxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group, etc., methacryloyl Substituted with a group, mercapto group, imino group, ureido group, isocyanate group, etc .;
Phenylthio group, tolylthio group, dimethylphenylthio group, ethylphenylthio group, butylphenylthio group, tert-butylphenylthio group, methoxyphenylthio group, ethoxyphenylthio group, butoxyphenylthio group, tert-butoxyphenylthio group, etc. An aromatic hydrocarbon thio group of
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

As a halogen atom as R < ² > of the said general formula (I-7), a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. are mentioned.

（上記式中、Ｒ^４は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１８の炭化水素基からなる群より選ばれ、全てが同一でも異なっていてもよく、ｒは、平均で２以上の数である。） As an aldehyde compound, a ketone compound and a multimer thereof to be reacted with the resorcinol derivative represented by the above general formula (I-7), the calixarene derivative obtained is more preferably the above general formula (I-1). Specifically, when the resorcinol derivatives represented by the general formula (I-7) are added to each other using an aldehyde compound, a ketone compound, and a multimer thereof, 2 in the general formula (I-1) as long as it can additionally to have a valence of substituents R ^1, in particular but not limited to, aldehyde compound represented by the following general formula (I-8), a ketone compound and the plurality monomer below These multimers shown by general formula (I-9) are mentioned.

(In the above formula, each R ⁴ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all may be the same or different. Well, r is an average number of 2 or more.)

In the general formulas (I-8) and (I-9), each R ⁴ is independently a hydrogen atom or a group consisting of a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. It will be chosen. In the aldehyde compound (I-8), at least one R ⁴ is H. R ⁴ in general formulas (I-8) and (I-9) is divalent in the general formula (I-1) obtained when reacted with general formula (I-7). Is selected to have R ¹ which is a group of

The hydrocarbon group having 1 to 18 carbon atoms which may have a substituent as R ^{4 in the} general formulas (I-8) and (I-9) may have a substituent. An aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl An aliphatic hydrocarbon group such as a group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups include an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group or other group containing an epoxy group, a methacryloyl group, a mercapto group, an imino group. Substituted by a group, ureido group, isocyanate group, etc .;
An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group;
A group containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group, a methacryloyl group , Mercapto group, imino group, ureido group, isocyanate group and the like substituted;
An aromatic hydrocarbon group such as phenyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group;
Further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a methacryloyl group, a mercapto group, and an imino group And the like substituted with a group, a ureido group or an isocyanate group.

  In reacting the resorcinol derivative represented by the general formula (I-7) with at least one compound selected from the group consisting of the aldehyde compound, the ketone compound and a multimer thereof, a solvent may be used. . The solvent that can be used is not particularly limited. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, water , Methanol, ethanol, isopropanol and the like.

The reaction conditions are not particularly limited as long as the reaction proceeds and the product can be obtained. For example, the reaction is performed at room temperature to 200 ° C., and if necessary after the reaction, a by-product, Examples thereof include a method of removing the solvent after removing unnecessary components, a method of distilling off the solvent, a method of filtering the solid precipitated by cooling, a method of filtering the solid deposited by pouring into a poor solvent, and the like.
In addition, if necessary, a compound that promotes the reaction of the resorcinol derivative represented by the above formula (I-7) and at least one compound selected from the group of the aldehyde compound, the ketone compound, and a multimer thereof is used. It doesn't matter. The compound that promotes the reaction that can be used is not particularly limited as long as the reaction is promoted, but inorganic acid, organic acid, Lewis acid, inorganic base, organic base, Lewis base, onium salt, curing Examples of the accelerator include compounds described later, known compounds that promote the reaction of phenols with aldehydes or ketones, among which inorganic acids such as hydrochloric acid, oxalic acid, boron trifluoride-diethyl ether complex, organic acids, Lewis Acid is preferred.

In addition, the resorcinol derivative shown by the said general formula (I-7) can be manufactured by a well-known method. For example, the resorcinol derivative represented by the above general formula (I-7) in which R ² = R ³ = hydrogen is an amount of allyl bromide to be introduced into resorcinol in a solvent in the presence of a basic catalyst such as potassium carbonate, The resorcinol derivative represented by the above general formula (I-7) having R ² = R ³ = hydrogen and p = 1 can be obtained by reacting at 30 to 200 ° C., for example, resorcinol monobenzoate The phenolic hydroxyl group can be allylated in the same manner as described above and then hydrolyzed in the presence of a base or acid to debenzoic acid.

<Curing agent for epoxy resin>
The curing agent for epoxy resin of the present invention is characterized by using the calixarene derivative of the present invention represented by the above general formula (I-1).

<Epoxy resin composition>
The epoxy resin composition of the present invention comprises the epoxy resin and the calixarene derivative of the present invention as a curing agent for epoxy resin.
(Epoxy resin)
The epoxy resin usable in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Examples of the epoxy resin include phenols such as phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α-naphthol, β- Novolac obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and hydroxybenzaldehyde under an acidic catalyst. Type epoxy resin;
Diglycidyl ethers (bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin) such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, and stilbene phenols;
Glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol;
Glycidyl ester type epoxy resins of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid;
Glycidyl-type or methylglycidyl-type epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as aniline or isocyanuric acid is substituted with a glycidyl group;
Vinylcyclohexene diepoxide obtained by epoxidizing an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro ( 3,4-epoxy) cycloaliphatic epoxy resins such as cyclohexane-m-dioxane;
Glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin;
Glycidyl ether of terpene-modified phenolic resin;
Glycidyl ether of dicyclopentadiene-modified phenolic resin;
Glycidyl ether of cyclopentadiene modified phenolic resin;
Glycidyl ether of polycyclic aromatic ring-modified phenolic resin;
Glycidyl ether of a naphthalene ring-containing phenolic resin;
Halogenated phenol novolac epoxy resin;
Hydroquinone type epoxy resin;
Trimethylolpropane type epoxy resin;
A linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid;
Diphenylmethane type epoxy resin;
Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins;
Sulfur atom-containing epoxy resin;
Naphthalene type epoxy resin; and the like. These may be used alone or in combination of two or more.

  Among the above epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin in terms of reflow crack resistance and fluidity, Preferred are hydroxybenzaldehyde type epoxy resins, epoxides of naphthols and phenols, epoxides of aralkyl type phenol resins such as phenol aralkyl resins, naphthol aralkyl resins, and naphthalene type epoxy resins. It may be used alone or in combination of two or more. However, in order to exhibit these performances, it is preferable to use 30% by mass or more, and more preferably 50% by mass or more, based on the total amount of the epoxy resin. Specific examples of preferable epoxy resins are shown below.

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, but an epoxy resin represented by the following general formula (II) is preferable. Among the epoxy resins represented by the following general formula (II), R ⁸ in the 3, 3 ′, 5, 5 ′ positions is methyl when the positions where oxygen atoms are substituted in the R ⁸ are 4 and 4 ′ positions. in group, YX-4000H (manufactured by Japan epoxy Resins Co., Ltd.) other ^{R 8} is a hydrogen atom, all the ^{R 8} are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, In the case where all R ⁸ are hydrogen atoms and the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 ′ positions, R ⁸ in the 3, 3 ′, 5, 5 ′ positions are methyl groups, Other products such as YL-6121H (manufactured by Japan Epoxy Resin Co., Ltd.), which are mixed products when R ⁸ is a hydrogen atom, are commercially available.

(In the above formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 4 to 18 carbon atoms, all of which may be the same or different, and n is an average value. , Represents a number from 0 to 10.)

