JP2006307131A - Preparation method for latent catalyst, and epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a latent catalyst which develops excellent catalytic action in molding and gives a resin composition with good curability, flowability, and storage stability. <P>SOLUTION: The preparation method of the latent catalyst comprises reacting a trialkoxysilane with an onium salt molecule represented by formula (1) (wherein A<SP>1</SP>is a nitrogen or phosphorus atom; R<SP>1</SP>to R<SP>4</SP>are each an optionally substituted aromatic, heterocyclic, or aliphatic group; X<SP>1</SP>is an organic group; Y<SP>1</SP>is a group formed by excluding a proton from a proton-donating substituent; Y<SP>2</SP>is a proton-donating group or an oxygen atom; and Y<SP>1</SP>and Y<SP>2</SP>can form a chelate structure by bonding to a silicon atom). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a latent catalyst and an epoxy resin composition.

  As a method for obtaining a semiconductor device by sealing semiconductor elements such as IC and LSI, transfer molding of an epoxy resin composition is widely used in that it is suitable for mass production at low cost. In addition, improvement of the characteristics and reliability of the semiconductor device has been achieved by improving the epoxy resin and the phenol resin which is a curing agent.

  However, in recent market trends of downsizing, weight reduction, and high performance of electronic devices, higher integration of semiconductors has been progressing year by year, and surface mounting of semiconductor devices has been promoted. Along with this, the demand for epoxy resin compositions used for sealing semiconductor elements has become increasingly severe. For this reason, the conventional epoxy resin composition also has a problem that cannot be solved (cannot be handled).

  In recent years, materials used for sealing semiconductor elements have been filled with inorganic materials to improve fast curing for the purpose of improving production efficiency and to improve heat resistance and reliability when sealing semiconductors. High fluidity that is not impaired even when the material is highly filled has been demanded.

  Epoxy resin compositions for the electrical and electronic materials field contain an addition reaction product of tertiary phosphine and quinones, which are excellent in rapid curing, for the purpose of promoting the curing reaction of the resin during curing. (For example, see Patent Document 1).

  By the way, in such a curing accelerator, a temperature range showing a curing acceleration effect extends to a relatively low temperature. For this reason, in the initial stage of the curing reaction, the reaction is promoted little by little, and this reaction causes the resin composition to have a high molecular weight. Such high molecular weight causes an increase in resin viscosity. As a result, in a resin composition that is highly filled with a filler for improving reliability, problems such as poor molding due to insufficient fluidity are caused.

  In order to improve fluidity, various attempts have been made to protect reactive substrates using components that suppress curability. For example, studies have been made to develop latency by protecting the active sites of curing accelerators with ion pairs, and latent catalysts having salt structures of various organic acids and phosphonium ions are known ( For example, see Patent Documents 2 to 3.) However, in such normal salts, since there are always inhibiting components from the initial stage to the final stage of the curing reaction, fluidity can be obtained, but sufficient curability cannot be obtained, and both cannot be achieved. there were.

  In recent years, as a curing accelerator for thermosetting resins such as epoxy resins, research has been conducted on latent catalysts that exhibit favorable behavior that achieves both curability during molding and flow characteristics, and onium salts having a chelate structure have been preserved. It is said that it exhibits a preferable behavior in which stability and curability / fluidity during molding are compatible (for example, see Patent Document 4).

Conventionally, as a method for synthesizing these onium salts having a chelate type structure, a method of removing sodium chloride from sodium salt of a chelate type anion in water or a mixed solvent of water and an organic solvent is known (for example, patents). Reference 5). Although the above method (formula (I)) can be applied as a method for synthesizing onium silicate salts having a chelate structure, sodium salts of unreacted chelate anions and alkali halide salts of by-products are mixed as ionic impurities. There is a problem to do. Furthermore, trialalkoxysilane as a starting material, when mixed with water under alkaline conditions, causes side reactions such as hydrolysis and self-condensation, and tends to decrease the yield.

［式中、Ａは、燐原子または窒素原子を表す。Ｒは、置換もしくは無置換の芳香環または複素環を有する有機基または脂肪族基を表す。Ｘは１価の陰イオンを表す。Ｒ’は脂肪族基を表し、ＹおよびＺはプロトン供与性置換基がプロトンを１個放出してなる基を表す。Ｒ’’はプロトン供与性置換基であるＹＨおよびＺＨと結合する有機基を表す。Ｒ’’’は置換もしくは無置換の芳香環または複素環を有する有機基または置換もしくは無置換の脂肪族基を表す。

[Wherein, A represents a phosphorus atom or a nitrogen atom. R represents an organic group or an aliphatic group having a substituted or unsubstituted aromatic ring or heterocyclic ring. X represents a monovalent anion. R ′ represents an aliphatic group, and Y and Z represent a group formed by releasing one proton from a proton-donating substituent. R ″ represents an organic group bonded to proton-donating substituents YH and ZH. R ′ ″ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group.

Japanese Patent Laid-Open No. 10-25335 (page 2) JP 2001-98053 A (page 5) U.S. Pat. No. 4,171,420 (pages 2-4) JP 11-5829 A (page 3-4) Japanese Patent Laying-Open No. 2003-277510 (page 5-6)

  It is an object of the present invention to provide a latent catalyst capable of giving good curability / flowability and a high-quality molded article, and capable of producing a high yield without mixing ionic impurities in a short time reaction. It is providing the manufacturing method of a sex catalyst.

  As a result of intensive studies to solve the above-described problems, the present inventors have found the following matters and have completed the present invention.

  By reacting an onium salt molecule compound having an anion with a molecule that forms a chelate structure by bonding with a silicon atom, and a trimethoxysilane compound, a latent catalyst can be obtained in a high yield in a short time without mixing ionic impurities. Found to produce onium silicate, working as.

  That is, the present invention is achieved by the following (1) to (5).

(1) A method for producing a latent catalyst, comprising reacting an onium salt molecular compound represented by the general formula (1) with a trialkoxysilane compound.

