JP5088146B2 - Liquid epoxy resin composition for sealant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid epoxy resin composition for a sealant that exhibits room temperature-curability and can be converted into a sealed item having a high glass transition temperature and excellent adhesive properties by heating and postcuring under a condition of a low temperature and a short time, and to provide an electronic part device exhibiting excellent heat resistance and adhesive properties that has an element sealed using the liquid epoxy resin composition for a sealant. <P>SOLUTION: The liquid epoxy resin composition for a sealant comprises an epoxy resin (A) bearing at least three epoxy groups in one molecule, an organic compound (B) bearing at least two mercapto groups in one molecule and a benzoxazine compound (C) having a specific structure, where the amount of the epoxy resin (A) is less than 90 mass% of the total amount of the epoxy resin (A) and the benzoxazine compound (C). The electronic part device comprises an element sealed using the liquid epoxy resin composition for a sealant. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

The present invention relates to a liquid epoxy resin composition for a sealant.
More specifically, the present invention has room temperature curability and can be a sealed body having a high glass transition temperature and excellent adhesiveness by heating and post-curing under low temperature and short time conditions. The present invention relates to a liquid epoxy resin composition for a sealant and an electronic component device having an element sealed with the liquid epoxy resin composition for a sealant and having excellent heat resistance and adhesiveness.

Conventionally, as a method for sealing a substrate and an element in response to a demand for higher integration, higher density, thinner package and smaller size of the element, for example, an element such as a flip chip is connected to the substrate, and then Capillary flow method that seals between and around the substrate with an underfill agent, or solder coating and underfill by reflow after applying the underfill agent to the substrate in advance and temporarily mounting the element here There has been proposed an underfill agent pre-adhesion method in which sealing with an agent is performed collectively.
And patent document 1 is proposed as an epoxy resin composition which can be used as an underfill agent.
Patent Documents 2 to 4 have been proposed as compositions that contain an epoxy resin and seal a semiconductor or the like.

JP 2006-16576 A JP-A-11-140278 Japanese Patent Laid-Open No. 2001-278554 JP 2006-206642 A

However, when a conventionally used epoxy resin composition for electronic materials is cured to form a sealed body, the epoxy resin composition is generally heated at a high temperature in order to increase the heat resistance of the sealed body. It was necessary to cure.
When a conventional epoxy resin composition is cured at a low temperature and used as a sealant for an electronic component device, it has been difficult to obtain sufficient heat resistance and adhesiveness of the sealant.
Therefore, the present invention is a sealant that has room temperature curability and can be a sealed body having a high glass transition temperature and excellent adhesiveness by heating and post-curing under low temperature and short time conditions. It is an object of the present invention to provide a liquid epoxy resin composition for use and an electronic component device having an element sealed using the liquid epoxy resin composition for a sealant and having excellent heat resistance and adhesiveness.

  As a result of diligent research to solve the above problems, the present inventor has obtained an epoxy resin (A) having three or more epoxy groups in one molecule and an organic compound having two or more mercapto groups in one molecule ( B) and a benzoxazine compound (C) having a specific structure, and the amount of the epoxy resin (A) is 90 mass of the total amount of the epoxy resin (A) and the benzoxazine compound (C). % Sealing resin having a high glass transition temperature and excellent adhesion by heating and post-curing under low temperature and short time conditions. And an electronic component device having an element sealed with the liquid epoxy resin composition for a sealant, having a heat resistance, And it found that the superior sex, has led to the completion of the present invention.

That is, the present invention provides the following (1) to ( 7 ).
(1) an epoxy resin (A) having three or more epoxy groups in one molecule;
An organic compound (B) having two or more mercapto groups in one molecule;
A benzoxazine compound (C) represented by the following formula ( 4 ),
A liquid epoxy resin composition for a sealant, wherein the amount of the epoxy resin (A) is less than 90% by mass of the total amount of the epoxy resin (A) and the benzoxazine compound (C), and the organic compound A liquid epoxy resin composition for a sealant, wherein (B) is a condensate (D) of a mercapto group-containing silane compound.