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, but an epoxy resin represented by the following general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), R ⁹ in the 3, 3 ′, 5, 5 ′ positions when the positions where oxygen atoms are substituted in the R ⁹ are 4 and 4 ′ positions are A methyl group, and other R ^9s are hydrogen atoms, and all of R ¹⁰ are hydrogen atoms, and three of the 3, 3 ′, 5, 5 ′ positions are methyl groups, and one is a tert-butyl group. ESLV-210 (manufactured by Sumitomo Chemical Co., Ltd.), which is a mixed product in the case where other than that is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, is commercially available.

(In the formula (III), R ⁹ and R ¹⁰ represents a monovalent organic group having 1 to 18 carbon hydrogen atom or a carbon, may all respectively be the same or different, n is an average value from 0 Indicates a number of 10.)

The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, but an epoxy resin represented by the following general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and the positions where oxygen atoms are substituted in R ¹² are 3, 3 ′, YSLV-80XY (manufactured by Nippon Steel Chemical Co., Ltd.) in which R ^{12 at the} 5,5′-position is a methyl group and the other R ¹² is a hydrogen atom is commercially available.

(In the formula (IV), R ¹¹ and R ¹² represents a monovalent organic group having 1 to 18 carbon hydrogen atom or a carbon, may all respectively be the same or different, n is an average value from 0 Indicates a number of 10.)

Although it will not specifically limit if it is an epoxy resin containing a sulfur atom as a sulfur atom containing type epoxy resin, For example, the epoxy resin shown by the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), R ¹³ in the 3 and 3 'positions when the positions where oxygen atoms are substituted in 4 and 4' positions in R ¹³ are tert-butyl groups. In addition, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.) in which R ^{13 at} the 6,6′-position is a methyl group and the other is a hydrogen atom is commercially available.

(In the formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, n is an average value, and a number of 0 to 10 Is shown.)

The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, but a novolak type phenol resin such as phenol novolak, cresol novolak, naphthol novolak or the like is glycidyl etherified. Epoxy resins epoxidized using the above method are preferred, and for example, epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), ESCN-190, ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.), etc., in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group and i = 1, etc. It is available as a commercial product.

(In the above formula (VI), R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 0 to 3, n Is an average value and represents a number from 0 to 10.)

The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material, but an epoxy resin represented by the following general formula (VII) is preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (manufactured by Dainippon Ink & Chemicals, Inc.) where i = 0 is available as a commercial product.

(In the formula (VII), R ¹⁶ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. And represents a number from 0 to 10.)

The hydroxybenzaldehyde type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a hydroxybenzaldehyde skeleton, but a novolak type phenol resin of a compound having a hydroxybenzaldehyde skeleton and a compound having a phenolic hydroxyl group, etc. A hydroxybenzaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a hydroxybenzaldehyde type phenol resin is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-502H (trade name of Nippon Kayaku Co., Ltd.), etc., where i = 0 and k = 0 are commercially available products. Is available as

(In the above formula (VIII), R ¹⁷ and R ¹⁸ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value and represents a number from 0 to 10.)

The copolymer type epoxy resin of naphthols and phenols is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton, but a compound having a naphthol skeleton And a novolak-type phenol resin using a compound having a phenol skeleton, which is glycidyl etherified, and more preferably an epoxy resin represented by the following general formula (IX). Among the epoxy resins represented by the following general formula (IX), NC-7300 (manufactured by Nippon Kayaku Co., Ltd.), in which R ²¹ is a methyl group, i = 1, j = 0, and k = 0, is a commercially available product. Is available as

(In the above formula (IX), R ^{19 to} R ²¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, j Is an integer of 0 to 2, k is an integer of 0 to 4, p is an average value of 0 to 1, l and m are average values of 0 to 11 and (l + m) is 1 Indicates the number of ~ 11.)

  As the epoxy resin represented by the general formula (IX), a random copolymer containing 1 structural unit and m structural units randomly, an alternating copolymer containing alternately, a copolymer containing regularly, The block copolymer contained in a block shape is mentioned, Any one of these may be used independently or may be used in combination of 2 or more type.

Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins include phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol, dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and the like. The epoxy resin is not particularly limited as long as it is made of a phenol resin synthesized from the above derivatives. For example, a phenol resin synthesized from phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and derivatives thereof is preferably glycidyl ether, Epoxy resins represented by the following general formulas (X) and (XI) are more preferable. Among epoxy resins represented by the following general formula (X), i = 0, R- ³⁸ is a hydrogen atom NC-3000S (manufactured by Nippon Kayaku Co., Ltd.), i = 0, R ³⁸ is a hydrogen atom epoxy resin And CER-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), which is an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms mixed at a weight ratio of 80:20, is available as a commercial product. Moreover, among epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel Chemical Co., Ltd.) where j = 0 and k = 0 are available as commercial products.

(In the above formulas (X) and (XI), R ^{37 to} R ^{41 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is 0 to 3). And j is an integer of 0 to 2, k is an integer of 0 to 4. n is an average value and represents a number of 0 to 10.)

The naphthalene type epoxy resin is not particularly limited as long as it is an epoxy compound containing a naphthalene ring. For example, a naphthol compound synthesized from a naphthol derivative such as naphthol, dihydroxynaphthalene, or dimethylnaphthol is preferably glycidyl etherified, and an epoxy resin represented by the following general formula (XI-a) is more preferable. Among the epoxy resins represented by the following general formula (XI-a), an n = ^1, EXA-4700 all ^{R 42} and ^{R 43} is a hydrogen ^atom, all ^{R 44} is glycidyl group, EXA-4701 (manufactured by Dainippon ink and chemicals, Inc.), n = ^0, all ^{R 42} and ^{R 43} is a hydrogen ^atom, (manufactured by Dainippon ink and chemicals, Inc.) HP-4032 ^{R 44} is glycidyl group, n = EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.), etc., which is 1, all of R ⁴² and R ⁴³ are hydrogen atoms, one of R ⁴⁴ is a hydrogen atom and the other is a glycidyloxy group Is possible.

(In the above formula (XI-a), R ⁴² and R ⁴³ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R ⁴⁴ represents a hydrogen atom or a glycidyloxy group, and all are the same. May be different, n is an average value and represents a number from 0 to 10.)

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{44 in the} above general formulas (II) to (XI) and (XI-a), “all may be the same or different” means, for example, the above general It means that all of 8-88 R ^{8 in} formula (II) may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴⁴ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²¹ and R ^{37 to} R ⁴⁴ may be the same as or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.

  “N” in the above general formulas (II) to (XI) and (XI-a) needs to be in the range of 0 to 10, and if it exceeds 10, the melt viscosity of the epoxy resin component becomes high. In addition, the viscosity of the epoxy resin composition during melt molding also increases, which tends to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n in one molecule of the epoxy resin is preferably set in the range of 0-4.

  In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the calixarene derivative of the present invention is the total number of epoxy groups of the epoxy resin and the sum of the total number of phenolic hydroxyl groups and the total number of allyl ether groups of the calixarene derivative. The ratio, that is, the total number of epoxy groups of the epoxy resin / (the total number of phenolic hydroxyl groups of the calixarene derivative + the total number of allyl ether groups) is preferably 0.5 to 2.0, preferably 0.7 to 1.5. More preferably, it is particularly preferably 0.8 to 1.3. When the blending ratio exceeds 2.0, the epoxy resin is insufficiently cured, and the heat resistance, moisture resistance, and electrical characteristics of the cured product tend to be lowered. On the other hand, if the blending ratio is less than 0.5, the curing agent component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance of the package are lowered. Tend to.