［式中、Ａ¹は窒素原子または燐原子を表す。式中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ¹は、置換基Ｙ¹およびＹ²と結合する有機基である。Ｙ¹はプロトン供与性置換基がプロトンを放出してなる基であり、Ｙ²はプロトン供与性置換基もしくは酸素原子であり、同一分子内の置換基Ｙ¹およびＹ²が珪素原子と結合してキレート構造を形成しうるものである。ａは１以上の整数を表す。］

[Wherein, A ¹ represents a nitrogen atom or a phosphorus atom. In the formula, each of R ¹ , R ² , R ³ and R ⁴ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and is the same as each other May be different. In the formula, X ¹ is an organic group bonded to the substituents Y ¹ and Y ² . Y ¹ is a group formed by releasing a proton from a proton-donating substituent, Y ² is a proton-donating substituent or an oxygen atom, and the substituents Y ¹ and Y ² in the same molecule are bonded to a silicon atom. Thus, a chelate structure can be formed. a represents an integer of 1 or more. ]

(2) The method for producing a latent catalyst according to the above (1), wherein the onium salt molecular compound represented by the general formula (1) is a quaternary phosphonium salt molecular compound represented by the general formula (2).

［式中、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ²は、置換基Ｙ³と結合する有機基である。Ｙ³はプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の２つの置換基Ｙ³が珪素原子と結合してキレート構造を形成しうるものである。ｂは１以上の整数を表す。］

[Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ represent an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, respectively, and are identical to each other. Or different. In the formula, X ² is an organic group bonded to the substituent Y ³ . Y ³ is a group formed by releasing a proton from a proton-donating substituent, and two substituents Y ³ in the same molecule can be bonded to a silicon atom to form a chelate structure. b represents an integer of 1 or more. ]

(3) The method for producing a latent catalyst according to the above (1), wherein the onium salt molecular compound represented by the general formula (1) is a quaternary phosphonium salt molecular compound represented by the general formula (3).

［式中、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ³は、芳香族基を表し、同一分子内の２つの酸素原子が珪素原子と結合してキレート構造を形成しうるものである。ｃは１以上の整数を表す。］

[Wherein R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represents a substituted or unsubstituted aromatic group or heterocyclic organic group, or a substituted or unsubstituted aliphatic group, and are identical to each other. Or different. In the formula, X ³ represents an aromatic group, and two oxygen atoms in the same molecule can combine with a silicon atom to form a chelate structure. c represents an integer of 1 or more. ]

(4) The latency according to any one of (1) to (3) above, wherein the latent catalyst obtained by the reaction of the onium salt molecular compound and the trimethoxysilane compound is represented by the general formula (4). Method for producing a catalytic catalyst.

［式中、Ａ²は窒素原子または燐原子を表す。式中、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵およびＲ¹⁶は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ⁴は、置換基Ｙ⁴およびＹ⁵と結合する有機基である。Ｙ⁴はプロトン供与性置換基がプロトンを放出してなる基であり、Ｙ⁵はプロトン供与性置換基がプロトンを放出してなる基、もしくは酸素原子であり、同一分子内の置換基Ｙ⁴およびＹ⁵が珪素原子と結合してキレート構造を形成するものである。Ｚ¹は置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表す。］

[Wherein, A ² represents a nitrogen atom or a phosphorus atom. In the formula, each of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and is identical to each other. May be different. In the formula, X ⁴ is an organic group bonded to the substituents Y ⁴ and Y ⁵ . Y ⁴ is a group proton donating substituent group releases a proton, Y ⁵ is a proton-donating substituent group releases a proton group or an oxygen atom, the substituent Y ⁴ in the same molecule And Y ⁵ binds to a silicon atom to form a chelate structure. Z ¹ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

(5) By the compound which has two or more epoxy groups in 1 molecule, the compound which has 2 or more phenolic hydroxyl groups in 1 molecule, and the manufacturing method of the latent catalyst in any one of Claims 1-4 An epoxy resin composition comprising the resulting latent catalyst.

  According to the method for producing a latent catalyst of the present invention, a latent catalyst made of onium silicate can be produced in a short time and in a high yield without mixing ionic impurities. The latent catalyst obtained by the present invention is extremely useful for accelerating the curing of an epoxy resin. When mixed with an epoxy resin composition, an epoxy resin composition having excellent fluidity, storage stability and curability is obtained. Can do.

  Hereinafter, preferred embodiments of the latent catalyst production method of the present invention will be described.

The onium salt molecular compound represented by the general formula (1) used in the present invention includes an ammonium cation or a phosphonium cation (R ¹ R ² R ³ R ⁴ A ¹⁺ ) and a compound having a proton donating group (Y ² X ¹ Y ¹ H) and an anion (Y ² X ¹ Y ¹⁻ ) formed by releasing a proton from the compound having the proton donating group. In the onium salt molecular compound, the anion portion is preferably capable of forming a chelate bond with a silicon atom.

Here, in the cation part constituting the onium salt molecular compound represented by the general formula (1), the atom A ¹ is a phosphorus atom or a nitrogen atom, and the substituents R ¹ , R ² , which are bonded to the atom A ¹ , R ³ and R ⁴ each represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, which may be the same or different from each other.

Examples of these substituents R ^{1 to} R ⁴ include organic compounds having a substituted or unsubstituted aromatic ring such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, and benzyl group. Group, furyl group, thienyl group, pyrrolyl group, pyridyl group, pyrimidyl group, piperidyl group, indolyl group, morpholinyl group, quinolyl group, isoquinolyl group, imidazolyl group and oxazolyl group, etc. , A substituted or unsubstituted aliphatic group such as a methyl group, an ethyl group, an n-butyl group, an n-octyl group and a cyclohexyl group. From the viewpoint of reaction activity and stability, a phenyl group, a methylphenyl group, Methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, etc. A substituted or unsubstituted aromatic group is more preferable. Examples of the substituent in the organic group having an aromatic ring, the organic group having a heterocyclic ring, and an aliphatic group include a methyl group, an ethyl group, and a hydroxyl group.

In addition, the compound having a proton donating group (Y ² X ¹ Y ¹ H) constituting the onium salt molecular compound represented by the general formula (1) and the compound having the proton donating group release protons. In the anion (Y ² X ¹ Y ¹⁻ ), the substituent X ¹ is an organic group bonded to the substituents Y ¹ and Y ² . Substituent Y ¹ is a group formed by releasing a proton from a proton-donating substituent, Y ² is a proton-donating substituent or an oxygen atom, and substituents Y ¹ and Y ² in the same molecule are silicon atoms. To form a chelate structure. The substituents Y ¹ and Y ² may be the same as or different from each other. a is an integer of 1 or more, and 1 is preferable.

