JP2000017054A - Latent catalyst, thermosetting resin composition and epoxy resin molding material comprising the catalyst, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a latent catalyst having extremely excellent moisture- resistant reliability, curability and storage stability at ordinary tamp., and a thermosetting resin compsn. contg. the same, and a semiconductor-encapsulating epoxy resin molding material which is blended comprising latent catalyst and has excellent moisture reliability, ordinary-temp. shelf stability and moldability corresponding to insertion- and surface-mounting, and a semiconductor device using the material. SOLUTION: A latent catalyst is a compd. expressed by the formula (wherein R1 through R4 are each a univalent organic group; and at least one of X1 through X4 is a group formed in such a way that a proton donor releases one proton), where the catalyst is low in the electric conductivity that a proton donor derived from a substituent bonding to the boron atom of tetrasubstd.- phosphonium tetrasubstd.-borate shows in water, and the catalyst displays an extremely excellent moisture-resistant reliability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a latent catalyst having extremely excellent moisture resistance reliability, curability and storage stability at room temperature, a thermosetting resin composition containing the same, and a blend of the latent catalyst. The present invention relates to an epoxy resin molding material for semiconductor sealing, which is compatible with insertion mounting and surface mounting, which has excellent moisture resistance reliability, room temperature storage properties, and moldability, and a semiconductor device using the same.

[0002]

2. Description of the Related Art Thermosetting resins are required to have storage stability at room temperature for the purpose of simplifying handling, and various latent catalysts have been developed so far. A latent catalyst is a catalyst having excellent curability and excellent storage stability at room temperature to exhibit catalytic activity at an appropriate temperature or higher. For example, JP-A-8-295721 discloses that a tetra-substituted phosphonium tetra-substituted borate having a specific structure of a substituent on boron has both excellent curability and storage stability at room temperature. I have. Since the tetra-substituted phosphonium tetra-substituted borate exhibits catalytic activity by dissociation of the ionic bond between the anion portion and the cation portion, the temperature at which the catalytic activity is exhibited can be changed by changing the temperature at which the bond is dissociated. If the substituent on boron has a specific structure, this ionic bond will be moderately strong,
It does not show activity at room temperature, but dissociates ionic bonds at the curing temperature and shows activity immediately. Therefore, it exhibits excellent curability and excellent storage stability, that is, latency. In fields where such latent catalysts play an important role, I
There are epoxy resin molding materials for semiconductor encapsulation such as C and LSI.

[0003] Conventionally used catalysts include imidazole, diazabicycloalkenes, and triarylphosphines. Since these catalysts work even at relatively low temperatures, molding materials using them are stored at room temperature. Therefore, when stored at room temperature, problems such as poor filling due to a decrease in fluidity during molding and disconnection of the gold wire of the IC chip and poor conduction occur.
For this reason, the epoxy resin molding material for semiconductor encapsulation (hereinafter, abbreviated as encapsulant) must be refrigerated for transportation and storage.

Further, in recent years, the required performance of the humidity resistance reliability of ICs is becoming more and more severe. For example, JP-A-7-24
Japanese Patent No. 2683 discloses a tetra-substituted phosphonium tetra-substituted borate in which a phenoxy group or the like is bonded to a phosphorus atom, that is, a P—O—C bond is formed, and is effective as a catalyst that exhibits the room-temperature storage characteristics of a sealing material. However, these tetra-substituted phosphonium tetra-substituted borates are readily hydrolyzed to form phosphoric acid,
Moisture resistance reliability may be significantly reduced.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a latent catalyst having extremely excellent moisture resistance reliability, curability and storage stability at room temperature, and a thermosetting resin composition containing the same.
Further, the present invention provides an epoxy resin molding material for semiconductor encapsulation for insertion and mounting, which is excellent in moisture resistance reliability, room temperature preservability, and moldability, comprising the latent catalyst, and a semiconductor device using the same. It is.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that tetra-substituted compounds described in Japanese Patent Application Laid-Open No. 8-295721 previously filed by the present inventors. After examining the structure of the substituent bonded to the boron atom of the phosphonium tetra-substituted borate and the moisture resistance reliability, it was found that the proton donor derived from the substituent bonded to the boron atom showed in water a certain type of electricity. Activity was closely related to humidity resistance reliability. In other words, it has been found that those having low conductivity of the extraction water of the proton donor, which will be described later in detail, exhibit extremely excellent moisture resistance reliability, and the present invention has been completed based on this finding.

That is, the present invention provides the following. (1) a latent catalyst comprising a phosphonium borate represented by the general formula (1), a thermosetting resin composition containing the catalyst,

Embedded image (However, R ¹ , R ² , R ³ and R ⁴ in the general formula (1) are
A monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, wherein R ¹ , R ² , R ³ and R ⁴ form a PC bond with a phosphorus atom; May be the same or different from each other. X ¹ , X ² , X ³
And at least one of X ⁴ and X ⁴ is a group in which a proton donor having at least one proton capable of being released outside the molecule releases one proton, and the other is a group having an aromatic ring or a heterocyclic ring. A monovalent organic group or a monovalent aliphatic group, which may be the same or different from each other. This proton donor is prepared by mixing 1 g of each proton donor with 50 g of pure water, and subjecting the mixture to a pressure cooker at 125 ° C. for 20 hours in a pressure cooker.
/ Cm or less. )

(2) a latent catalyst comprising a phosphonium borate represented by the general formula (2), a thermosetting resin composition comprising the catalyst,

Embedded image (However, R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (2) are
A monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ form a PC bond with a phosphorus atom; May be the same or different from each other. In the formula, Z ¹ is an organic group bonded to the substituents Y ¹ and Y ² . Where Z
² is an organic group bonded to the substituents Y ³ and Y ⁴ . Y
¹ and Y ² are groups in which a monovalent proton donating substituent emits a proton, and the substituents Y ¹ and Y ² in the same molecule are bonded to a boron atom to form a chelate structure . Y ³ and Y ⁴ are groups in which a monovalent proton donating substituent emits a proton, and the substituents Y ³ and Y ⁴ in the same molecule are bonded to a boron atom to form a chelate structure. is there. Z ¹ and Z ² may be the same or different from each other, and Y ¹ , Y ² , Y ³ and Y ⁴ may be the same or different from each other. Further, the ligand Y ¹ Z ¹ Y of boron
The proton donors, HY ¹ Z ¹ Y ² H and HY ³ Z ² Y ⁴ H, before ² and Y ³ Z ² Y ⁴ release protons,
1 g of each of these proton donors is mixed with 50 g of pure water, and the resulting mixture is subjected to a pressure cooker treatment at 125 ° C. for 20 hours in a pressure cooker, so that the conductivity of the extracted water is 1000 μS / cm or less. . )

(3) a latent catalyst comprising a phosphonium borate represented by the general formula (3), a thermosetting resin composition comprising the catalyst,