(Other curing agents)
The epoxy resin composition of the present invention can be used in combination with another curing agent other than the calixarene derivative of the present invention shown above as a curing agent. The compound that can be used in combination as the other curing agent is not particularly limited as long as it is a compound that can cure the epoxy resin.
For example, phenol compounds such as phenol resin; amine compounds such as diamine and polyamine; organic anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; carboxylic acid compounds such as dicarboxylic acid and polycarboxylic acid; These may be used in combination of one or more. Among these, it is preferable to use a compound having two or more phenolic hydroxyl groups in one molecule. Specific examples of other preferable curing agents are shown below.
The phenol compound is not particularly limited as long as it is a phenol compound having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent.
Specific examples of the phenol compound include compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol;
Phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, A novolak-type phenol resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and hydroxybenzaldehyde under an acidic catalyst;
Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
Triphenylmethane phenol resin;
Examples thereof include phenol resins obtained by copolymerizing two or more of these resins; these may be used alone or in combination of two or more.

Among the above phenol compounds, from the viewpoint of reflow crack resistance, aralkyl type phenol resins, dicyclopentadiene type phenol resins, hydroxybenzaldehyde type phenol resins, benzaldehyde type and aralkyl type copolymer type phenol resins, and novolak type phenol resins are used. preferable. These aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, hydroxybenzaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins can be used alone or in combination. A combination of the above may also be used.
However, in order to exert the effect of the calixarene derivative of the present invention, these phenol resins are preferably 70% by mass or less, more preferably, in total with respect to the total amount of the calixarene derivative of the present invention and the other curing agent. Is preferably used in combination so as to be 50% by mass or less, more preferably 30% by mass or less.

The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from phenols and / or naphthols and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or a derivative thereof. Phenol resins represented by (XII) to (XIV) are preferred.

(In the above formulas (XII) to (XIV), R ^{22 to} R ^{28 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. , K is an integer of 0 to 4, j is an integer of 0 to 2, n is an average value, and represents a number of 0 to 10.)

Among the phenol resins represented by the general formula (XII), MEH-7851 (Maywa Kasei Co., Ltd.) where i = 0 and R ²³ are all hydrogen atoms is commercially available.

  Among the phenol resins represented by the above general formula (XIII), XL-225, XLC (manufactured by Mitsui Chemicals), MEH-7800 (Maywa Kasei Co., Ltd.), etc., where i = 0 and k = 0 are commercially available products. It is available.

Among the phenol resins represented by the above general formula (XIV), SN-170 (Nippon Steel Chemical Co., Ltd.) where j = 0, R ²⁷ k = 0, R ²⁸ k = 0 is available as a commercial product. Is possible.

The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a dicyclopentadiene skeleton as a raw material, but a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (manufactured by Nippon Petrochemical Co., Ltd.) where i = 0 is available as a commercial product.

(In the above formula (XV), R ²⁹ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. And represents a number from 0 to 10.)

  The hydroxybenzaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a hydroxybenzaldehyde skeleton as a raw material, but a phenol resin represented by the following general formula (XVI) is preferable.

Among phenol resins represented by the following general formula (XVI), MEH-7500 (manufactured by Meiwa Kasei Co., Ltd.) with i = 0 and k = 0 is available as a commercial product.

(In the above formula (XVI), R ³⁰ and R ³¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value and represents a number from 0 to 10.)

  The copolymer type phenol resin of benzaldehyde type and aralkyl type is not particularly limited as long as it is a copolymer type phenol resin of a phenol resin and an aralkyl type phenol resin using a compound having a benzaldehyde skeleton as a raw material. A phenol resin represented by the following general formula (XVII) is preferable.

Among the phenol resins represented by the following general formula (XVII), HE-510 (manufactured by Air Water Chemical Co., Ltd.) having i = 0, k = 0, and q = 0 is available as a commercial product.

(In the above formula (XVII), R ^{32 to} R ³⁴ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 0 to 3, k Is an integer of 0 to 4, q is an integer of 0 to 5, l and m are average numbers of 0 to 11, and (l + m) is a number of 1 to 11.)

  The novolac type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or cocondensation of phenols and / or naphthols and aldehydes in the presence of an acidic catalyst, but the following general formula (XVIII ) Is preferred.

Following general formula TAMANOL 758, 759 (manufactured by Arakawa Chemical Industries, Ltd.) is also ^{i = 0, k = 0,} R 35 are all hydrogen atoms in the phenolic resin represented by (XVIII), HP-850N (manufactured by Hitachi Chemical stock Company) etc. are available as commercial products.

(In the above formula (XVIII), R ³⁵ and R ^{36 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value, and represents a number from 0 to 10.)

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) means, for example, all of i R ^{22 in} the above general formula (XII). Means that they may be the same or different from each other. For the other R ^{23 to} R ³⁶ , it means that all the numbers contained in the formula may be the same or different from each other. R ^{22 to} R ³⁶ may be the same as or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  In the above general formulas (XII) to (XVIII), “n” needs to be in the range of 0 to 10, and when it exceeds 10, a curing agent component containing the calixarene derivative of the present invention and other curing agents. Since the melt viscosity of the epoxy resin composition becomes high, the viscosity at the time of melt molding of the epoxy resin composition also increases, which tends to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n per molecule is preferably set in the range of 0-4.

  In the epoxy resin composition of the present invention, when other curing agent is used in combination with the calixarene derivative of the present invention, the blending amount of the calixarene derivative is based on the total amount of the calixarene derivative and the other curing agent. It is preferable to set it as 30 mass% or more, and it is more preferable to set it as 50 mass% or more. When the blending amount of the calixarene derivative is less than 30% by mass, the heat resistance property of the cured product may be lowered, and the effect achievable by the present invention tends to be reduced.

  In the epoxy resin composition of the present invention, in addition to the calixarene derivative of the present invention, when a phenol compound is used in combination as the other curing agent, the calixarene derivative is added to the total amount of the calixarene derivative and the phenolic compound. The amount is preferably 30% by mass or more, and more preferably 50% by mass or more. When the blending amount of the calixarene derivative is less than 30% by mass, the heat resistance property of the cured product may be lowered, and the effect achievable by the present invention tends to be reduced.

  Further, in the epoxy resin composition of the present invention, when a compound having two or more phenolic hydroxyl groups in one molecule is used as another curing agent in addition to the calixarene derivative of the present invention, the total number of epoxy groups of the epoxy resin And the total number of phenolic hydroxyl groups of the calixarene derivative, the total number of alkenyl ether groups, and the number of phenolic hydroxyl groups of other curing agents, the sum of the total number of phenolic hydroxyl groups and the total number of alkenyl ether groups, that is, epoxy The total number of epoxy groups of the resin / (total number of phenolic hydroxyl groups of calixarene derivative + total number of allyl ether groups + number of phenolic hydroxyl groups of other curing agents) is preferably 0.5 to 2.0, 0.7 -1.5 is more preferable, and 0.8-1.3 is particularly preferable. When the blending ratio exceeds 2.0, the epoxy resin is insufficiently cured, and the heat resistance, moisture resistance, and electrical characteristics of the cured product tend to be lowered. On the other hand, if the blending ratio is less than 0.5, the curing agent component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance of the package are lowered. Tend to.