Examples of the compound having a proton donating group (Y ² X ¹ Y ¹ H) in the onium salt molecular compound represented by the general formula (1) include 1,2-cyclohexanediol and 1,2-ethane. Aliphatic hydroxy compounds such as diol and glycerin, aliphatic carboxylic acid compounds such as glycolic acid and thioacetic acid, benzoin, catechol, pyrogallol, propyl gallate, tannic acid, 2-hydroxyaniline, 2-hydroxybenzyl alcohol, 1,2 -Aromatic hydroxy compounds such as dihydroxynaphthalene and 2,3-dihydroxynaphthalene, and aromatic carboxylic acid compounds such as salicylic acid, 1-hydroxy-2-naphthoic acid and 3-hydroxy-2-naphthoic acid, etc. Among them, benzoin and glycol , Catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene from the standpoint of reactivity, more preferably.
The anion (Y ² X ¹ Y ¹⁻ ) of the compound having a proton donating group constituting the onium salt compound represented by the general formula (1) is the compound having the proton donating group (Y ² X ¹ Y ¹ H) releases protons.

Among these onium salt molecular compounds, more preferable molecular compounds include quaternary phosphonium salt molecular compounds represented by the general formula (2). The molecular compounds include phosphonium cations ( R ⁵ R ⁶ R ⁷ R ⁸ P ⁺ ), a compound having a proton donating group (X ² (Y ³ H) ₂ ), and an anion (HY) formed by releasing a proton from the compound having the proton donating group ³ X ² Y ^3- ).

Here, in the cation part constituting the quaternary phosphonium salt molecular compound represented by the general formula (2), the substituents R ⁵ , R ⁶ , R ⁷ and R ⁸ bonded to the phosphorus atom are each substituted. Alternatively, it represents an organic group having an unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and these may be the same or different from each other.

Examples of these substituents R ^{5 to} R ⁸ include organic compounds having a substituted or unsubstituted aromatic ring such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, and benzyl group. Group, furyl group, thienyl group, pyrrolyl group, pyridyl group, pyrimidyl group, piperidyl group, indolyl group, morpholinyl group, quinolyl group, isoquinolyl group, imidazolyl group and oxazolyl group, etc. , Substituted or unsubstituted aliphatic groups such as methyl group, ethyl group, n-butyl group, n-octyl group and cyclohexyl group. From the viewpoint of reaction activity and stability, phenyl group, methylphenyl group, methoxy Such as phenyl, hydroxyphenyl and hydroxynaphthyl A substituted or unsubstituted aromatic group is more preferable. Examples of the substituent in the organic group having an aromatic ring, the organic group having a heterocyclic ring, and an aliphatic group include a methyl group, an ethyl group, and a hydroxyl group.

In the compound (X ² (Y ³ H) ₂ ) having a proton donating group constituting the quaternary phosphonium salt molecular compound represented by the general formula (2), X ² is a substituent Y An organic group that binds to ³ . The substituent Y ³ is a group formed by releasing a proton from a proton-donating substituent, and two substituents Y ³ in the same molecule can be bonded to a silicon atom to form a chelate structure. b is an integer of 1 or more, and 1 is preferable.

Examples of the compound having a proton donating group (X ² (Y ³ H) ₂ ) in the quaternary phosphonium salt molecular compound represented by the general formula (2) include catechol, pyrogallol, propyl gallate, Aromatic hydroxy compounds such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, tannic acid and 2-hydroxybenzyl alcohol, and aliphatic hydroxy compounds such as 1,2-cyclohexanediol, 1,2-ethanediol and glycerin Among these, catechol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable from the viewpoint of reactivity.
Further, the anion (HY ³ X ² Y ³⁻ ) of the compound having a proton donating group constituting the quaternary phosphonium salt molecular compound represented by the general formula (2) is the compound having the proton donating group ( X ² (Y ³ H) ₂ ) releases protons.

Among these phosphonium salt molecular compounds, more preferable molecular compounds include quaternary phosphonium salt molecular compounds represented by the general formula (3), and the molecular compounds include phosphonium cations. (R ⁹ R ¹⁰ R ¹¹ R ¹² P ⁺ ), a compound having a proton donating group (X ³ (OH) ₂ ), and an anion (HOX ³ ) formed by releasing a proton from the compound having the proton donating group O ⁻ ).

Here, in the cation moiety constituting the quaternary phosphonium salt molecular compound represented by the general formula (3), the substituents R ⁹ , R ¹⁰ , R ¹¹ and R ¹² bonded to the phosphorus atom are each substituted. Alternatively, it represents an organic group having an unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and these may be the same or different from each other.

Examples of these substituents R ^{9 to} R ¹² include organic compounds having a substituted or unsubstituted aromatic ring such as a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, and a benzyl group. Group, furyl group, thienyl group, pyrrolyl group, pyridyl group, pyrimidyl group, piperidyl group, indolyl group, morpholinyl group, quinolyl group, isoquinolyl group, imidazolyl group and oxazolyl group, etc. , Substituted or unsubstituted aliphatic groups such as methyl group, ethyl group, n-butyl group, n-octyl group and cyclohexyl group. From the viewpoint of reaction activity and stability, phenyl group, methylphenyl group, methoxy Such as phenyl, hydroxyphenyl and hydroxynaphthyl A substituted or unsubstituted aromatic group is more preferable. Examples of the substituent in the organic group having an aromatic ring, the organic group having a heterocyclic ring, and an aliphatic group include a methyl group, an ethyl group, and a hydroxyl group.

In the compound (X ³ (OH) ₂ ) having a proton donating group constituting the quaternary phosphonium salt molecular compound represented by the general formula (3), X ³ represents an aromatic group. , Two oxygen atoms in the same molecule can combine with a silicon atom to form a chelate structure. c is an integer of 1 or more, and 1 is preferable.