Embedded image (However, R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 in} the general formula (3)
Is a monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, and a phosphorus atom and R ⁹ , R ¹⁰ , R
¹¹ and R ¹² form a PC bond, which may be the same or different from each other. Where Z ³
Is an organic group bonded to the substituents Y ⁵ and Y ⁶ . Y ⁵
And Y ⁶ are groups in which a monovalent proton-donating substituent emits a proton, and may be the same or different from each other. When substituents Y ⁵ and Y ⁶ in the same molecule are bonded to a boron atom, It forms a chelate structure. X ⁵ and X ^{6 each} have at least one proton capable of being released outside the molecule.
The proton donors having one or more protons are a group that releases one proton, or a monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, which are the same or different. You may. Boron ligand Y ⁵ Z ³ Y
Proton donor HY ⁵ Z ³ before ⁶ releases a proton
Y ⁶ H, and X ⁵ and X ⁶ are proton donor when a proton donor having at least one proton capable of releasing to the outside of the molecule is one release was formed by based on proton H
X ⁵ and HX ⁶ are those each proton donor 1g was mixed with pure water 50 g 125 ° C. it in a pressure cooker vessel, the value of the conductivity of extracted water obtained by 20 hours pressure cooker treatment 1000 .mu.s / cm or less. )

(4) A phosphonium borate consisting of a monovalent cation moiety having four groups bonded to a phosphorus atom and a monovalent anion moiety having four groups bonded to a boron atom is used as a repeating unit to form a boron atom. A latent catalyst having a structure in which two or more of these repeating units are connected via at least one of four groups bonded to an atom (hereinafter, this type of latent catalyst is abbreviated as an intermolecular reaction type latent catalyst). And a thermosetting resin composition containing the catalyst.
(However, the group linking the repeating units is a group in which one proton donor emits two or more protons,
They may be the same or different from each other. The group bonded to the phosphorus atom is a monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, and each group forms a PC bond with the phosphorus atom. They may be the same or different. Of the groups bonded to the boron atom, those that do not participate in the linking of the repeating unit include a group in which a proton donor having at least one proton that can be released outside the molecule releases one proton, or an aromatic ring or a heterocyclic group. A monovalent organic group having a ring or a monovalent aliphatic group, which may be the same as or different from each other; The proton donor derived from the group bonded to the boron atom is obtained by mixing 1 g of each proton donor with 50 g of pure water and subjecting the mixture to a pressure cooker at 125 ° C. for 20 hours in a pressure cooker to extract water. The value of the rate is 1000 μS / cm or less. )

(5) A latent catalyst which is at least one selected from the group consisting of (A) an epoxy resin, (B) a phenolic resin, and (C) a latent catalyst defined in (1) to (4). (D) The inorganic filler is an essential component, the equivalent ratio of the epoxy group of all epoxy resins to the phenolic hydroxyl group of all phenolic resins is 0.5 to 2, and the blending amount of the inorganic filler (D) is:
An epoxy resin molding material characterized by being 200 to 2400 parts by weight per 100 parts by weight of the total amount of all epoxy resins and all phenol resins, and a semiconductor device using the same.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R ¹ , R ² ,
R ³ and R ⁴ and R ⁵ , R ⁶ , R ⁷ and R ^{8 in the} general formula (2)
R ⁹ , R ¹⁰ , R ¹¹ , R ^{12 in the} general formula (3) and the group bonded to the phosphorus atom of the intermolecular latent catalyst described in the above item (4) have an aromatic ring or a heterocyclic ring. It is a monovalent organic group or a monovalent aliphatic group, and the phosphorus atom and each group form a PC bond, which may be the same or different. Examples of such a phosphonium group include a tetraphenylphosphonium group, a tetratolylphosphonium group, a tetraethylphenylphosphonium group, a tetramethoxyphenylphosphonium group, a tetranaphthylphosphonium group, a tetrabenzylphosphonium group, an ethyltriphenylphosphonium group,
Examples include, but are not limited to, an n-butyltriphenylphosphonium group, a 2-hydroxyethyltriphenylphosphonium group, a trimethylphenylphosphonium group, a methyldiethylphenylphosphonium group, a methyldiallylphenylphosphonium group, and a tetra-n-butylphosphonium group. It is not something to be done.

[0013] The proton donors derived from the groups and ligands on boron are obtained by adding 1 g of each proton donor to 50 g of pure water.
And mix it in a pressure cooker container with 125
The value of the conductivity of the extracted water obtained by pressure cooker treatment at 20 ° C. for 20 hours is 1000 μS / cm or less.
The group and the ligand on boron referred to here are X ¹ , X ² , X ³ , X ^{4 in} the general formula (1), X ⁵ , X ⁶ in the general formula (3), and an intermolecular reaction type. Of the groups that do not participate in the linkage of the phosphonium borate repeating unit, a group in which a proton donor releases a proton, Y ¹ Z ¹ Y in the general formula (2)
² , Y ³ Z ² Y ⁴ , Y ⁵ Z ³ Y ⁶ in the general formula (3) and a group involved in the connection of repeating units of the intermolecular latent catalyst. Further, each group and each ligand on boron have the following structural features.

X ¹ , X ² , X ³ and X ^{4 in the} general formula (1)
At least one of the proton donors has at least one proton that can be released outside the molecule.
A monovalent organic group or monovalent aliphatic group having an aromatic ring or a heterocyclic ring, which may be the same or different from each other. In the general formula (3), X ⁵ and X ⁶ and the group which does not participate in the connection of the repeating unit of the intermolecular latent catalyst are the proton donor having at least one proton which can be released outside the molecule. A self-releasing group, a monovalent organic group having an aromatic or heterocyclic ring, or an aliphatic group, which may be the same or different from each other. X ¹ , X ² , etc. in such a general formula (1)
The proton donor derived from X ³ , X ⁴ , X ⁵ , X ⁶ in the general formula (3) and a group not involved in the connection of the repeating unit of the intermolecular phosphonium borate has a value of the conductivity of the extraction water. It is 1000 μS / cm or less, and is not limited as long as it is a compound capable of donating a proton, but other than carboxylic acids and organic acids such as phenolic compounds, isocyanuric acid, and benzotriazole,
Alcohols are also included. Here, the phenolic compound in the present invention means a compound in which at least one of hydrogen bonded to an aromatic ring is substituted with a hydroxyl group, and also includes a compound in which a hydroxyl group is substituted with naphthalene or other condensed polycyclic aromatics. .

As the carboxylic acids, preferred are two carboxylic groups or aromatic carboxylic acids having no carboxyl group and no phenolic hydroxyl group at positions adjacent to each other. Examples thereof include benzoic acid, m-hydroxybenzoic acid and 1-naphthoic acid. , 2,6-naphthalenedicarboxylic acid and the like. In this case, the aromatic carboxylic acids include those having a substituent other than a carboxyl group such as m-hydroxybenzoic acid, but substituted or unsubstituted benzoic acid and substituted or unsubstituted naphthoic acid are particularly preferred. Phenol compounds include phenol, naphthol,
Examples include p-phenylphenol, resorcin, 1,6-dihydroxynaphthalene, bisphenol A and the like, with substituted or unsubstituted phenol and substituted or unsubstituted naphthol being particularly preferred. Examples of alcohols include methanol, butanol, 2-propen-1-ol, and the like. Further, different proton donors, for example, a carboxylic acid and an alcohol, or a phenol compound and an isocyanuric acid may be bonded to the same boron atom.