(Curing accelerator)
The epoxy resin composition of this invention can contain a hardening accelerator as needed. Examples of usable curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, and the like. Cycloamidine compounds, derivatives thereof, phenol novolac salts thereof;
And these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5 Intramolecular polarization formed by adding a quinone compound such as methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane. A compound having:
Tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof;
Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole;
Tetrasubstituted boron salts such as tetraphenylphosphonium and tetraphenylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, N-methylmorpholine and tetraphenylborate;
Triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, Organic phosphines such as tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, or Complexes of these organic phosphines and organic borons;
These organic phosphines, maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5 Intramolecular polarization formed by adding a quinone compound such as methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane. A compound having:
These organic phosphines, 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2- Iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2, Reaction with halogenated phenol compounds such as 6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl And a compound having intramolecular polarization obtained by dehydrohalogenation (Japanese Patent Laid-Open No. 2004-15 See JP 036); and the like.

When these curing accelerators are used in combination, from the viewpoint of fluidity, a compound having an intramolecular polarization formed by adding a compound having an organic phosphines and a π bond, an organic phosphine and a halogenated phenol compound are reacted. After that, a compound having intramolecular polarization obtained through a dehydrohalogenation step is preferable. From the viewpoint of curability, after reacting an organic phosphine with a halogenated phenol compound, a dehydrohalogenation step is performed. The resulting compound having intramolecular polarization is preferred. In particular, it is preferable to use a phosphonium compound represented by the following general formula (I-6) or an intermolecular salt thereof.

(In the formula (I-6), each R ⁴ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all are the same. Or two or more R ⁴ may be bonded to each other to form a cyclic structure,
R ^{5 s} are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group and an organic group having 1 to 18 carbon atoms which may have a substituent, all of which may be the same or different. R ⁵ may be bonded to each other to form a cyclic structure;
Y ⁻ is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms having one or more releasable protons (H ⁺ ), and is bonded to one or more R ⁵ to form a cyclic structure. May be formed. )

In the general formula (I-6), R ⁴ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. An aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and the like, which may have, for example, a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group; Aliphatic hydrocarbon groups such as n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group;
These aliphatic hydrocarbon groups substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, halogen atoms, etc .; cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclopentenyl groups, cyclohexenyls An alicyclic hydrocarbon group such as a group; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, and a halogen atom substituted on these alicyclic hydrocarbon groups;
Aromatic hydrocarbon groups such as phenyl and tolyl groups;
Alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, And those further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, and the like.

In R ⁴ of the above general formula (I-6), two or more R ⁴ may be bonded to each other to form a cyclic structure, and two or three R ⁴ may be bonded to form a divalent or three as a whole. Valent hydrocarbon group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene and hexylene, which can be bonded to a P atom to form a cyclic structure, an alkenyl group such as ethenyl, propenyl and butenyl groups, an aralkylene group such as a methylenephenylene group, phenylene and naphthylene And arylene groups such as anthracenylene, which may be substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

R ^{4 in the} general formula (I-6) is preferably a monovalent substituent selected from the group consisting of an alkyl group and an aryl group. Among these, from the viewpoint of easy availability of raw materials, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p -Hydroxyphenyl group, m-hydroxyphenyl group, o-hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2 -Hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) group, etc., unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl-substituted aryl group, methyl group, ethyl group, propyl group, isopropyl group, n- Selected from chain or cyclic alkyl groups such as butyl, sec-butyl, tert-butyl, octyl and cyclohexyl Substituent is more preferable. Phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p-hydroxyphenyl group, m-hydroxyphenyl group, o- Hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2-hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) It is more preferable that it is an unsubstituted or alkyl group and / or an alkoxy group and / or a hydroxyl group-substituted aryl group.

In the general formula (I-6), R ⁵ is selected from the group consisting of a hydrogen atom, a hydroxyl group, and an organic group having 1 to 18 carbon atoms which may have a substituent. , An optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an alicyclic hydrocarbon oxy group, Aromatic hydrocarbon oxy group, aliphatic hydrocarbon carbonyl group, alicyclic hydrocarbon carbonyl group, aromatic hydrocarbon carbonyl group, aliphatic hydrocarbon oxycarbonyl group, alicyclic hydrocarbon oxycarbonyl group, aromatic hydrocarbon An oxycarbonyl group, an aliphatic hydrocarbon carbonyloxy group, an alicyclic hydrocarbon carbonyloxy group, an aromatic hydrocarbon carbonyloxy group, and the like.

Specific examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms, the alicyclic hydrocarbon group and the aromatic hydrocarbon group which may have a substituent as R ^{5 in the} general formula (I-6) are as follows. The same as those mentioned for R ⁴ above can be used.

R ^{5 in the} general formula (I-6) is an optionally substituted aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms, an alicyclic hydrocarbon oxy group, or an aromatic hydrocarbon oxy group. Specific examples include aliphatic hydrocarbon oxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, allyloxy group and vinyloxy group;
Alicyclic hydrocarbon oxy groups such as cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group;
Aromatic hydrocarbon oxy groups such as phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group;
These hydrocarbon oxy groups and the like are substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc.

R ^{5 in the} general formula (I-6) is an optionally substituted aliphatic hydrocarbon carbonyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon carbonyl group, an aromatic hydrocarbon carbonyl group. Specific examples include aliphatic hydrocarbon carbonyl groups such as formyl group, acetyl group, ethylcarbonyl group, butyryl group and allylcarbonyl; alicyclic hydrocarbon carbonyl groups such as cyclohexylcarbonyl group; phenylcarbonyl group, methylphenylcarbonyl group Aromatic hydrocarbon carbonyl groups such as those obtained by substituting these hydrocarbon carbonyl groups with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc.

As R ^{5 in} formula (I-6), an optionally substituted aliphatic hydrocarbon oxycarbonyl group, alicyclic hydrocarbon oxycarbonyl group, aromatic hydrocarbon oxy which may have a substituent. Specific examples of the carbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and allyloxycarbonyl group; alicyclic hydrocarbon oxycarbonyl groups such as cyclohexyloxycarbonyl group; phenoxycarbonyl Groups, aromatic hydrocarbon oxycarbonyl groups such as methylphenoxycarbonyl group; those substituted with alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom, etc .; It is done.

R ^{5 in the} general formula (I-6), which may have a substituent, an aliphatic hydrocarbon carbonyloxy group having 1 to 18 carbon atoms, an alicyclic hydrocarbon carbonyloxy group, an aromatic hydrocarbon carbonyl Specific examples of the oxy group include an aliphatic hydrocarbon carbonyloxy group such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group and an allylcarbonyloxy group; an alicyclic hydrocarbon carbonyloxy such as a cyclohexylcarbonyloxy group Group; aromatic hydrocarbon carbonyloxy group such as phenylcarbonyloxy group and methylphenylcarbonyloxy group; alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like in these hydrocarbon carbonyloxy group And the like.

In R ⁵ of the above general formula (I-6), two or more R ⁵ may be bonded to each other to form a cyclic structure, and 2 to 4 R ⁵ may be bonded to form a divalent to 4 as a whole. It becomes a valent organic group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene, and hexylene that can form a cyclic structure; an alkenyl group such as an ethenyl, propenyl, and butenyl group; an aralkylene group such as a methylenephenylene group; and an arylene group such as phenylene, naphthylene, and anthracenylene A group in which an oxy group or a dioxy group is bonded to an alkylene group, an alkenyl group, an aralkylene group or an arylene group; and the like. These include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, and a halogen. It may be substituted with an atom or the like.