Examples of the compound (X ³ (OH) ₂ ) having a proton donating group in the quaternary phosphonium salt molecular compound represented by the general formula (3) include catechol, pyrogallol, propyl gallate, 1, 2 -Aromatic hydroxy compounds such as dihydroxynaphthalene, 2,3-dihydroxynaphthalene and tannic acid, among these, catechol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are reactive surfaces. To more preferable.
The anion (HOX ³ O ⁻ ) of the compound having a proton donating group constituting the quaternary phosphonium salt molecular compound represented by the general formula (3) is the compound having the proton donating group (X ³ ( OH) ₂ ) releases protons.

  Examples of trialkoxysilane compounds used in the present invention include trialkoxysilane compounds having a substituted or unsubstituted aromatic ring, such as phenyltrimethoxysilane, phenyltriethoxysilane, and (N-phenylaminopropyl) trimethoxysilane. Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3- Trialkoxysilane compounds having a substituted or unsubstituted aliphatic group such as aminopropyltrimethoxysilane, 2- (trimethoxysilylethyl) pyridine, N- (3-trimethoxysilylpropylene ) Such as pyrrole, include trialkoxysilane compound having a substituted or unsubstituted heterocyclic. In addition, examples of the substituent in the aliphatic group include a glycidyl group, a mercapto group, and an amino group. Examples of the substituent in the aromatic ring and the heterocyclic ring include a methyl group, an ethyl group, a hydroxyl group, and an amino group. It is done.

  Here, the manufacturing method of the latent catalyst of this invention is demonstrated.

  Examples of the method for producing the latent catalyst of the present invention include a method using a synthetic route in which the onium salt molecular compound capable of forming a chelate bond with a silicon atom and a trialkoxysilane compound are mixed and heated. By this production method, it is possible to synthesize easily and with high yield.

  The above reaction proceeds without solvent, but there is no problem even if various organic solvents including alcohol solvents such as methanol, ethanol and propanol are used.

  In the above reaction, it is preferable from the viewpoint of cost and purity that the onium salt molecular compound and the trialkoxysilane compound are reacted in equimolar amounts, but the reaction proceeds even if they are not equimolar, and used as a latent catalyst. Is possible.

  Although the reaction temperature in the above reaction proceeds slowly even at room temperature, heating at 80 ° C. to 150 ° C. is preferable in order to obtain a desired latent catalyst efficiently in a short time.

  The reaction product obtained by the above reaction may be purified to increase purity by washing with an alcohol solvent such as ethanol, an ether solvent such as diethyl ether or tetrahydrofuran, or an aliphatic hydrocarbon solvent such as n-hexane. Is possible.

  The method for producing a latent catalyst of the present invention is generally the above synthetic reaction route, but is not limited to these.

  As a latent catalyst obtained by said manufacturing method, it is preferable that it is an onium silicate represented by the said General formula (4). The onium silicate is composed of a phosphonium cation or an ammonium cation and a silicate anion.

Here, in the cation moiety constituting the onium silicate represented by the general formula (4), the atom A ² is a phosphorus atom or a nitrogen atom, and the substituents R ¹³ , R ¹⁴ , R ¹⁵ bonded to the atom A ² are used. And R ¹⁶ each represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, which may be the same as or different from each other.

Examples of these substituents R ^{13 to} R ¹⁶ include organic compounds having a substituted or unsubstituted aromatic ring such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, and benzyl group. Group, furyl group, thienyl group, pyrrolyl group, pyridyl group, pyrimidyl group, piperidyl group, indolyl group, morpholinyl group, quinolyl group, isoquinolyl group, imidazolyl group and oxazolyl group, etc. , Substituted or unsubstituted aliphatic groups such as methyl group, ethyl group, n-butyl group, n-octyl group and cyclohexyl group. From the viewpoint of reaction activity and stability, phenyl group, methylphenyl group, methoxy Such as phenyl, hydroxyphenyl and hydroxynaphthyl Any substituted or unsubstituted aromatic group is more preferred. Examples of the substituent in the organic group having an aromatic ring, the organic group having a heterocyclic ring, and an aliphatic group include a methyl group, an ethyl group, and a hydroxyl group.

In the silicate anion constituting the onium silicate represented by the general formula (4), the substituent X ⁴ is an organic group bonded to the substituents Y ⁴ and Y ⁵ . Substituent Y ⁴ is a group formed by proton-donating substituents releasing protons, Y ⁵ is a group formed by proton-donating substituents releasing protons, or oxygen atoms. Y ⁴ and Y ⁵ are bonded to a silicon atom to form a chelate structure. The substituents Y ⁴ and Y ⁵ may be the same as or different from each other.

The group represented by Y ⁴ X ⁴ Y ⁵ in the silicate anion constituting the onium silicate represented by the general formula (4) is a group formed by releasing a proton from a compound having a proton-donating substituent. Examples of the compound having a proton donating substituent include benzoin, glycolic acid, thioacetic acid, catechol, pyrogallol, propyl gallate, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, salicylic acid, 1- Hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxyaniline, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-ethanediol, glycerin and the like Among them, among them, catechol, 1, 2 Dihydroxynaphthalene and 2,3-dihydroxynaphthalene from the surface of the thermal stability, more preferably.

Z ¹ in the silicate anion constituting the onium silicate represented by the general formula (4) represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, Specific examples thereof include substituted or unsubstituted groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and octyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group. Organic groups having a substituted or unsubstituted aromatic ring such as aliphatic group, phenyl group, benzyl group, naphthyl group and biphenyl group, organic groups having a substituted or unsubstituted heterocyclic ring such as pyridine group and pyrrole group, etc. Among these, methyl group, phenyl group, naphthyl group and glycidyloxypropylene In terms of radical thermal stability, more preferably. In addition, examples of the substituent in the aliphatic group include a glycidyl group, a mercapto group, and an amino group. Examples of the substituent in the aromatic ring and the heterocyclic ring include a methyl group, an ethyl group, a hydroxyl group, and an amino group. It is done.

  Hereinafter, the epoxy resin composition using the latent catalyst obtained in the present invention will be described.

  The epoxy resin composition includes a compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and a latent catalyst (C). It is a waste. Furthermore, an inorganic filler (D) can optionally be included.