Z ¹ in the general formula (2) is an organic group bonded to the substituents Y ¹ and Y ² . Y ¹ and Y ² are groups in which a monovalent proton donating substituent emits a proton, and the substituents Y ¹ and Y ² in the same molecule are bonded to a boron atom to form a chelate structure. is there. Z ² is an organic group bonded to the substituents Y ³ and Y ⁴ . Y ³ and Y ⁴ are groups in which a monovalent proton donating substituent emits a proton, and the substituents Y ³ and Y ⁴ in the same molecule are bonded to a boron atom to form a chelate structure. is there.
Z ^1, Z ² may be the same or different, Y ^1,
Y ² , Y ³ and Y ⁴ may be the same or different.
Z ³ in the general formula (3) is an organic group bonded to the substituents Y ⁵ and Y ⁶ . Y ⁵ and Y ⁶ are groups in which a monovalent proton-donating substituent emits a proton, and the substituents Y ⁵ and Y ⁶ in the same molecule are bonded to a boron atom to form a chelate structure. is there. The group linking the repeating units of the intermolecular latent catalyst is one proton donor
It is a group that emits two or more protons, which may be the same or different from each other.

In the general formula (2), Y ¹ Z ¹ Y ² ,
Examples of the proton donor derived from Y ³ Z ² Y ⁴ , Y ⁵ Z ³ Y ⁶ in the general formula (3) and the group connecting the repeating units of the intermolecular latent catalyst are carboxylic acids and phenols. In addition to organic acids such as series compounds, polyhydric alcohols and the like are also included. Such carboxylic acids and phenolic compounds include a carboxyl group and two or more substituents selected from the group consisting of phenolic hydroxyl groups and two carboxyl groups or carboxyl groups and phenolic hydroxyl groups at positions adjacent to each other. Non-existent aromatic carboxylic acids or phenolic compounds are preferred, for example, m-hydroxybenzoic acid, 3-hydroxy-1-naphthoic acid, isophthalic acid, 1,6-naphthalenedicarboxylic acid, catechol, resorcinol, 2,3- Dihydroxynaphthalene,
2,2'-biphenol, bisphenol A, bisphenol
Examples thereof include S, 2,2'-methylenebis-4-methylphenol, and dihydroxybenzene, dihydroxynaphthalene, bisphenols, and biphenols are particularly preferable. Examples of the polyhydric alcohol include 1,2-cyclohexanediol and 1,2-propanediol.
Further, different proton donors, for example, carboxylic acid and alcohol may be bonded to the same boron atom.

The intermolecular reaction type latent catalyst in the above item (4) is a multimolecular phosphonium borate in which the number of moles of the phosphorus atom of the phosphonium group on the cation side is equal to the number of moles of the boron atom of the borate on the anion side. The cation side is phosphonium, the substituent of which is a monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, and each substituent forms a PC bond with a phosphorus atom. It consists of phosphonium, all of whose phosphonium groups form an ion pair with the anion-side boron anion (borate). On the anion side, at least one of the four groups on the boron is bonded to one or more other borons via a conjugate base of a divalent or higher-valent proton donor, and a repeating unit 2 that has undergone an intermolecular reaction on the anion side It has more than one continuous structure. The number of repeating units is not particularly limited, and the conjugate bases of the divalent or higher valent proton donor that contributed to the linkage may be the same or different. The group on boron that does not participate in the connection of the repeating unit is a group in which a proton donor having at least one proton that can be released outside the molecule releases one proton, or a monovalent group having an aromatic ring or a heterocyclic ring. An organic group or a monovalent aliphatic group, which may be the same or different from each other. A repeating unit refers to a pair of tetra-substituted phosphonium tetra-substituted borates.

The pressure cooker container according to the present invention is a container having an inner volume of about 70 cc and having a double structure made of Teflon on the inside and stainless steel on the outside. This means that the pressurized state of the contents can be maintained and impurities are hardly eluted from the inner Teflon container during the pressure cooker treatment. The conductivity of pure water used in the present invention is 5 μS
/ Cm or less.

The conductivity of the extraction water in the present invention is
After the pressure cooker treatment at 125 ° C for 20 hours, the contents of the pressure cooker container are taken out and centrifuged, and the electric conductivity of the water layer obtained is measured using a conductivity meter (Horiba Seisakusho's ES-14 model). )).

In the present invention, the latent catalyst represented by the general formula (1), the general formula (2) or the general formula (3) and the latent catalyst comprising the intermolecular reaction type latent catalyst according to the item (4). In the evaluation of moisture resistance reliability, the groups and ligands on boron may come into contact with water to gradually generate a proton donor. And there is a concern that this proton donor may adversely affect the resin-sealed electric / electronic parts at the time of evaluating the moisture resistance reliability, but the proton donor which can be generated from the latent catalyst in the present invention, that is, under the above conditions Proton donors having an extracted water conductivity value of 1000 μS / cm or less have no such adverse effects, and the latent catalyst in the present invention has extremely excellent moisture resistance reliability. Found by them.

Although the reason why the proton donor having an extraction water conductivity value of not more than a certain value does not adversely affect the moisture resistance reliability is unknown, the conductivity value of the extraction water is generally limited to the proton donor value. Is determined by the solubility in water, pKa, and the mobility of the dissociated proton donor in water, and reflects the behavior of the proton donor during the evaluation of humidity resistance reliability. Can mean that it is likely to have some chemical action on the internal electrical and electronic components. The present inventors have studied the correlation between the electrical conductivity of the extracted water of the proton donor obtained under the above conditions and the moisture resistance reliability. As a result, if the electrical conductivity is 1000 μS / cm or less, extremely excellent moisture resistance reliability is exhibited. This led to the discovery of a proton donor exhibiting good moisture resistance reliability.

When the latent catalyst of the present invention is added to a thermosetting resin, the total addition amount is preferably 0.4 to 20 parts by weight based on 100 parts by weight of the thermosetting resin. If the amount is less than 0.4 part by weight, the amount is too small to exhibit a sufficient catalytic action, and if the amount exceeds 20 parts by weight, problems such as a decrease in fluidity may occur.

The thermosetting resin in the thermosetting resin composition of the present invention includes, in addition to the epoxy resin and the maleimide resin, resins whose reactive monomers are cyanates, isocyanates and acrylates, and alkenyl and alkynyl resins. In the present invention, the term thermosetting resin is to be interpreted as meaning all resin systems in which thermosetting can be accelerated by use of the latent catalyst of the present invention. Among them, the most preferable thermosetting resins are an epoxy resin and a maleimide resin. However, the above-mentioned various thermosetting resins may be used singly or in combination of two or more. Hereinafter, specific examples of the epoxy resin and the maleimide resin will be described.