R ^{5 in the} general formula (I-6) is preferably a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, from the viewpoint of easy availability of raw materials, an unsubstituted or alkyl group such as hydrogen atom, hydroxyl group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, or / And an aryl group substituted with an alkoxy group or / and a hydroxyl group, and a chain or cyclic group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an octyl group, and a cyclohexyl group A substituent selected from an alkyl group is more preferable. When two or more R ⁵ are bonded to each other to form a cyclic structure, a 1-(-2-hydroxynaphthyl) group, 1-(-4-hydroxynaphthyl) group is combined with a benzene ring to which R ⁵ is bonded. An organic group forming a polycyclic aromatic group such as a group is preferred.

In the above general formula (I-6), Y ⁻ is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms and having one or more releasable protons (H ⁺ ). R ⁵ may be bonded to each other to form a cyclic structure. For example, Y ^- represents a hydroxyl group, a mercapto group, a monovalent group proton is eliminated from the organic group having a hydrogen atom bonded to the Group 16 atoms such as hydro seleno group, a carboxyl group, a carboxymethyl group, a carboxyethyl group, carboxyphenyl A group in which a proton of a carboxylic acid is eliminated from a monovalent organic group having 1 to 18 carbon atoms having a carboxyl group such as a carboxynaphthyl group, a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, Examples include a group in which a phenolic proton is eliminated from a monovalent organic group having 1 to 18 carbon atoms having a phenolic hydroxyl group such as a hydroxythienyl group and a hydroxypyridyl group.

Y ⁻ may combine with one or more R ⁵ to form a cyclic structure. For example, Y ⁻ may be 2-(-6-hydroxynaphthyl) together with the benzene ring to which it is bonded. And a divalent organic group that forms a group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as a group.

Previously illustrated Y ^- Among the oxygen anions proton from the hydroxyl group is eliminated, or hydroxyphenyl group, hydroxyphenyl methyl group, hydroxynaphthyl group, hydroxy furyl group, hydroxy thienyl group, a phenolic hydroxyl group such as hydroxy pyridyl group It is preferably a monovalent organic group having an oxygen anion formed by elimination of protons from.

When Y ⁻ is bonded to one or more R ⁵ to form a cyclic structure, for example, Y ⁻ is a 2-(-6-hydroxynaphthyl) group together with the benzene ring to which it is bonded. A group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as

  Further, the intermolecular salt of the phosphonium compound represented by the general formula (I-6) is not limited, but the phosphonium compound represented by the general formula (I-6), phenol, naphthol, molecule Compounds having a phenolic hydroxyl group such as the compounds exemplified above as phenol compounds having two or more phenolic hydroxyl groups therein, compounds having a silanol group such as triphenylsilanol, diphenylsilanediol, trimethylsilanol, oxalic acid, acetic acid, Examples include intermolecular salt compounds with organic acids such as benzoic acid, inorganic acids such as hydrochloric acid, hydrogen bromide, sulfuric acid, and nitric acid.

  The compounding amount of the curing accelerator in the epoxy resin composition of the present invention is not particularly limited as long as a curing acceleration effect is achieved. However, from the viewpoint of improvement in curability and fluidity at the time of moisture absorption of the epoxy resin composition, it is preferable to add a total of 0.1 to 10 parts by mass of a curing accelerator to 100 parts by mass of the epoxy resin. 1 to 7.0 parts by mass is more preferable. When the blending amount of the curing accelerator is less than 0.1 parts by mass, it is difficult to cure the epoxy resin composition in a short time, and when it exceeds 10 parts by mass, the curing rate is too fast and a good molded product may not be obtained. .

(Inorganic filler)
The epoxy resin composition of this invention can contain an inorganic filler as needed. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to blend an inorganic filler. The inorganic filler used in the present invention is not particularly limited as long as it is generally used for a sealing molding material. Specific examples of inorganic fillers include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Examples include spinel, mullite, titania, talc, clay, mica, and the like, or beads formed by spheroidizing these. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate. Among these inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.

  The blending amount of the inorganic filler is not particularly limited as long as the effect of the present invention is obtained, but is preferably in the range of 55 to 90% by volume with respect to the epoxy resin composition. These inorganic fillers are blended for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. If the blending amount is less than 55% by volume, these properties tend to be insufficiently improved. If it exceeds 90% by volume, the viscosity of the epoxy resin composition is increased, the fluidity is lowered, and molding tends to be difficult.

  Moreover, 1-50 micrometers is preferable and, as for the average particle diameter (D50) of an inorganic filler, 10-30 micrometers is more preferable. When the average particle size is less than 1 μm, the viscosity of the epoxy resin composition tends to increase, and when it exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in unevenness of the cured product and variations in the properties of the cured product. Or, there is a tendency that the filling property into a narrow gap is lowered.

  From the viewpoint of fluidity, the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably distributed over a wide range. For example, when the inorganic filler is blended in an amount of 75% by volume or more with respect to the epoxy resin composition, 70% by weight or more of the inorganic filler is a spherical particle, and the particle size distribution of the inorganic filler is distributed over a wide range of 0.1 to 80 μm. It is preferable that Since such an inorganic filler tends to have a close-packed structure, even if the blending amount is increased, an increase in the viscosity of the epoxy resin composition is small, and an epoxy resin composition excellent in fluidity can be obtained.

(Various additives)
The epoxy resin composition of the present invention includes the above-mentioned epoxy resin, epoxy resin curing agent, other curing agent, curing accelerator, inorganic filler, coupling agent exemplified below, ion exchanger, mold release Various additives such as an agent, a stress relaxation agent, a flame retardant, and a colorant can be contained as necessary. However, the epoxy resin composition of the present invention is not limited to the following additives, and various additives known in the art may be added as necessary.

(Coupling agent)
The epoxy resin composition of the present invention includes various silanes such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane as necessary in order to enhance the adhesion between the resin component and the inorganic filler. Known coupling agents such as compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added.

  The blending amount of the coupling agent is preferably 0.05 to 5% by mass and more preferably 0.1 to 2.5% by mass with respect to the inorganic filler. If the blending amount is less than 0.05% by mass, the adhesion to the frame tends to decrease, and if it exceeds 5% by mass, the moldability of the package tends to decrease.

Examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) ) Aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzyl) Silane coupling agents such as (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane;
Isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1 -Butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, Isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctylfo Feto) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate coupling agents such as titanate; and the like, may be used in combination of two or more even with these alone. Among these, a coupling agent having a secondary amino group is preferable from the viewpoint of fluidity and wire flow.

(Ion exchanger)
The epoxy resin composition of the present invention can contain an anion exchanger as required. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to contain an anion exchanger from the viewpoint of improving moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be sealed. . The anion exchanger used in the present invention is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcite, and hydrous hydroxide of an element selected from magnesium, aluminum, titanium, zirconium, and bismuth The thing is mentioned, These can be used individually or in combination of 2 or more types. Of these, hydrotalcites represented by the following general formula (XIX) are preferred.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XIX)
(In the above formula (XIX), 0 <X ≦ 0.5, m is a positive number.)
The blending amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions. The range of ˜5% by mass is more preferable.

(Release agent)
In the epoxy resin composition of the present invention, a mold release agent may be blended in order to give good mold releasability from the mold during molding. There is no restriction | limiting in particular as a mold release agent used in this invention, A conventionally well-known thing can be used. Examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. It may be used in combination of two or more.
Among these, an oxidized or non-oxidized polyolefin wax is preferable, and the blending amount of the polyolefin wax is preferably 0.01 to 10% by mass with respect to the epoxy resin, and 0.1 to 5% by mass. % Is more preferable. If the blending amount of the polyolefin wax is less than 0.01% by mass, the releasability tends to be insufficient, and if it exceeds 10% by mass, the adhesion may be inhibited. Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst.