  The compound (A) having two or more epoxy groups in one molecule used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule. Examples of such a compound (A) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and brominated bisphenol type epoxy resin; biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, stilbene Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, dihydroxybenzene type epoxy resin, and the like; Epoxy compound produced by reacting with epoxichlorohydrin, epoxy resin obtained by oxidizing olefin with peracid, glycidyl ester type epoxy resin and glycidyl Amine type epoxy resins may be used singly or in combination of two or more of them.

  The compound (B) having two or more phenolic hydroxyl groups in one molecule used in the present invention has two or more phenolic hydroxyl groups in one molecule and acts as a curing agent for the compound (A) (function). ) Examples of such compounds (B) include phenol novolak resins, cresol novolak resins, bisphenol resins, phenol aralkyl resins, biphenyl aralkyl resins, trisphenol resins, xylylene-modified novolak resins, terpene-modified novolak resins, and dicyclopentadiene-modified phenols. Resins can be used, and one or more of these can be used in combination.

Examples of the latent catalyst (C) used in the epoxy resin composition include the latent catalyst obtained in the present invention.
Moreover, in this invention, another catalyst can be added in the range which does not affect the characteristic of an epoxy resin composition.

  As an optional inorganic filler (D), when the epoxy resin of the present invention is used in a semiconductor device, it may be blended (mixed) in the epoxy resin composition for the purpose of improving the solder resistance of the resulting semiconductor device. The type is not particularly limited, and those generally used for sealing materials can be used.

  In the epoxy resin composition containing the latent catalyst obtained by the present invention, the content (blending amount) of the latent catalyst (C) is not particularly limited, but is about 0.01 to 10% by weight with respect to the resin component. It is preferable that it is about 0.1 to 5% by weight. Thereby, the sclerosis | hardenability, preservability, fluidity | liquidity, and hardened | cured material characteristic of an epoxy resin composition are expressed with sufficient balance.

  Further, the compounding ratio of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule is not particularly limited. It is preferable that the phenolic hydroxyl group of the compound (B) is used in an amount of about 0.5 to 2 mol, and about 0.7 to 1.5 mol with respect to 1 mol of the epoxy group of (A). More preferably it is used. Thereby, various characteristics improve more, maintaining the balance of the various characteristics of an epoxy resin composition to a suitable thing.

  The content (blending amount) of the inorganic filler (D) is not particularly limited, but is about 200 to 2400 parts by weight per 100 parts by weight of the total amount of the compound (A) and the compound (B). It is preferable that the amount is about 400 to 1400 parts by weight. When content of an inorganic filler (D) is less than the said lower limit, there exists a possibility that the reinforcement effect by an inorganic filler (D) may not fully express, On the other hand, content of an inorganic filler (D) is the said upper limit. In the case of exceeding the above, the fluidity of the epoxy resin composition is lowered, and there is a possibility that poor filling or the like may occur when the epoxy resin composition is molded (for example, during manufacturing of a semiconductor device).

  In addition, if content (blending amount) of an inorganic filler (D) is 400-1400 weight part per 100 weight part of total amounts of the said compound (A) and the said compound (B), an epoxy resin composition The moisture absorption rate of the cured product becomes low, and the occurrence of solder cracks can be prevented. Since such an epoxy resin composition also has good fluidity when heated and melted, it is suitably prevented from causing deformation of the gold wire inside the semiconductor device.

  Further, in the epoxy resin composition of the present invention, in addition to the compounds (components) of (A) to (D), if necessary, for example, coupling of γ-glycidoxypropyltrimethoxysilane or the like Agents, colorants such as carbon black, flame retardants such as brominated epoxy resins, antimony oxide and phosphorus compounds, low stress components such as silicone oil and silicone rubber, natural wax, synthetic wax, higher fatty acids or their metal salts, paraffin, etc. Various additives such as mold release agents and antioxidants may be blended (mixed).

  Next, specific examples of the present invention will be described.

Example 1
In a separable flask (capacity: 200 mL) equipped with a condenser and a stirrer, 12.8 g (0.080 mol) of 2,3-dihydroxynaphthalene and 1.60 g (0.04 mol) of sodium hydroxide were previously dissolved in 10 mL of methanol. The prepared sodium hydroxide solution and 50 mL of methanol were charged and stirred to dissolve uniformly. When a solution prepared by previously dissolving 16.0 g (0.040 mol) of butyltriphenylphosphonium bromide in 50 mL of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain a phosphonium salt molecular compound represented by the following formula (6). This compound was designated C1.

Next, 3.97 g (0.020 mol) of phenyltrimethoxysilane and 12.8 g (0.020 mol) of the compound C1 obtained above were charged into a separable flask (volume: 200 mL) equipped with a condenser and a stirrer. The reaction was heated at 100 ° C. with stirring. The product was washed with 50 mL ethanol and cold water. Thereafter, filtration and vacuum drying were performed to obtain 13.4 g of white crystals.
This product was designated C2. The results of analyzing Compound C2 by ¹ H-NMR, mass spectrum, and elemental analysis were as follows.
Elemental analysis of the product:
(Experimental value) C: 77.4%, H: 5.4%, P: 4.0%, Si: 3.9
(Theoretical value) C: 77.8%, H: 5.6%, P: 4.2%, Si: 3.8
FIG. 1 shows the ¹ H-NMR spectrum of the reaction product C1, and FIG. 2 shows the ¹ H-NMR spectrum of the product C2.
From the analysis result, it was confirmed that the obtained product C2 was the target phosphonium silicate represented by the following formula (7). The yield of C2 obtained was 90%.

(Example 2)
Example 1 except that 8.81 g (0.080 mol) of catechol was used instead of 2,3-dihydroxynaphthalene, and 16.8 g (0.040 mol) of tetraphenylphosphonium bromide was used instead of butyltriphenylphosphonium bromide. In the same manner as above, a phosphonium salt molecular compound was obtained. This compound was designated as C3. C3 is represented by the following formula (8).

  The same as Example 1 except that C3: 11.2 g (0.020 mol) was used instead of Compound C1, and 4.13 g (0.020 mol) of n-hexyltrimethoxysilane was used instead of phenyltrimethoxysilane. The product C4 was obtained. From the analysis result, it was confirmed that the obtained product C4 was the target phosphonium silicate represented by the following formula (9).