The epoxy resin in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic type Epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, naphthalene type epoxy resin, glycidyl ether compound of resin synthesized by condensation of naphthol and carbonyl compound, stilbene type epoxy resin, 4,4'-bis (1 , 2-epoxyethyl) diphenyl ether, 4,4'-bis (1,2-epoxyethyl) biphenyl, glycidyl ether compound of phenolic resin obtained by reacting dicyclopentadiene with phenols, and mononuclear resorcinol Glycidyl ethers of catechol can be mentioned, which alone or in combination of two or more thereof are also possible.

In the present invention, it reacts with an epoxy group,
Any curing agent that can cause a curing reaction can be used as needed. Specifically, linear aliphatic amines such as diethylenetriamine and triethylenetetramine as organic di and polyamines, aliphatic amines such as N-aminoethylpiperazine and bis (4-aminocyclohexyl) methane, m-xylenediamine And aromatic amines such as diaminodiphenylmethane, dicyandiamide and guanidines, various polyamides and modified polyamines. Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride and the like. Examples of phenols include phenol resins and bisphenols which are co-condensation products of phenols and aldehydes or ketones, and phenol aralkyl resins which are co-condensation products of phenols and dimethoxyparaxylene. Nuclear resorcin, catechol, etc. can be used as long as they cause a curing reaction, but since the definition of "phenol" is generally a compound in which the hydrogen atom bonded to the aromatic ring has been replaced with a hydroxyl group, condensed polycyclic aromatic compounds such as naphthol can be used. A co-condensation reaction product of a hydroxyl group-containing compound derived from a group and a carbonyl compound is also included.

As the maleimide resin in the present invention,
For example, N, N'-m-phenylenebismaleimide, N, N'-m-
Toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'-4,4 '-[3,3'-dimethylbiphenylene] bismaleimide, N, N'-4,4'-[3,3'-dimethyldiphenylmethane] bismaleimide, N, N'-4,4'-diphenylmethanebismaleimide, N, N'-4,4'-diphenyletherbismaleimide, N, N'-4,4 ' -Diphenylsulfone bismaleimide, 2,2-bis- (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis- (4- (4-maleimidophenoxy) phenyl) hexafluoropropane,
Maleimides such as 2-bis- (4- (4-maleimidophenoxy) phenyl) sulfone, or those obtained by reacting these maleimides with amines by Michael addition, or compounds containing double bonds of maleimides and unsaturated groups And those obtained by the addition reaction of an unsaturated bond of the above. It is also possible to use a single compound or a combination of two or more compounds. In addition, these can contain alkenylphenol as needed.

The thermosetting resin composition of the present invention may contain, if necessary, inorganic fillers such as alumina, fused silica, crystalline silica, clay and talc, various reinforcing agents such as glass cloth, release agents, flame retardants, Additives such as a coupling agent, a coloring agent, an antioxidant, a surfactant, and a conventionally known curing catalyst can also be blended.

In the epoxy resin molding material of the present invention,
The epoxy resin of component (A) included in addition to the latent catalyst of the present invention of component (C) refers to all monomers, oligomers, and polymers having two or more epoxy groups in one molecule. For example, biphenyl type epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin,
Orthocresol novolak type epoxy resin, phenol novolak type epoxy resin, triphenol methane type epoxy resin, alkyl-modified triphenol methane type epoxy resin, triazine nucleus containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin and the like are exemplified. They may be used alone or as a mixture. Among these epoxy resins, a crystalline epoxy resin having a melting point of 50 to 150 ° C. is preferable. Such a crystalline epoxy resin has a rigid structure such as a biphenyl skeleton, a bisphenol skeleton, or a stilbene skeleton in a main chain, and is relatively low in molecular weight, and thus exhibits crystallinity. The crystalline epoxy resin is a solid that crystallizes at room temperature, but rapidly melts and changes to a low-viscosity liquid in a temperature range higher than the melting point. The melting point of the crystalline epoxy resin indicates the temperature at the top of the endothermic peak of crystal melting when the temperature is raised from room temperature at a temperature rising rate of 5 ° C./min using a differential scanning calorimeter.

As the crystalline epoxy resin satisfying these conditions, in particular, one or more selected from the general formulas (4) and (5) or a stilbene type epoxy resin represented by the general formula (6) is generally used. A mixture with the stilbene type epoxy resin represented by the formula (7) is preferable.

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

The substituent R ¹³ of the biphenyl type epoxy resin represented by the general formula (4) and the substituent R ¹⁴ of the bisphenol type epoxy resin represented by the general formula (5) each represent a hydrogen atom, a carbon atom having 1 to 1 carbon atoms. 6, a group or atom selected from a chain or cyclic alkyl group, a phenyl group, and a halogen, which may be the same or different, such as a methyl group, an ethyl group, a propyl group, and a butyl group. Groups, a cyclohexyl group, a phenyl group, a chlorine atom, a bromine atom and the like, and a methyl group is particularly preferred.

The substituents R15 to R26 of the stilbene type epoxy resins represented by the general formulas (6) and (7) are a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms,
And a group or atom selected from halogen.
They may be the same or different from each other, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group,
Examples include an amyl group, a hexyl group (including each isomer), a cyclohexyl group, a chlorine atom, a bromine atom, and the like. Particularly, from the low melt viscosity of the epoxy resin, a methyl group, an ethyl group,
A propyl group or a butyl group is preferred.

This type of epoxy resin is a mixture of a stilbene type epoxy resin represented by the general formula (6) and a stilbene type epoxy resin represented by the general formula (7). Equation (7)
There are various types of stilbene-type epoxy resins having different structures depending on the type of substituents and the like, and each of the stilbene-type epoxy resins of general formulas (6) and (7) has a single structure. However, a mixture of two or more structures may be used.

Mixing of the stilbene type epoxy resin of the general formula (6) and the stilbene type epoxy resin of the general formula (7) is only required to lower the melting point by mixing both compounds, and the mixing method is not particularly limited. do not do. For example,
There is a method of mixing stilbene-type phenols, which are raw materials of the stilbene-type epoxy resin, before glycidyl etherification, or a method of melting and mixing both stilbene-type epoxy resins. In any case, the melting point is 50%.
Adjust so as to be ~ 150 ° C.

As the stilbene type epoxy resin represented by the general formula (6), from the viewpoint of availability, performance and raw material price, 5
-Tert-butyl-4,4'-dihydroxy-2,
Glycidyl etherified products of 3 ', 5'-trimethylstilbene and 3-tert-butyl-4,4'-dihydroxy-3', 5,5'-trimethylstilbene are particularly preferred.

As the stilbene type epoxy resin represented by the general formula (7), 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylstilbene, 4,4′- Dihydroxy-3,3'-ditert-butyl-6,6'-dimethylstilbene, 4,4'-dihydroxy-3,3'-ditert-butyl-5,5 '
Glycidyl etherified dimethylstilbene is particularly preferred.

The phenolic resin used as the component (B) in the epoxy resin molding material of the present invention refers to all monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule. For example, phenol novolak resin, cresol novolak resin, para-xylylene-modified phenol resin, para-xylylene / met-xylylene-modified phenol resin, terpene-modified phenol resin,
Examples thereof include dicyclopentadiene-modified phenol resins, and these may be used alone or as a mixture. These phenol resins can be used without any limitation in molecular weight, softening point, hydroxyl equivalent, and the like. Among these phenolic resins, the molded product has a low water absorption rate due to a small number of hydroxyl groups in the molecule, and the molecule has an appropriate flexibility, so that the reactivity in the curing reaction is good and the viscosity can be reduced. Therefore, a phenol aralkyl resin is particularly preferable.