  Moreover, when using another mold release agent together with polyolefin-type wax, it is preferable that the compounding quantity is 0.1-10 mass% with respect to an epoxy resin, and it is more preferable that it is 0.5-3 mass%. preferable.

(Stress relaxation agent)
The epoxy resin composition of the present invention may contain a stress relaxation agent such as silicone oil or silicone rubber powder as required. By blending a stress relaxation agent, the amount of warp deformation and package cracking of the package can be reduced. The stress relaxation agent that can be used is not particularly limited as long as it is a known flexible agent (stress relaxation agent) that is generally used.
Commonly used flexible agents include, for example, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR, and the like. (Acrylonitrile-butadiene rubber), rubber particles such as acrylic rubber, urethane rubber, silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate Examples thereof include rubber particles having a core-shell structure such as a copolymer, and these may be used alone or in combination of two or more. Among these, a silicone-based flexible agent is preferable, and examples of the silicone-based flexible agent include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

(Flame retardants)
In the epoxy resin composition of the present invention, a flame retardant can be blended as necessary to impart flame retardancy. There is no restriction | limiting in particular as a flame retardant used in this invention, For example, the well-known organic or inorganic compound and metal hydroxide containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom are mentioned, These 1 type is mentioned. It may be used alone or in combination of two or more. The blending amount of the flame retardant is not particularly limited as long as the flame retardant effect is achieved, but is preferably 1 to 30% by mass and more preferably 2 to 15% by mass with respect to the epoxy resin.

(Coloring agent)
The epoxy resin composition of the present invention may contain known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, bengara and the like.

  The epoxy resin composition of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt kneaded by a mixing roll, an extruder or the like, and then cooled and pulverized. More specifically, for example, a method in which predetermined amounts of the above-described components are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C., cooled, and pulverized. Can be obtained at The epoxy resin composition is easy to handle if it is tableted with dimensions and mass that match the molding conditions of the package.

<Electronic component device>
An electronic component device according to the present invention includes an element sealed with the above-described epoxy resin composition of the present invention. Such electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils Examples include those equipped with elements such as passive elements such as those in which these element portions are sealed with the epoxy resin composition of the present invention.
More specifically, for example, after fixing a semiconductor element on a lead frame and connecting the terminal part of the element such as a bonding pad and the lead part by wire bonding or bump, the transfer is performed using the epoxy resin composition of the present invention. Sealed by molding or the like, DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-Tap) Common resin-sealed ICs such as Outline Package (TQFP) and TQFP (Thin Quad Flat Package), half connected to the tape carrier by bumps A semiconductor chip, a transistor, and a semiconductor chip connected to a wiring formed on a TCP (Tape Carrier Package), a wiring board or glass sealed with the epoxy resin composition of the present invention by wire bonding, flip chip bonding, solder, etc. A COB (Chip On Board) module, a hybrid IC, a multichip module, and a back surface in which active elements such as diodes and thyristors and / or passive elements such as capacitors, resistors and coils are sealed with the epoxy resin composition of the present invention. The device is mounted on the surface of the organic substrate on which the terminals for connecting the wiring board are formed, and the device and the wiring formed on the organic substrate are connected by bump or wire bonding, and then the device is sealed with the epoxy resin composition of the present invention BGA (Ball Grid Array), CSP Chip Size Package), and the like.
Especially, since the epoxy resin composition of this invention has few elastic modulus fall at high temperature, it can be used conveniently for the use as which heat resistance, high temperature operation guarantee, etc. are requested | required. Specifically, a power module package, an in-vehicle package, a semiconductor package that operates even at high temperatures, such as SiC, and the like can be given. Moreover, the epoxy resin composition of this invention can be used effectively also in a printed circuit board.

  As a method for sealing an electronic component device using the epoxy resin composition of the present invention, a low pressure transfer molding method is the most general method, but a method such as an injection molding method or a compression molding method may be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited to these Examples.

<Synthesis of calixarenes>
(Synthesis Example 1): Synthesis of calixarenes 1 Using a 300 ml four-necked flask, 33.0 g (0.3 mol) of resorcinol was dissolved in 120 ml of ethanol, and 40 ml of concentrated hydrochloric acid was added under ice-cooling at about 5 ° C. Stir for 30 minutes. To this was added dropwise 12.1 g (0.1 mol) of paraaldehyde, followed by heating to reflux for about 30 minutes. The reaction mixture was cooled to room temperature and a solid produced by filtration was obtained. The obtained solid was washed once with water and three times with methanol, recrystallized twice with methanol, and then vacuum-dried at 60 ° C. for 24 hours to obtain 20.8 g of a white solid.

The obtained white solid was subjected to ¹ H-NMR spectrum measurement, IR spectrum measurement, and GPC measurement, and as a result, it was confirmed to be calixarenes having a structure represented by the following general formula. Since calixarenes having a structure represented by the following general formula are known compounds, measurement results of various spectra are omitted.

<Synthesis of calixarene derivative>
Example 1 Synthesis of Calixarene Derivative 1 24.0 g (44.1 mmol) of calixarene 1 obtained in Synthesis Example 1 was added to a 1000 ml three-necked flask equipped with a thermometer, a Dimroth condenser, and a dropping funnel. Then, 24.5 g (177.3 mmol) of potassium carbonate and 240 ml of N, N-dimethylacetamide were added and stirred for dissolution. To this was added 2.88 g (8.93 mmol) of tetrabutylammonium bromide and the atmosphere was replaced with nitrogen. Next, 21.6 g (178.5 mmol) of allyl bromide was dropped over about 35 minutes with a dropping funnel. Then, it heated to the internal temperature of 80 degreeC with the oil bath, and was made to react for 7 hours. 1N Hydrochloric acid, water and ethyl acetate were added to the reaction solution, transferred to a separatory funnel and shaken well, and the aqueous layer (lower layer) was confirmed to be acidic and separated. The organic layer (upper layer) was washed 5 times with distilled water, and the solvent was distilled off. When 200 ml of chloroform was added thereto, a solid was precipitated. When 2500 ml of hexane was added thereto, a solid was further precipitated. The precipitated solid was filtered and then dried under reduced pressure at 80 ° C. for 24 hours to obtain 24.6 g of a brown solid.

About the obtained reaction product, as a result of measuring ¹ H-NMR spectrum and measuring IR spectrum, calixarene in which 49% of the hydroxyl groups of calixarenes 1 obtained in Synthesis Example 1 were β-allyletherified. It was confirmed to be derivative 1.

The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. 1, and the measurement result (cm ⁻¹ ) of IR spectrum is shown in FIG. The yield of the calixarene derivative was 62%.

(Example 2): Synthesis of calixarene derivative 2 The same operation as in Example 1 was carried out except that 8.54 g (70.6 mmol) of allyl bromide was used, to obtain 19.9 g of a brown solid.
About the obtained reaction product, it confirmed that 19% of the hydroxyl groups of the calixarene 1 obtained by the synthesis example 1 were the calixarene derivative 2 which beta-allyl-etherified, as a result of a < ¹ > H-NMR spectrum measurement. .
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 82%.