(Example 3)
A phosphonium salt molecular compound was obtained in the same manner as in Example 1 except that 16.8 g (0.040 mol) of tetraphenylphosphonium bromide was used instead of butyltriphenylphosphonium bromide. This compound was designated as C5. C5 is represented by the following formula (10).

  Example except that C5: 13.2 g (0.020 mol) was used instead of compound C1, and 4.72 g (0.020 mol) of 3-glycidoxypropyltrimethoxysilane was used instead of phenyltrimethoxysilane 1 to give product C6. From the analysis results, it was confirmed that the obtained product C6 was the target phosphonium silicate represented by the following formula (11).

Example 4
Instead of 2,3-dihydroxynaphthalene, 8.81 g (0.080 mol) of catechol was used, and 17.5 g (0.040 mol) of (3-hydroxyphenyl) triphenylphosphonium bromide was used instead of butyltriphenylphosphonium bromide. Except for the above, a phosphonium salt molecular compound was obtained in the same manner as in Example 1. This compound was designated as C7. C7 is represented by the following formula (12).

  Implemented except that C7: 11.5 g (0.020 mol) was used instead of compound C1, and 5.10 g (0.020 mol) of (N-phenylaminopropyl) trimethoxysilane was used instead of phenyltrimethoxysilane. In the same manner as in Example 1, the product C8 was obtained. From the analysis result, it was confirmed that the obtained product C8 was the target phosphonium silicate represented by the following formula (13).

(Example 5)
A phosphonium salt molecular compound was obtained in the same manner as in Example 1 except that 17.5 g (0.040 mol) of (3-hydroxyphenyl) triphenylphosphonium bromide was used instead of butyltriphenylphosphonium bromide. This compound was designated as C9. C9 is represented by the following formula (14).

  The same as Example 1 except that C9: 13.5 g (0.020 mol) was used instead of compound C1, and 4.97 g (0.020 mol) of 1-naphthyltrimethoxysilane was used instead of phenyltrimethoxysilane. The product C10 was obtained. From the analysis result, it was confirmed that the obtained product C10 was the target phosphonium silicate represented by the following formula (15).

(Example 6)
Example except that 7.37 g (0.080 mol) of mercaptoacetic acid was used instead of 2,3-dihydroxynaphthalene, and 16.8 g (0.040 mol) of tetraphenylphosphonium bromide was used instead of butyltriphenylphosphonium bromide. In the same manner as in Example 1, a phosphonium salt molecular compound was obtained. This compound was designated as C11. C11 is represented by the following formula (16).

  Example 1 except that C11: 10.5 g (0.020 mol) was used instead of compound C1, and 3.92 g (0.020 mol) of 3-mercaptopropyltrimethoxysilane was used instead of phenyltrimethoxysilane. In the same manner, product C12 was obtained. From the analysis result, it was confirmed that the obtained product C12 was the target phosphonium silicate represented by the following formula (17).

(Example 7)
Example 1 except that 16.9 g (0.080 mol) of benzoin was used instead of 2,3-dihydroxynaphthalene, and 12.9 g (0.040 mol) of tetrabutylammonium bromide was used instead of butyltriphenylphosphonium bromide. In the same manner, an ammonium salt molecular compound was obtained. This compound was designated as C13. C13 is represented by the following formula (18).

  The same procedure as in Example 1 was conducted except that C13: 13.3 g (0.020 mol) was used instead of compound C1, and 2.72 g (0.020 mol) of methyltrimethoxysilane was used instead of phenyltrimethoxysilane. The product C14 was obtained. From the analysis results, it was confirmed that the obtained product C14 was the target ammonium silicate represented by the following formula (19).

(Example 8)
A product C15 was obtained in the same manner as in Example 1 except that C5: 13.2 g (0.020 mol) obtained in the same manner as in Example 3 was used instead of Compound C1. From the analysis results, it was confirmed that the obtained product C15 was the target phosphonium silicate represented by the following formula (24).

The synthesis results and analysis results of Examples 1 to 8 are summarized in Table 1.

(Comparative Example 1)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 7.92 g (0.04 mol) of phenyltrimethoxysilane, 12.8 g (0.080 mol) of 2,3-dihydroxynaphthalene, sodium hydroxide 1 A sodium hydroxide solution in which 60 g (0.04 mol) was dissolved in 10 mL of methanol and 50 mL of methanol were charged and stirred to dissolve uniformly. A solution prepared by dissolving 16.0 g (0.040 mol) of butyltriphenylphosphonium bromide in advance in 50 mL of methanol was gradually dropped into the flask, and after stirring for 2 hours, crystals were precipitated by dropping water. did. The precipitated crystals were filtered, washed with water, and dried under vacuum to obtain pink crystals. As a result of analyzing the obtained crystal by ¹ H-NMR, mass spectrum, and elemental analysis, the target compound C2 was obtained. (Yield 35%)

(Comparative Example 2)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 4.13 g (0.020 mol) of hexyltrimethoxysilane, 8.81 g (0.080 mol) of catechol, and 1.60 g of sodium hydroxide (0. 04 mol) was dissolved in 10 mL of methanol and sodium hydroxide solution and 50 mL of methanol were charged and stirred to dissolve uniformly. A solution prepared by dissolving 16.8 g (0.040 mol) of tetraphenylphosphonium bromide in 50 mL of methanol was gradually dropped into the flask, and after stirring for 2 hours, crystals were precipitated by dropping water. . The precipitated crystals were filtered, washed with water, and dried under vacuum to obtain pink crystals. As a result of analyzing the obtained crystal by ¹ H-NMR, mass spectrum, elemental analysis, and ion chromatography, a mixture of the target compound C4 and sodium silicate was obtained. (Yield 42%)

  In Comparative Examples 1 and 2, since the reaction is a dilute homogeneous reaction in a solvent, the reaction takes longer than a solventless reaction, and the yield is low because the solvent solubility of the product is high. Further, it is not preferable because sodium silicate which is a reaction intermediate may be mixed as an ionic impurity.