The equivalent ratio of the epoxy groups of all epoxy resins used in the epoxy resin molding material of the present invention to the phenolic hydroxyl groups of all phenolic resins is 0.5 to 2, preferably 0.7 to 1.5. . If the ratio is out of the range of 0.5 to 2, the curability, moisture resistance and the like are undesirably reduced.

The type of the inorganic filler used in the epoxy resin molding material of the present invention is not particularly limited, and those generally used for a sealing material can be used. For example, fused silica powder, fused spherical silica powder, crystalline silica powder, secondary aggregated silica powder, alumina,
Titanium white, aluminum hydroxide, talc, clay, glass fiber and the like are mentioned, and particularly, fused spherical silica powder is preferable. The shape is preferably infinitely spherical, and the filling amount can be increased by mixing particles having different particle sizes.

The amount of the inorganic filler is 20 parts per 100 parts by weight of the total amount of all epoxy resins and all phenol resins.
0 to 2400 parts by weight. If it is less than 200 parts by weight, the reinforcing effect of the inorganic filler may not be sufficiently exhibited, and if it is more than 2400 parts by weight, the fluidity of the resin composition may be reduced, and poor filling may occur during molding. Absent. In particular, the compounding amount of the inorganic filler is 2 per 100 parts by weight of the total amount of all epoxy resins and all phenol resins.
When the amount is 50 to 1400 parts by weight, the moisture absorption of the cured product of the resin composition becomes low, so that the occurrence of solder cracks can be prevented. This is more preferable since there is no possibility of causing gold wire deformation. It is preferable that the inorganic filler is sufficiently mixed in advance.

The epoxy resin molding material of the present invention comprises (A)
In addition to the components (D), if necessary, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a coloring agent such as carbon black, a brominated epoxy resin, an antimony oxide, a flame retardant such as a phosphorus compound, and silicone. Various additives such as oils, low-stress components such as silicone rubber, natural wax, synthetic wax, higher fatty acids and their metal salts or releasing agents such as paraffin, and antioxidants can be blended. There is no problem if used in combination with other known catalysts such as triphenylphosphine, 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole as long as the properties of the acidic catalyst are not impaired. .

The epoxy resin molding material of the present invention comprises (A)
-Component (D), other additives, etc. are mixed at room temperature using a mixer, kneaded with a kneader such as a roll or an extruder, cooled, and pulverized. In order to manufacture a semiconductor device by encapsulating an electronic component such as a semiconductor using the epoxy resin molding material of the present invention, it is sufficient to cure and mold by a molding method such as a transfer mold, a compression mold, and an injection mold.

[0047]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

1. Example compounds 1 to 4 relating to a latent catalyst and a thermosetting resin composition containing the catalyst ,
Preliminary 7-14 Examples, and represent compounds 1-4 was used as a catalyst (curing accelerator), and the structure of the compound 7-14 below in Comparative Examples by the chemical structural formula.

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Compounds 5 and 6 Compounds 5 and 6 are latent catalysts of the intermolecular reaction type according to claim 4. That is, it is a multimolecular phosphonium borate in which the number of moles of the phosphorus atom of the phosphonium group on the cation side is equal to the number of moles of the boron atom of the borate on the anion side.

A) Compound 5 The cation side is a tetraphenylphosphonium group, and all the phosphonium groups form an ion pair with the anion side boron anion. On the anion side, all four groups on boron are conjugate bases of isophthalic acid (isophthalate)
Is substituted with one of the two carboxylates, and further has a repeating structure bonded to boron of another molecule through the other carboxylate. In this case, the structure is such that the boron atom and the isophthalate react on average at a molar ratio of 1: 2.

B) Compound 6 The cation side is a tetraphenylphosphonium group, and all the phosphonium groups form an ion pair with the boron anion on the anion side. On the anion side, all four groups on boron are substituted with one of the two phenoxides of the conjugate base of bisphenol A, and the other phenoxide has a repeating structure in which, on average, two are bonded to boron of another molecule Things. In this case, the structure is such that the boron atom and bisphenol A react at an average molar ratio of 1: 3.

The name of the proton donor derived from the group and the ligand on boron and 1 g of this proton donor were added to 50 g of pure water.
And mix it in a pressure cooker at 125 ° C, 2
Table 1 shows the values of the conductivity of the extracted water obtained by the pressure cooker treatment for 0 hour.

[0065]

[Table 1]

The proton donor corresponding to compound 13 is
An aromatic carboxylic acid having one carboxyl group in the molecule and one hydroxyl group in the adjacent position, and the proton donor corresponding to compound 14 is located at a position adjacent to each other in the molecule.
Aromatic carboxylic acid having one carboxyl group.

(1) Evaluation in epoxy / (maleimide) / phenol resin curing system Various catalysts were blended in the thermosetting resin composition as shown in Table 2, and the fluidity, curability, The storage stability and the moisture resistance reliability were evaluated.

[0068]

[Table 2]

Hereinafter, a specific evaluation method will be described. (I) Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, mold temperature 175 ° C, injection pressure 70 kg / c
Measured in m 2 and curing time 2 minutes. Spiral flow is a parameter of fluidity, with higher values indicating better fluidity. (Ii) Curing torque Curast meter (Orientec Co., Ltd., JSR
(Curastometer PS type), and obtain the torque after 175 ° C. and 90 seconds. The torque in the curast meter is a parameter of curability, and the larger the value, the better the curability. (Iii) Spiral flow residual ratio After the sample was stored at 25 ° C. for 30 days, the spiral flow was measured again and expressed as a percentage with respect to the initial spiral flow immediately after sample preparation, as shown in the following formula. The higher the value of the residual spiral flow, the better the storage stability. Spiral flow residual rate (%) = (spiral flow value after storage / initial spiral flow value) × 100 (iv) Evaluation of moisture resistance reliability A 16-pin DIP was prepared using a resin composition obtained by blending and kneading various components. Sealed in it for a predetermined time of 125 ° C, relative humidity of 10
After applying a voltage of 20 V in 0% steam, disconnection failure was examined. The time until half of the evaluated packages failed was defined as PCBT failure time. The evaluation time was 500 hours at the maximum, and when the number of defects was less than half at that time, the defect time was described as 500 hours or more.
The longer this time, the better the moisture resistance reliability.

Example 1 Orthocresol novolak type epoxy (EOCN-1020-65, manufactured by Nippon Kayaku Co., Ltd.) (67 parts by weight), phenol novolak resin (manufactured by Sumitomo Durez Co., Ltd.) PR-51470) 33 parts, 4.3
Parts, further, 300 parts of fused silica and 2 parts of carnauba wax were mixed and roll-kneaded at 90 ° C. for 8 minutes to obtain a molding material. This molding material has a spiral flow of 70 cm and a curing torque of 78
kgfcm. The residual spiral flow after 30 days at 25 ° C. was 99%. The PCBT failure time was 500 hours or more.