(2) The liquid epoxy resin composition for sealing agents according to (1), wherein the epoxy resin (A) is represented by the following formula (2).

(In the formula, each R ² is independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may have a substituent, and R ² may be the same or different. , N is an integer from 0 to 4.)
( 3 ) In the above (1) or (2) , the amount of the mercapto group that the organic compound (B) has is 0.1 to 0.5 equivalents relative to the epoxy group that the epoxy resin (A) has. The liquid epoxy resin composition for sealing agents as described.
(4) A sealed electronic material obtained by sealing an electronic material using the liquid epoxy resin composition for a sealant according to any one of (1) to (3).
( 5 ) An electronic component device obtained by sealing a substrate and an element using the liquid epoxy resin composition for a sealant according to any one of (1) to ( 3 ).
( 6 ) After mounting the element on the substrate, the element and the substrate are sealed by sealing with the liquid epoxy resin composition for sealant according to any one of (1) to ( 3 ) above. An electronic component device manufacturing method for manufacturing a stopped electronic component device.
( 7 ) After apply | coating the liquid epoxy resin composition for sealing agents in any one of said (1)-( 3 ) to one or both of an element and a board | substrate, the said element is mounted in the said board | substrate. An electronic component device manufacturing method for manufacturing a sealed electronic component device by bonding the element to the substrate.

The liquid epoxy resin composition for a sealant of the present invention has room temperature curability and has a high glass transition temperature and excellent adhesion by heating and post-curing under low temperature and short time conditions. Can be.
The electronic component device of the present invention is excellent in heat resistance and adhesiveness.

The present invention will be described in detail below.
First, the liquid epoxy resin composition for a sealant of the present invention will be described.
The liquid epoxy resin composition for sealant of the present invention is
An epoxy resin (A) having three or more epoxy groups in one molecule;
An organic compound (B) having two or more mercapto groups in one molecule;
A benzoxazine compound (C) represented by the following formula (1):
In the composition, the amount of the epoxy resin (A) is less than 90% by mass of the total amount of the epoxy resin (A) and the benzoxazine compound (C).
In the formula, each R ¹ is independently a hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group may have a substituent, and R ¹ may be the same or different, n is an integer of 0-4 each independently.

The epoxy resin (A) will be described below.
The epoxy resin (A) contained in the liquid epoxy resin composition for sealant of the present invention has three or more epoxy groups in one molecule.

  Examples of the epoxy resin (A) include N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyl-m-xylylenediamine, triglycidyl-p-aminocresol, 1,3-bis. Glycidylamine type epoxy resin such as (N, N-diglycidylaminomethyl) cyclohexane; Multifunctional glycidyl ether type such as phenol novolac type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type An epoxy resin is mentioned.

An epoxy resin can be used individually or in combination of 2 types or more, respectively.
Moreover, as an epoxy resin (A), the epoxy resin represented by following formula (2) is mentioned, for example.

In the formula, each R ² is independently a hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group may have a substituent, and R ² may be the same or different, n is an integer of 0-4.

The hydrocarbon group having 1 to 10 carbon atoms is not particularly limited.
Moreover, the hydrocarbon group can have a substituent.
Examples of the substituent that the hydrocarbon group having 1 to 10 carbon atoms may have include an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group; an alkenyl group such as a vinyl group, an allyl group, and a butenyl group; An aryl group such as a phenyl group, a naphthyl group and a biphenyl group; an alkyl group such as a methyl group, an ethyl group, a butyl group and a t-butyl group; an ether bond and an ester bond.

  Examples of the hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, and an octyl group. , A branched alkyl group such as decyl group; an alicyclic hydrocarbon group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group; benzyl group, phenethyl group Aryl group-substituted alkyl groups such as: methoxy group-substituted alkyl groups, ethoxy group-substituted alkyl groups, alkoxy group-substituted alkyl groups such as butoxy group-substituted alkyl groups; alkenyl groups such as vinyl groups, allyl groups, and butenyl groups; phenyl Group, aryl group such as naphthyl group; tolyl group, dimethylphenyl group, ethylphenyl group, butyl group Group, an alkyl group substituted aryl group such as t- butylphenyl group; methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, an alkoxy group-substituted aryl group such as a t- butoxyphenyl group.