[Preparation of epoxy resin composition and manufacture of semiconductor device]
As described below, an epoxy resin composition containing the compounds C2, C4, C6, C8, C10, C12, C14, and C15 was prepared, and a semiconductor device was manufactured.

Example 9
First, a biphenyl type epoxy resin (YX-4000HK manufactured by Japan Epoxy Resin Co., Ltd.) represented by the following formula (20) as the compound (A), and a phenol aralkyl resin represented by the following formula (21) as the compound (B). (However, the number of repeating units: 3 represents an average value. XLC-LL manufactured by Mitsui Chemicals, Inc.) Compound C1 as the latent catalyst (C), fused spherical silica (average particle diameter as the inorganic filler (D)) 15 μm), carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives.

＜式（２０）で表される化合物の物性＞
融点 ：１０５℃
エポキシ当量 ：１９３
１５０℃のＩＣＩ溶融粘度：０．１５ｐｏｉｓｅ

<Physical Properties of Compound Represented by Formula (20)>
Melting point: 105 ° C
Epoxy equivalent: 193
ICI melt viscosity at 150 ° C .: 0.15 poise

＜式（２１）で表される化合物の物性＞
軟化点 ：７７℃
水酸基当量 ：１７２
１５０℃のＩＣＩ溶融粘度：３．６ｐｏｉｓｅ

<Physical Properties of Compound Represented by Formula (21)>
Softening point: 77 ° C
Hydroxyl equivalent: 172
ICI melt viscosity at 150 ° C .: 3.6 poise

  Next, the biphenyl type epoxy resin: 52 parts by weight, the phenol aralkyl resin: 48 parts by weight, compound C2: 3.70 parts by weight, fused spherical silica: 730 parts by weight, carbon black: 2 parts by weight, brominated bisphenol A Type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature, then kneaded at 95 ° C. for 8 minutes using a hot roll, then cooled and crushed to obtain an epoxy resin composition (thermosetting Resin composition) was obtained.

  Next, using this epoxy resin composition as a mold resin, 8 100-pin TQFP packages (semiconductor devices) and 15 16-pin DIP packages (semiconductor devices) were produced, respectively.

  The 100-pin TQFP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 7.4 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.

  The package size of the 100-pin TQFP was 14 × 14 mm, the thickness was 1.4 mm, the silicon chip (semiconductor element) size was 8.0 × 8.0 mm, and the lead frame was 42 alloy.

  The 16-pin DIP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.

  The package size of the 16-pin DIP is 6.4 × 19.8 mm, the thickness is 3.5 mm, the silicon chip (semiconductor element) size is 3.5 × 3.5 mm, and the lead frame is made of 42 alloy. .

(Example 10)
First, as a compound (A), a biphenylaralkyl type epoxy resin represented by the following formula (22) (however, the number of repeating units: 3 shows an average value. NC-3000 manufactured by Nippon Kayaku Co., Ltd.), a compound ( B) as a biphenyl aralkyl type phenol resin represented by the following formula (23) (however, the number of repeating units: 3 indicates an average value. MEH-7785SS manufactured by Meiwa Kasei Co., Ltd.), and latent catalyst (C) Compound C2, fused spherical silica (average particle size of 15 μm) as inorganic filler (D), and carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives.

＜式（２２）で表される化合物の物性＞
軟化点 ：６０℃
エポキシ当量 ：２７２
１５０℃のＩＣＩ溶融粘度：１．３ｐｏｉｓｅ

<Physical Properties of Compound Represented by Formula (22)>
Softening point: 60 ° C
Epoxy equivalent: 272
ICI melt viscosity at 150 ° C .: 1.3 poise

＜式（２３）で表される化合物の物性＞
軟化点 ：６８℃
水酸基当量 ：１９９
１５０℃のＩＣＩ溶融粘度：０．９ｐｏｉｓｅ

<Physical Properties of Compound Represented by Formula (23)>
Softening point: 68 ° C
Hydroxyl equivalent: 199
ICI melt viscosity at 150 ° C .: 0.9 poise

  Next, said biphenyl aralkyl type epoxy resin: 57 parts by weight, said biphenyl aralkyl type phenol resin: 43 parts by weight, compound C2: 3.70 parts by weight, fused spherical silica: 650 parts by weight, carbon black: 2 parts by weight, bromine Bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature, then kneaded at 105 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin composition ( A thermosetting resin composition) was obtained.

  Next, using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 9.

(Example 11)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 9, except that 3.34 parts by weight of compound C4 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 9, a package (semiconductor device) was manufactured.

(Example 12)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 10, except that 3.34 parts by weight of compound C4 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 10, a package (semiconductor device) was manufactured.

(Example 13)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 9 except that 3.91 parts by weight of compound C6 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 9, a package (semiconductor device) was manufactured.

(Example 14)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 10 except that 3.91 parts by weight of compound C6 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 10, a package (semiconductor device) was manufactured.

(Example 15)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 9, except that 3.66 parts by weight of compound C8 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 9, a package (semiconductor device) was manufactured.

(Example 16)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 10 except that 3.66 parts by weight of compound C8 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 10, a package (semiconductor device) was manufactured.

(Example 17)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 9 except that 4.12 parts by weight of compound C10 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 9, a package (semiconductor device) was manufactured.

(Example 18)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 10 except that 4.12 parts by weight of compound C10 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 10, a package (semiconductor device) was manufactured.

(Example 19)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 9 except that 3.11 parts by weight of compound C12 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 9, a package (semiconductor device) was manufactured.

(Example 20)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 10 except that 3.11 parts by weight of compound C12 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 10, a package (semiconductor device) was manufactured.

(Example 21)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 9 except that 3.52 parts by weight of compound C14 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 9, a package (semiconductor device) was manufactured.

(Example 22)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 10 except that 3.52 parts by weight of compound C14 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 10, a package (semiconductor device) was manufactured.

(Example 23)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 9 except that 3.80 parts by weight of compound C15 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 9, a package (semiconductor device) was manufactured.

(Example 24)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 10 except that 3.80 parts by weight of compound C15 was used instead of compound C2, and this epoxy resin composition was used. In the same manner as in Example 10, a package (semiconductor device) was manufactured.

(Comparative Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 9 except that 1.85 parts by weight of triphenylphosphine-benzoquinone adduct was used instead of compound C2. Using the resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 9.