Example 2 52 parts of biphenol-type glycidyl ether epoxy (YX-4000H, manufactured by Yuka Shell Epoxy Co., Ltd.) and 48 parts of para-xylene-type phenol resin (XL-225, manufactured by Mitsui Toatsu Chemicals, Inc.)
Parts, 2.9 parts of compound 2 as a catalyst, and 800 parts of fused silica
Parts and 3 parts of carnauba wax were mixed and roll-kneaded at 90 ° C. for 8 minutes to obtain a molding material. The spiral flow of this molding material was 90 cm, and the curing torque was 83 kgf · cm. twenty five
After 30 days at 30 ° C., the residual spiral flow rate was 93%.
The PCBT failure time was 500 hours or more.

Examples 3 to 11, Comparative Examples 1 and 2 Each component was blended in accordance with the composition shown in Table 2, and
Preparation and evaluation of a molding material were performed in the same manner as in Example 2. Table 2 summarizes the results. However, in Examples 5 and 9, as the resin component, according to the composition shown in Table 2,
In addition to EOCN-1020-65 and PR-51470, 2,2-bis- (4-
70 parts of (4-maleimidophenoxy) phenyl) propane (bismaleimide manufactured by Mitsubishi Yuka Co., Ltd., MB-8000) were blended, and a molding material was prepared and evaluated in the same manner as in Example 1.

The PCBT failure time in each of Examples 1 to 11 was
500 hours or more. On the other hand, the PCBT failure time in Comparative Examples 1 and 2 is much shorter than 500 hours. From this, it is clear that the thermosetting resin composition containing the latent catalyst in the present invention exhibits extremely excellent moisture resistance reliability. Further, from the curing torque and the flow residual ratio of Examples 1 to 11 and Comparative Examples 1 and 2, it is clear that the latent catalyst in the present invention exhibits excellent curability and storage stability at room temperature.

(2) Evaluation in epoxy / amine curing system Example 12 95 parts of bisphenol A type epoxy resin (EP-1001 manufactured by Yuka Shell Epoxy), 4 parts of diaminodiphenylmethane, 1 part of dicyandiamide, and 13.3 parts of compound It was dissolved in 100 parts of a 1: 1 mixed solvent of N, N-dimethylformamide and methyl ethyl ketone to prepare a varnish.
After impregnating 100μ glass cloth with this varnish,
The prepreg was obtained by drying at 50 ° C. for 4 minutes. 16 sheets of this prepreg are stacked, and a copper foil having a thickness of 35 μ is stacked on the outside thereof,
170 ° C, 40kg / c between two stainless steel plates
Pressing at m2 for 50 minutes gave a double-sided copper-clad board with a thickness of 1.6 mm. The obtained double-sided copper-clad plate was subjected to etching as necessary, and the glass transition temperature was measured at a heating rate of 5 ° C./min with a dynamic viscoelasticity measuring device. In addition, the evaluation of the prepreg preservability was conducted by removing the resin component from the prepreg, measuring the initial gel time (abbreviated as GT) at 170 ° C.
GT after RH and storage for 7 days was measured and calculated by the following equation.
The larger the value of the residual gel time, the better the storage stability. Gel time remaining rate (%) = (40 ° C., 35% RH, GT (second) after 7 days / initial GT (second)) × 100

Examples 13 to 17 and Comparative Example 3 Each component was blended according to the composition shown in Table 3 and
A sample was prepared and evaluated in the same manner as described above. Table 3 summarizes the results.

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[Table 3]

(3) Evaluation with maleimide system Example 18 BMI-80 (2,2-bis- (4- (4
-Maleimidophenoxy) phenyl) propane) 10
0 parts, Compound 1 3.1 parts are dissolved in chloroform, N, N-dimethylformamide 1: 1 mixed solvent 100 parts,
After preparing the varnish, the solvent was quickly removed by drying under reduced pressure to obtain a solid content. The initial gel time of the solid content at 175 ° C. and the gel time after storage at 40 ° C. for 3 days were measured, and the gel time remaining ratio was calculated by the following formula. The larger the value of the residual gel time, the better the storage stability. Gel time residual rate (%) = (GT at 40 ° C., 3 days later)
/ Initial GT (sec)) x 100

Examples 19 to 23 and Comparative Example 4 Each component was blended according to the composition shown in Table 4 and the results were obtained in Example 18.
A sample was prepared and evaluated in the same manner as described above. The results are summarized in Table 4.

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[Table 4]

2. Example relating to epoxy resin molding material and semiconductor device Example 24 51 parts by weight of a resin mainly composed of a biphenyl type epoxy resin of the formula (8) (epoxy equivalent: 185, melting point: 105 ° C.),
49 parts by weight of the phenol resin of the formula (9) (hydroxyl equivalent: 167, softening point: 73 ° C.), 6.0 parts by weight of compound 1, 500 parts by weight of fused spherical silica (average particle size: 15 μm), 2 parts by weight of carbon black, bromine Bisphenol A type epoxy resin (2 parts by weight) and carnauba wax (2 parts by weight) were mixed, kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain a resin molding material. The obtained resin molding material was evaluated by the following method. Table 5 shows the results.

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[Table 5]

Evaluation method (i) Spiral flow: Using a mold for measuring spiral flow according to EMMI-I-66, mold temperature 175
C., injection pressure was 70 kg / cm ² , and curing time was 2 minutes. Spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity. The unit is cm. (Ii) Shore D hardness: mold temperature 175 ° C, injection pressure 70
Molding was performed at a curing time of 2 minutes in kg / cm ² , and the value of Shore D hardness measured 10 seconds after opening the mold was defined as curability. Shore D
Hardness is an index of curability, and the larger the value, the better the curability. (Iii) Storage at 30 ° C .: After storing at 30 ° C. for one week, the spiral flow was measured and expressed as a percentage of the spiral flow immediately after preparation. Units%. (Iv) Humidity reliability: mold temperature 175 ° C, pressure 70kg /
After sealing 16 pDIP with a resin molding material in cm ² and a curing time of 2 minutes, post-curing was performed at 175 ° C. for 8 hours. 12
After applying a voltage of 20 V in water vapor at 5 ° C. and a relative humidity of 100%, disconnection failure was examined. The time required for failure to appear in eight or more of the 15 packages was defined as the failure time. The unit is time. Note that the measurement time was 500 hours at the maximum, and when the number of defective packages was less than 8 at that time, the defective time was indicated as 500 hours or more. The longer the failure time, the better the moisture resistance reliability.