R ² may be the same or different.
n is an integer of 0 to 4, among which 0 or 1 is preferable, and 0 is more preferable.

Especially, it is preferable that an epoxy resin (A) is what is represented by Formula (2) from a viewpoint that a glass transition temperature becomes higher and the viscosity of a composition can be made low.
Examples of the epoxy resin represented by the formula (2) include triglycidyl-p-aminophenol, triglycidyl-p-aminocresol, and triglycidyl-m-aminophenol.
Among these, triglycidyl-p-aminophenol is preferable from the viewpoint that the glass transition temperature becomes higher and the viscosity of the composition can be lowered.

The weight average molecular weight of the epoxy resin (A) is preferably 200 to 2,000, more preferably 200 to 500, from the viewpoint that the composition can be easily made uniform.
The epoxy resin (A) is preferably in a liquid state at room temperature from the viewpoint that the composition can be easily made uniform and the viscosity of the composition can be within an appropriate range.
Using an E-type viscometer as the viscometer of the epoxy resin (A), using a 3 ° cone, the rotational speed is 1 r. p. m, the viscosity measured under conditions of 25 ° C. is preferably 100 to 2,000 mPa · s, more preferably 100 to 1,000 mPa · s.
An epoxy resin (A) can be used individually or in combination of 2 types or more, respectively.

The organic compound (B) will be described below.
The organic compound (B) contained in the liquid epoxy resin composition for an encapsulant of the present invention has two or more mercapto groups in one molecule.
The number of mercapto groups contained in one molecule of the organic compound (B) is preferably 3 or more from the viewpoint of superior room temperature curability.
The mercapto group can be bonded to the end, both ends or the skeleton of the organic compound (B).
In addition to the mercapto group, the organic compound (B) includes, for example, a functional group such as a carbonyl group, a urea group (carbamide group), an isocyanate group, and an alkoxysilyl group; an ether bond, a thioether bond, an ester bond, an amide bond, and a urethane. There can be at least one bond, such as a bond.

Examples of the organic compound (B) include a compound represented by the following formula (6) and a condensate (D) of a mercapto group-containing silane compound.
R- (SH) _n (6)
In formula (6), R is a hydrocarbon group, and n is an integer of 2 or more.
The hydrocarbon group is not particularly limited. Examples thereof include a chain or branched alkyl group, an aliphatic hydrocarbon group containing an unsaturated bond, a cycloalkyl group, an aromatic hydrocarbon group, and an aralkyl group.
n is preferably an integer of 3 or more from the viewpoint of superior room temperature curability.
Examples of the compound represented by the formula (6) include dithiol compounds having two mercapto groups and trifunctional or more thiol compounds having three or more mercapto groups.

  Examples of the dithiol compound include ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol, heptanedithiol, octanedithiol, nonanedithiol, decanedithiol, benzenedithiol, toluene-3,4-dithiol, and 3,6-dichloro. -1,2-benzenedithiol, 1,5-naphthalenedithiol, benzenedimethanethiol, 4,4'-thiobisbenzenethiol, 2-di-n-butylamino-4,6-dimercapto-s-triazine, 5 , 5-bis (mercaptomethyl) -3,7-dithianonane-1,9-dithiol, dimercaptopropanol, dithioerythritol, dimercaptoethylsulfite.

  Examples of the tri- or more functional thiol compound include polythiol (for example, “QE-340M” manufactured by Toray Fine Chemical Co., Ltd.), trithioglycerin, , 3,5-triazine-2,4,6-trithiol (trimercapto-triazine), trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, 1,2,4-tris (mercaptomethyl) benzene 1,3,5-tris (mercaptomethyl) benzene, 2,4,6-tris (mercaptomethyl) mesitylene, tris (mercaptomethyl) isocyanurate, tris (3-mercaptopropyl) isocyanurate, 2,4,5 -Tris (mercaptomethi) ) -1,3-dithiolane-like trithiols; pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, 1,2,4,5-tetrakis (mercaptomethyl) benzene, tetramercaptobutane, pentaerythrithiol And tetrathiols such as dipentaerythritol hexa-3-mercaptopropionate.