(Example 3): Synthesis of calixarene derivative 3 The same operation as in Example 1 was carried out except that 13.2 g (109.4 mmol) of allyl bromide was used to obtain 20.3 g of a brown solid.
About the obtained reaction product, it confirmed that 30% of the hydroxyl groups of the calixarene 1 obtained by the synthesis example 1 were the calixarene derivative 3 which beta-allyl-etherified, as a result of a < ¹ > H-NMR spectrum measurement. .
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 82%.

(Example 4): Synthesis of calixarene derivative 4 The same operation as in Example 1 was carried out except that 17.1 g (141.1 mmol) of allyl bromide was used, to obtain 17.8 g of a brown solid.
About the obtained reaction product, it confirmed that 36% of the hydroxyl groups of the calixarene 1 obtained by the synthesis example 1 were the calixarene derivative 4 which beta-allyl-etherified, as a result of a < ¹ > H-NMR spectrum measurement. .
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 71%.

(Example 5): Synthesis of calixarene derivative 5 The procedure of Example 1 was repeated, except that 32.4 g (268.1 mmol) of allyl bromide was used, to obtain 18.0 g of a brown solid.
About the obtained reaction product, it confirmed that 66% of the hydroxyl groups of the calixarene 1 obtained by the synthesis example 1 were the calixarene derivative 5 which beta-allyl-etherified, as a result of a < ¹ > H-NMR spectrum measurement. .
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 70%.

(Example 6): Synthesis of calixarene derivative 6 The procedure of Example 1 was repeated, except that 64.0 g (529.2 mmol) of allyl bromide was used, to obtain 10.4 g of a brown solid.
About the obtained reaction product, it confirmed that 100% of the hydroxyl groups of the calixarene 1 obtained by the synthesis example 1 were the calixarene derivative 6 which carried out beta-allyl etherification, as a result of a < ¹ > H-NMR spectrum measurement. .
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 39%.

(Example 7): Synthesis of calixarene derivative 7 Resorcinol monoallyl ether 4.9 g (32.4 mmol) was weighed into a three-necked flask with a septum, purged with nitrogen, and then paraaldehyde 1.3 g (9.3 mmol) with a syringe. In addition, 100 ml of diethyl ether was added. Next, 8.0 ml (64.8 mmol) of boron trifluoride-diethyl ether complex was gradually added dropwise with a syringe while cooling with ice. After completion of the dropwise addition, the temperature was returned to room temperature and stirring was continued for 2 hours, and then 150 ml of ion-exchanged water was added to stop the reaction. After transferring to a separatory funnel and washing with water (4-5 times) until the aqueous layer became neutral, magnesium sulfate was added to the organic layer for drying, the solvent was distilled off, and the residue was dried under reduced pressure to obtain a yellow solid. The obtained yellow solid was dissolved in a small amount of diethyl ether and added dropwise to hexane, and the resulting solid was collected by filtration and dried under reduced pressure at 100 ° C. for 3 hours to obtain 4.68 g of a yellow solid.

About the obtained reaction product, it confirmed that 50% of the hydroxyl groups of the calixarenes 1 were the calixarene derivative 7 which carried out beta-allyl etherification, as a result of a < ¹ > H-NMR spectrum and GPC measurement.
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. 8, and the measurement result of GPC is shown in FIG. The yield of the calixarene derivative was 90%.

(Example 8): Synthesis of calixarene derivative 8 20.0 g (36.8 mmol) of calixarene 1 obtained in Synthesis Example 1 in a 500 ml three-necked flask equipped with a thermometer, a Dimroth condenser, and a dropping funnel. Then, 20.3 g (146.9 mmol) of potassium carbonate and 100 ml of ethanol were added and stirred for dissolution. To this, 17.8 g (147.1 mmol) of allyl bromide was dropped with a dropping funnel over about 20 minutes. Then, it heated with the oil bath and made it react under reflux (80 degreeC) for 5 hours. This reaction solution was gradually added to 500 ml of 5N hydrochloric acid aqueous solution, and a solid was precipitated while stirring. The precipitated solid was filtered, washed 5 times with 100 ml of distilled water, and dried under reduced pressure at 80 ° C. for 24 hours to obtain 21.1 g of a brown solid.

As a result of measuring the ¹ H-NMR spectrum of the obtained reaction product, 50% of the hydroxyl groups of the calixarenes 1 obtained in Synthesis Example 1 are β-allyl etherified calixarene derivative 8. It was confirmed.
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 82%.

(Example 9): Synthesis of calixarene derivative 9 Except for using 10.7 g (88.4 mmol) of allyl bromide, the same operation as in Example 8 was performed to obtain 19.1 g of a brown solid.
As a result of measuring the ¹ H-NMR spectrum of the obtained reaction product, 30% of the hydroxyl groups of the calixarenes 1 obtained in Synthesis Example 1 are β-allyletherized calixarene derivative 9 It was confirmed.
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 81%.

(Example 10): Synthesis of calixarene derivative 10 The procedure of Example 8 was repeated, except that 14.2 g (117.4 mmol) of allyl bromide was used, to obtain 18.6 g of a brown solid.
As a result of measuring the ¹ H-NMR spectrum of the obtained reaction product, 40% of the hydroxyl groups of the calixarenes 1 obtained in Synthesis Example 1 are β-allyletherized calixarene derivatives 10. It was confirmed.
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 75%.

(Example 11): Synthesis of calixarene derivative 11 The procedure of Example 8 was repeated, except that 21.4 g (176.9 mmol) of allyl bromide was used, to obtain 21.6 g of a brown solid.
As a result of measuring the ¹ H-NMR spectrum of the obtained reaction product, 60% of the hydroxyl groups of the calixarenes 1 obtained in Synthesis Example 1 are β-allyl etherified calixarene derivative 11. It was confirmed.
The measurement result (ppm) of ¹ H-NMR spectrum is shown in FIG. The yield of the calixarene derivative was 80%.

Details of the measurement method of ¹ H-NMR spectrum and IR spectrum in Synthesis Examples and Examples are as follows.

(1) Measurement of ¹ H-NMR spectrum (Example 1)
The sample was dissolved in deuterated dimethyl sulfoxide to form a solution, and placed in a φ5 mm sample tube for measurement. Measurement was performed using a 500 MHz nuclear magnetic resonance apparatus “JEOL ECA-500” manufactured by JEOL Ltd.

(2) Measurement of IR spectrum It measured by the film method using "Nicolet 380FT-IR" by Thermo ELECTRON Corporation.

(3) Measurement of ¹ H-NMR spectrum (Examples 2 to 7)
The sample was dissolved in deuterated dimethyl sulfoxide to form a solution, and placed in a φ5 mm sample tube for measurement. Measurement was performed using a 600 MHz nuclear magnetic resonance apparatus “JNM-ECA-600” manufactured by JEOL Ltd.

(4) Measurement of ¹ H-NMR spectrum (Examples 8 to 11)
The sample was dissolved in heavy acetone to form a solution, and placed in a φ5 mm sample tube for measurement. The measurement was performed using Bruker's 400 MHz nuclear magnetic resonance apparatus “AM-400”.

(5) Measurement of GPC Using a HLC-8220 system manufactured by Tosoh Corporation, in which a sample was dissolved in tetrahydrofuran and two TSK GEL SUPER HZM-M columns manufactured by Tosoh Corporation were connected, 40 ° C, 0.35 ml / min. The flow rate was measured. It was detected by UV using Tosoh Corporation HLC-8200 as a detector.