Examples 25 to 31 and Comparative Examples 5 to 7 Resin molding materials were prepared and evaluated in the same manner as in Example 24, according to the formulations shown in Tables 5 and 6. Tables 5 and 6 show the results.
Shown in

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[Table 5]

[0087]

[Table 6]

The crystalline epoxy resin A used in Example 25 was composed mainly of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylstilbene. Resin and 60% by weight of 4,4′-bis (2,
3-epoxypropoxy) -5-tert-butyl-
It is a mixture of 2,3 ′, 5′-trimethylstilbene and a resin containing 40% by weight as a main component (an epoxy equivalent of 20%).
9, melting point 120 ° C). The ortho-cresol novolak type epoxy resin used in Example 26 had an epoxy equivalent of 20.
0, softening point 65 ° C (EOCN-10 manufactured by Nippon Kayaku Co., Ltd.)
20-65). The phenol novolak resin used in Example 26 had a hydroxyl equivalent of 104 and a softening point of 105 ° C.
It is.

When triphenylphosphine was used as a catalyst (curing accelerator), the storage time at 30 ° C. was lowered, although the failure time in the humidity resistance reliability was good. (Refer to Comparative Example 5) When compounds 13 and 14 having a conductivity of the extraction water of the corresponding proton donor exceeding 1000 μS / cm were used as the curing accelerator, the moisture resistance reliability was lowered. (See Comparative Examples 6 and 7)

[0090]

As apparent from the above examples, the latent catalyst of the present invention and the thermosetting resin composition containing the catalyst have excellent moisture resistance reliability, curability, and storage stability at room temperature. Further, the epoxy resin molding compound for semiconductor encapsulation using the catalyst has extremely excellent room temperature storage characteristics and moldability, and the semiconductor device using the same has a moisture resistance reliability as a device for insertion mounting and surface mounting. Excellent and useful.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Yoshiyuki Go, 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Hiroshi Nagata 2-5-2 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Minoru Kobayashi 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo F-term (reference) 4J002 BH02W CC04X CD02W CD04W CD05W CD06W CD08W CD12W CD13W CE00X DE138 DE148 DJ018 DJ038 DJ048 DJ048 DL008 EL137 EN047 EN077 ER027 ET007 EU137 EW176 FD018 FD147 FD156 GQ05 4J034 HA01 KB02 KD14 RA07 4J036 AA01 AD07 AD08 AD10 DA10 FA01 FA05 FB06 FB07 GA23 JA07 4J043 PA02 QC07 QC08 RA08 SA06 SBUA 122 012 012 012 012 012 012 012 012 ZA46 ZB50

Claims (28)