(Comparative Example 4)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 10 except that triphenylphosphine-benzoquinone adduct: 1.85 parts by weight was used instead of compound C2, and this epoxy was obtained. A package (semiconductor device) was manufactured using the resin composition in the same manner as in Example 10.

[Characteristic evaluation]
Characteristic evaluation (1) to (3) of the epoxy resin composition obtained in each example and each comparative example, and characteristic evaluation (4) and (5) of the semiconductor device obtained in each example and each comparative example ) Was performed as follows.

(1): Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, measurement was performed at a mold temperature of 175 ° C, an injection pressure of 6.8 MPa, and a curing time of 2 minutes.

  This spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.

(2): Curing torque Using a curast meter (Orientec Co., Ltd., JSR curast meter IV PS type), the torque after 175 ° C. and 45 seconds was measured.
This hardening torque shows that curability is so favorable that a numerical value is large.

(3): Flow residual ratio After the obtained epoxy resin composition was stored in the atmosphere at 30 ° C for 1 week, the spiral flow was measured in the same manner as in (1) above, and the percentage (% )
This flow residual ratio indicates that the larger the numerical value, the better the storage stability.

(4): Solder crack resistance 100 pin TQFP was left in an environment of 85 ° C. and relative humidity 85% for 168 hours, and then immersed in a solder bath at 260 ° C. for 10 seconds.

  Then, the presence or absence of the occurrence of external cracks was observed under a microscope, and displayed as a percentage (%) as crack generation rate = (number of packages in which cracks occurred) / (total number of packages) × 100.

  Further, the ratio of the peeled area between the silicon chip and the cured epoxy resin composition was measured using an ultrasonic flaw detector, and the peel rate = (peeled area) / (silicon chip area) × 100. The average value of the package was obtained and expressed as a percentage (%).

  These crack generation rate and peel rate indicate that the smaller the numerical value, the better the solder crack resistance.

(5): Moisture resistance reliability A voltage of 20 V was applied to a 16-pin DIP in water vapor at 125 ° C. and a relative humidity of 100%, and the disconnection failure was examined. The time until a defect appears in 8 or more of the 15 packages was defined as a defect time.

Note that the measurement time is 500 hours at the longest, and when the number of defective packages is less than 8 at that time, the defective time is indicated as over 500 hours (> 500).
This failure time indicates that the larger the numerical value, the better the moisture resistance reliability.
Tables 2 and 3 show the results of the characteristic evaluations (1) to (5).

  As shown in Tables 2 and 3, the epoxy resin compositions obtained in Examples 9 to 24 (epoxy resin compositions containing a latent catalyst obtained according to the present invention) have both curability and fluidity. Each of the packages (semiconductor devices of the present invention) sealed with the cured product was good in solder crack resistance and moisture resistance reliability.

  On the other hand, the epoxy resin compositions obtained in Comparative Examples 3 to 4 are all inferior in storage stability and fluidity, and the packages obtained in these comparative examples are inferior in solder crack resistance. In addition, the moisture resistance reliability was extremely low.

  According to the present invention, it is possible to stably store a resin composition for a long period of time, without mixing ionic impurities in a short time, in a high yield, without exhibiting a catalytic action at room temperature, and an excellent catalyst at a molding temperature. A latent catalyst that exhibits an action can be produced. Epoxy resin compositions containing such latent catalysts are useful for sealing electronic components such as semiconductor elements.

¹ H-NMR spectrum of reactant C1 ¹ H-NMR spectrum of product C2

Claims (5)

A method for producing a latent catalyst, comprising reacting an onium salt molecular compound represented by the general formula (1) with a trialkoxysilane compound.

[Wherein, A ¹ represents a nitrogen atom or a phosphorus atom. In the formula, each of R ¹ , R ² , R ³ and R ⁴ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and is the same as each other May be different. In the formula, X ¹ is an organic group bonded to the substituents Y ¹ and Y ² . Y ¹ is a group formed by releasing a proton from a proton-donating substituent, Y ² is a proton-donating substituent or an oxygen atom, and the substituents Y ¹ and Y ² in the same molecule are bonded to a silicon atom. Thus, a chelate structure can be formed. a represents an integer of 1 or more. ] The method for producing a latent catalyst according to claim 1, wherein the onium salt molecular compound represented by the general formula (1) is a quaternary phosphonium salt molecular compound represented by the general formula (2).

[Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ represent an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, respectively, and are identical to each other. Or different. In the formula, X ² is an organic group bonded to the substituent Y ³ . Y ³ is a group formed by releasing a proton from a proton-donating substituent, and two substituents Y ³ in the same molecule can be bonded to a silicon atom to form a chelate structure. b represents an integer of 1 or more. ] The method for producing a latent catalyst according to claim 1, wherein the onium salt molecular compound represented by the general formula (1) is a quaternary phosphonium salt molecular compound represented by the general formula (3).

[Wherein R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represents a substituted or unsubstituted aromatic group or heterocyclic organic group, or a substituted or unsubstituted aliphatic group, and are identical to each other. Or different. In the formula, X ³ represents an aromatic group, and two oxygen atoms in the same molecule can combine with a silicon atom to form a chelate structure. c represents an integer of 1 or more. ] The method for producing a latent catalyst according to any one of claims 1 to 3, wherein the latent catalyst obtained by the reaction of the onium salt molecular compound and the trimethoxysilane compound is represented by the general formula (4).

[Wherein, A ² represents a nitrogen atom or a phosphorus atom. In the formula, each of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and is identical to each other. May be different. In the formula, X ⁴ is an organic group bonded to the substituents Y ⁴ and Y ⁵ . Y ⁴ is a group proton donating substituent group releases a proton, Y ⁵ is a proton-donating substituent group releases a proton group or an oxygen atom, the substituent Y ⁴ in the same molecule And Y ⁵ binds to a silicon atom to form a chelate structure. Z ¹ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]   A compound having two or more epoxy groups in one molecule, a compound having two or more phenolic hydroxyl groups in one molecule, and a latency obtained by the method for producing a latent catalyst according to any one of claims 1 to 4. An epoxy resin composition comprising a catalytic catalyst.

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