[Preparation of epoxy resin composition and evaluation of its properties]
The following components were blended in parts by mass shown in Tables 1 and 2, respectively, and by roll kneading under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, Examples 12 to 21 and Comparative Examples 1 to 4, respectively. An epoxy resin composition was obtained.

  In addition, the compounding quantity of the inorganic filler in each epoxy resin composition was 85% on a weight basis, and 75% on a volume basis.

(Epoxy resin)
Epoxy resin 1: Hydroxybenzaldehyde type epoxy resin having an epoxy equivalent of 170 and a softening point of 67 ° C. (trade name “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 2: biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name “YX-4000H” manufactured by Japan Epoxy Resin Co., Ltd.)

(Curing agent)
Curing agent 1: calixarene derivative 1 obtained in Example 1
Curing agent 2: calixarene derivative 2 obtained in Example 2
Curing agent 3: calixarene derivative 3 obtained in Example 3
Curing agent 4: calixarene derivative 4 obtained in Example 4
Curing agent 5: calixarene derivative 5 obtained in Example 5
Curing agent 6: calixarene derivative 6 obtained in Example 6
Curing agent 7: calixarene derivative 7 obtained in Example 7
Curing agent 8: calixarene derivative 9 obtained in Example 9
Curing agent 9: calixarene derivative 10 obtained in Example 10
Curing agent 10: calixarene derivative 8 obtained in Example 8
Curing agent 11: calixarene derivative 11 obtained in Example 11
Curing agent 12: calixarenes 1 obtained in Synthesis Example 1
Curing agent 13: Hydroxybenzaldehyde type phenolic resin having a hydroxyl equivalent weight of 103 (trade name “MEH-7500” manufactured by Meiwa Kasei Co., Ltd.)

(Curing accelerator)
Curing accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone (inorganic filler)
Inorganic filler: Spherical fused silica (various additives) having an average particle size (D50) of 17.5 μm and a specific surface area of 3.8 m ² / g
Coupling agent: Epoxy silane (γ-glycidoxypropyltrimethoxysilane)
Colorant: Carbon black (trade name “MA-100” manufactured by Mitsubishi Chemical Corporation)
Mold release agent: Carnauba wax (manufactured by Celerica NODA)
Each epoxy resin composition obtained in Examples 12 to 21 and Comparative Examples 1 to 4 was evaluated by the following tests. The evaluation results are shown in Tables 1-2 and FIGS.

  The epoxy resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours or at 250 ° C. for 6 hours.

(1) Spiral flow (fluidity index)
Each epoxy resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was measured. The results are shown in Table 1.

(2) Hardness during heating Each epoxy resin composition is molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D type hardness meter (HD-1120 (Type D) manufactured by Ueshima Seisakusho) is used. And measured. The results are shown in Table 1.

(3) Dynamic viscoelastic behavior 1 (heat resistance index)
The epoxy resin compositions of Example 12 and Comparative Examples 1 and 2 were molded into the size of length 80 mm × width 10 mm × thickness 3 mm under the above conditions and post-cured at 175 ° C. for 6 hours or 250 ° C. for 6 hours. . The obtained cured product was cut into a length of 55 mm, a width of 10 mm, and a thickness of 3 mm using a diamond cutter, and a viscoelasticity measuring apparatus (“ARES”, manufactured by Rheometric Scientific FE Co., Ltd.) was used to dynamically In the mode, the storage elastic modulus was measured under conditions of a temperature rising rate of 5 ° C. and a frequency of 6.28 rad / s. FIG. 13 shows the result of measurement using a cured product after curing at 175 ° C. for 6 hours as a sample, and FIG. 14 shows the result of measurement using a cured product after curing at 250 ° C. for 6 hours as a sample.

(4) Dynamic viscoelastic behavior 2 (heat resistance index)
Examples 12 to 21 and Comparative Examples 1, 3, and 4 epoxy resin compositions were molded into a size of length 80 mm × width 10 mm × thickness 3 mm under the above conditions, and post-cured at 250 ° C. for 6 hours. Next, the obtained cured product was cut into a length of 55 mm × a width of 5 mm × a thickness of 3 mm using a diamond cutter, and a temperature rising rate in a three-point bending mode using a viscoelasticity measuring device RSA3 (manufactured by TA Instruments). The measurement was performed at 5 ° C. and a frequency of 6.28 rad / s. 15 and 16 show the results of measurement using a cured product that was post-cured at 250 ° C. for 6 hours as a sample.

(5) Solubility of curing agent in epoxy resin 100 parts by mass of epoxy resin (Nippon Kayaku Co., Ltd., trade name “EPPN-502H”) / total number of epoxy groups of epoxy resin / (total phenolic hydroxyl group of curing agent) Each curing agent was mixed so that the number + the total number of allyl ether groups of the curing agent was 1, and heated at 120 ° C. for 3 minutes using a hot plate, and the appearance of the mixture was visually observed. Table 3 shows the transparent ones as ○ and those that remain cloudy as ×. When the curing agent is uniformly dissolved in the epoxy resin, the mixture becomes transparent, and when the curing is insufficient, the mixture becomes cloudy.

  The calixarene derivative of the present invention is excellent in solubility in an epoxy resin, and the examples using it as a curing agent are excellent in fluidity and heat hardness. When the same epoxy resin is used according to FIGS. It turns out that it is excellent in high-temperature elastic modulus compared with the hardening | curing agent of a comparative example, and is high heat resistance. In particular, excellent performance is exhibited by post-curing at 250 ° C. On the other hand, it can be seen that calixarenes 1 obtained in Synthesis Example 1 are poor in solubility in epoxy resin, and Comparative Examples 1 and 3 using it as curing agent 12 are poor in fluidity. Moreover, it turns out that the comparative examples 2 and 4 which used the hydroxy benzaldehyde type phenol resin as the hardening | curing agent 13 are inferior in the point of a high-temperature elastic modulus by FIGS.

Claims (4)

An epoxy resin composition comprising an epoxy resin and an epoxy resin curing agent, wherein the epoxy resin curing agent includes a calixarene derivative represented by the following general formula (I-1): Composition.

(In the above formula, n ′ is 0 to 4 and n ″ is 1 to 4, n ′ + n ″ is 1 to 4, m is an average number of 2 to 20, m × n ″> 0, m For each of the repeats, R ¹ , R ² , R ³ , n ′, n ″ may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all may be the same or different,
R ³ is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , Selected from the group consisting of optionally substituted hydrocarbon thio groups having 1 to 18 carbon atoms, all of which may be the same or different. ) 2. The calixarene derivative according to claim 1, wherein 5 to 100% of the phenolic hydroxyl group of the calixarene (b1) represented by the following general formula (I-2) is β-alkenyl etherified. Epoxy resin composition.

(In the above formula, n is 1 to 4, m is an average of 2 to 20, and R ¹ , R ² , and n may be the same or different for each of m repetitions,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. ) The calixarene (b1) is, Ru compound der represented by the following formula (I-3), the epoxy resin composition according to claim 2.

(In the above formula, m is an average number of 2 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. ) The calixarene (b1) is, Ru compound der represented by the following general formula (I-4), the epoxy resin composition of claim 2 or 3.

(In the above formula, m is an average number of 2 to 20, and for each of m repetitions, R ¹ and R ² may be the same or different,
R ¹ is selected from the group consisting of divalent organic groups having 0 to 18 carbon atoms, all of which may be the same or different;
R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or a hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent. , A hydrocarbon thio group having 1 to 18 carbon atoms which may have a substituent, and a halogen atom, all of which may be the same or different. )

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