[Claims] 1. A latent catalyst comprising a phosphonium borate represented by the general formula (1). Embedded image (However, R ¹ , R ² , R ³ and R ⁴ in the general formula (1) are
A monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, wherein R ¹ , R ² , R ³ and R ⁴ form a PC bond with a phosphorus atom; May be the same or different from each other. X ¹ , X ² , X ³
And at least one of X ⁴ and X ⁴ is a group in which a proton donor having at least one proton capable of being released outside the molecule releases one proton, and the other is a group having an aromatic ring or a heterocyclic ring. A monovalent organic group or a monovalent aliphatic group, which may be the same or different from each other. This proton donor is prepared by mixing 1 g of each proton donor with 50 g of pure water, and subjecting the mixture to a pressure cooker at 125 ° C. for 20 hours in a pressure cooker.
/ Cm or less. ) 2. A latent catalyst comprising a phosphonium borate represented by the general formula (2). Embedded image (However, R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (2) are
A monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ form a PC bond with a phosphorus atom; May be the same or different from each other. In the formula, Z ¹ is an organic group bonded to the substituents Y ¹ and Y ² . Where Z
² is an organic group bonded to the substituents Y ³ and Y ⁴ . Y
¹ and Y ² are groups in which a monovalent proton donating substituent emits a proton, and the substituents Y ¹ and Y ² in the same molecule are bonded to a boron atom to form a chelate structure . Y ³ and Y ⁴ are groups in which a monovalent proton donating substituent emits a proton, and the substituents Y ³ and Y ⁴ in the same molecule are bonded to a boron atom to form a chelate structure. is there. Z ¹ and Z ² may be the same or different from each other, and Y ¹ , Y ² , Y ³ and Y ⁴ may be the same or different from each other. Further, the ligand Y ¹ Z ¹ Y of boron
The proton donors, HY ¹ Z ¹ Y ² H and HY ³ Z ² Y ⁴ H, before ² and Y ³ Z ² Y ⁴ release protons,
1 g of each of these proton donors is mixed with 50 g of pure water, and the resulting mixture is subjected to a pressure cooker treatment at 125 ° C. for 20 hours in a pressure cooker, so that the conductivity of the extracted water is 1000 μS / cm or less. . ) 3. A latent catalyst comprising a phosphonium borate represented by the general formula (3). Embedded image (However, R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 in} the general formula (3)
Is a monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, and a phosphorus atom and R ⁹ , R ¹⁰ , R
¹¹ and R ¹² form a PC bond, which may be the same or different from each other. Where Z ³
Is an organic group bonded to the substituents Y ⁵ and Y ⁶ . Y ⁵
And Y ⁶ are groups in which a monovalent proton-donating substituent emits a proton, and may be the same or different from each other. When substituents Y ⁵ and Y ⁶ in the same molecule are bonded to a boron atom, It forms a chelate structure. X ⁵ and X ^{6 each} have at least one proton capable of being released outside the molecule.
The proton donors having one or more protons are a group that releases one proton, or a monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, which are the same or different. You may. Boron ligand Y ⁵ Z ³ Y
Proton donor HY ⁵ Z ³ before ⁶ releases a proton
Y ⁶ H, and X ⁵ and X ⁶ are proton donor when a proton donor having at least one proton capable of releasing to the outside of the molecule is one release was formed by based on proton H
X ⁵ and HX ⁶ are those each proton donor 1g was mixed with pure water 50 g 125 ° C. it in a pressure cooker vessel, the value of the conductivity of extracted water obtained by 20 hours pressure cooker treatment 1000 .mu.s / cm or less. ) 4. A boron atom, wherein a phosphonium borate composed of a monovalent cation portion in which four groups are bonded to a phosphorus atom and a monovalent anion portion in which four groups are bonded to a boron atom is a repeating unit. A latent catalyst having a structure in which two or more of these repeating units are linked via at least one of the four groups bonded to the compound. (However, the group linking the repeating units is a group in which one proton donor emits two or more protons, and they may be the same or different from each other. Is
A monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring, wherein the phosphorus atom and each group form a PC bond; You may. Of the groups bonded to the boron atom, those that do not participate in the linking of the repeating unit include a group in which a proton donor having at least one proton that can be released outside the molecule releases one proton, or an aromatic ring or a heterocyclic group. A monovalent organic group having a ring or a monovalent aliphatic group, which may be the same as or different from each other; The proton donor derived from the group bonded to the boron atom is obtained by mixing 1 g of each proton donor with 50 g of pure water and subjecting the mixture to a pressure cooker at 125 ° C. for 20 hours in a pressure cooker to extract water. The value of the rate is 1000 μS / cm or less. ) 5. The latent catalyst according to claim 1, wherein the proton donor having at least one proton which can be released outside the molecule is an aromatic carboxylic acid or a phenolic compound. 6. HY ¹ Z ¹ Y ² H or HY ³ Z according to claim 2
² Y ⁴ proton donor represented by H are aromatic carboxylic acids or phenolic compounds, according to claim 2, wherein the latent catalyst. 7. HX ⁵ or HX ^{6 according to} claim 3, wherein X ⁵ or X ⁶ is a group wherein at least one proton capable of being released outside the molecule is a proton donor which releases one proton. ) or HY ⁵ Z ³ Y ⁶ proton donor represented by H are aromatic carboxylic acids or phenolic compounds, according to claim 3, wherein the latent catalyst. 8. The latent catalyst according to claim 4, wherein the proton donor not involved in the connection of the repeating unit or the proton donor involved in the connection of the repeating unit is an aromatic carboxylic acid or a phenol compound. . 9. The position of claim 1, wherein the proton donor having at least one proton which can be released outside the molecule has at least one substituent selected from the group consisting of a carboxyl group and a phenolic hydroxyl group and is adjacent to each other. 2. The latent catalyst according to claim 1, wherein the latent catalyst is an aromatic carboxylic acid or phenolic compound having no carboxyl group or carboxyl group and phenolic hydroxyl group. 10. HX ⁵ or HX ^{6 according to} claim 3, wherein X ⁵ or X ⁶ is a group wherein at least one proton capable of being released outside the molecule is a proton donor which releases one proton. A) wherein the proton donor represented by) has at least one substituent selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and does not have two carboxyl groups or carboxyl groups and phenolic hydroxyl groups at positions adjacent to each other. The latent catalyst according to claim 3, which is an aromatic carboxylic acid or a phenolic compound. 11. The proton donor which does not participate in the connection of the repeating unit according to claim 4, has at least one substituent selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and has two carboxyl groups at positions adjacent to each other. 5. The latent catalyst according to claim 4, wherein the latent catalyst is an aromatic carboxylic acid or a phenolic compound having no carboxyl group and no phenolic hydroxyl group. 12. The HY ¹ Z ¹ Y ² H or HY ^{3 according to} claim 2,
The proton donor represented by Z ² Y ⁴ H has two or more substituents selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and two carboxyl groups or carboxyl groups and a phenolic hydroxyl group at positions adjacent to each other. 3. The latent catalyst according to claim 2, wherein the latent catalyst is an aromatic carboxylic acid or a phenolic compound in which is not present. 13. The proton donor represented by HY ⁵ Z ³ Y ⁶ H according to claim 3, which has two or more substituents selected from the group consisting of a carboxyl group and a phenolic hydroxyl group and is located at a position adjacent to each other. 4. An aromatic carboxylic acid or phenolic compound having no two carboxyl groups or a carboxyl group and a phenolic hydroxyl group.
The latent catalyst as described. 14. The proton donor involved in the connection of the repeating unit according to claim 4, which has two or more substituents selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and two carboxyl groups at positions adjacent to each other. 5. The latent catalyst according to claim 4, wherein the latent catalyst is an aromatic carboxylic acid or a phenolic compound having no carboxyl group and no phenolic hydroxyl group. 15. A substituted or unsubstituted benzoic acid, a substituted or unsubstituted naphthoic acid, a substituted or unsubstituted phenol, and a substituted or unsubstituted phenol, wherein the proton donor having at least one proton which can be released outside the molecule according to claim 1 is substituted or unsubstituted. The latent catalyst according to claim 1, which is a proton donor selected from the group consisting of unsubstituted naphthol. 16. HX ⁵ or HX ^{6 according to} claim 3, wherein X ⁵ or X ⁶ is a group wherein at least one proton capable of being released outside the molecule is a proton donor which releases one proton. ) Wherein the proton donor is a proton donor selected from the group consisting of substituted or unsubstituted benzoic acid, substituted or unsubstituted naphthoic acid, substituted or unsubstituted phenol, and substituted or unsubstituted naphthol. Item 4. The latent catalyst according to item 3. 17. The method according to claim 4, wherein the proton donor not involved in the connection of the repeating unit is a substituted or unsubstituted benzoic acid, a substituted or unsubstituted naphthoic acid, a substituted or unsubstituted phenol, and a substituted or unsubstituted naphthol. 5. A proton donor selected from the group consisting of:
The latent catalyst as described. 18. The method of claim 2, wherein HY ¹ Z ¹ Y ² H or HY ³
When the proton donor represented by Z ² Y ⁴ H is dihydroxybenzene, dihydroxynaphthalene, a bisphenol,
Or the latent catalyst according to claim 2, which is a biphenol. 19. The latent catalyst according to claim 3, wherein the proton donor represented by HY ⁵ Z ³ Y ⁶ H is dihydroxybenzene, dihydroxynaphthalene, bisphenols, or biphenols. 20. The latent catalyst according to claim 4, wherein the proton donor involved in the connection of the repeating unit is dihydroxybenzene, dihydroxynaphthalene, bisphenols, or biphenols. 21. A latent catalyst selected from the group consisting of the latent catalysts according to claim 1, 2, 3 and 4,
A thermosetting resin composition which is contained in an amount of 20 parts by weight and 100 parts by weight of the thermosetting resin. 22. The thermosetting resin composition according to claim 21, wherein the thermosetting resin is at least one selected from the group consisting of an epoxy resin and a maleimide resin. 23. An epoxy resin comprising (A) an epoxy resin, (B) a phenol resin, (C) the latent catalyst according to any one of claims 1 to 20 and (D) an inorganic filler as essential components. The equivalent ratio of the epoxy group of the resin to the phenolic hydroxyl group of the total phenolic resin is 0.5 to 2, and the blending amount of the inorganic filler (D) is 200 to 2400 per 100 parts by weight of the total amount of the total epoxy resin and the total phenolic resin. An epoxy resin molding material characterized by being in parts by weight. 24. An epoxy resin (A) having a melting point of 50 to 1
The epoxy resin molding material according to claim 23, which is a crystalline epoxy resin at 50 ° C. 25. The epoxy resin molding according to claim 24, wherein the crystalline epoxy resin having a melting point of 50 to 150 ° C. is at least one selected from the group consisting of epoxy resins of general formulas (4) and (5). material. Embedded image (Wherein, R ¹³ is a group or atom selected from hydrogen, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen, and may be the same or different from each other. ). (Wherein, R ¹⁴ is a group or atom selected from hydrogen, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen, and may be the same or different from each other. .) 26. The crystalline epoxy resin having a melting point of 50 to 150 ° C. is a mixture of a stilbene type epoxy resin represented by the general formula (6) and a stilbene type epoxy resin represented by the general formula (7). Item 24. The epoxy resin molding material according to item 24. Embedded image (Wherein, R ^{15 to} R ²² each independently represent a group or an atom selected from a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, and halogen.
The two aryl groups attached to the carbon-carbon double bond are different from each other. ) (Wherein, R ^{23 to} R ²⁶ each independently represent a group or an atom selected from a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, and halogen.
The two aryl groups attached to the carbon-carbon double bond are the same as each other. ) 27. The phenol resin (B) is a phenol aralkyl resin.
The epoxy resin molding material according to the above. 28. The method according to claim 23,24,25,26 or 2.
A semiconductor device, wherein the device is sealed with the epoxy resin molding material according to claim 7.