  Among these, from the viewpoint of superior room temperature curability, a hexathiol compound such as dipentaerythritol hexa-3-mercaptopropionate; a condensate of a mercapto group-containing silane compound is preferable.

The condensate (D) of the mercapto group-containing silane compound is not particularly limited as long as it has a structure in which the mercapto group is bonded to the polysiloxane skeleton through a hydrocarbon group. For example, it can be obtained by condensing a mercapto group-containing silane compound.
The mercapto group-containing silane compound used when producing the condensate (D) is not particularly limited as long as it is a compound having a mercapto group and a silicon atom. For example, a silane coupling agent having a mercapto group can be mentioned.
The silicon atom contained in the mercapto group-containing silane compound is preferably a silicon atom contained in a hydrolyzable silyl group (silyl group having hydrolyzability) or a silanol group.
The hydrolyzable silyl group is not particularly limited as long as it becomes a silanol group after hydrolysis. Examples of the hydrolyzable silyl group include those in which 1 to 3 alkoxy groups and phenoxy groups are bonded to a silicon atom. Examples of the alkoxy group include a methoxy group and an ethoxy group.
When there are 1 to 2 alkoxy groups and phenoxy groups bonded to the silicon atom, the remaining groups bonded to the silicon atom are not particularly limited. Examples thereof include a methyl group and an ethyl group.

Examples of the mercapto group-containing silane compound include those represented by the following formula (7).
^{_{(HS) n -R 3 -Si (}} -OR 4) a (-R 5) 3-a (7)
In Formula (7), R ³ is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ and R ⁵ are each independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is a substituent. A is an integer of 1 to 3, and n is an integer of 1 or more.
Examples of the hydrocarbon group having 1 to 10 carbon atoms as R ⁴ or R ⁵ include a methyl group, an ethyl group, and a phenyl group.
The hydrocarbon group having 1 to 10 carbon atoms as R ³ is divalent, for example, an alkylene group such as methylene group, ethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group; phenylene group An aromatic ring group such as
The substituents that the hydrocarbon group can have are as defined above.
n is preferably an integer of 1 to 2 from the viewpoint of excellent viscosity and storage stability.

Examples of the mercapto group-containing silane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 3-mercaptopropylethyldiethoxy. Examples include silane.
Among these, 3-mercaptopropyltrimethoxysilane is preferable from the viewpoint of excellent adhesiveness and higher glass transition temperature.
The mercapto group-containing silane compounds can be used alone or in combination of two or more.

  The condensate (D) is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. Specifically, the condensate (D) can be produced by reacting a mercapto group-containing silane compound with a silanol condensation catalyst such as dibutyltin laurate.

Examples of the condensate (D) of the mercapto group-containing silane compound include those represented by the following formula (8).
In formula (8), R ⁶ and R ⁸ are each independently a hydrocarbon group having 1 to 10 carbon atoms, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is substituted. R ⁷ may be —OR ⁴ or —R ⁵ in Formula (7), n is an integer of 1 or more, and m is an integer of 1 or more.
Examples of the hydrocarbon group having 1 to 10 carbon atoms as R ⁶ and R ⁸ include a methyl group, an ethyl group, and a phenyl group.
Hydrocarbon group having 1 to 10 carbon atoms as R ³ are the same as R ³ in the formula (7).
The substituents that the hydrocarbon group can have are as defined above.

Examples of the condensate (D) of the mercapto group-containing silane compound include a condensate of 3-mercaptopropyltrimethoxysilane, a condensate of 3-mercaptopropyltriethoxysilane, and a condensate of 3-mercaptopropylmethyldimethoxysilane, 3 -Mercaptopropylmethyldiethoxysilane condensates.
Among these, a condensate of 3-mercaptopropyltrimethoxysilane is preferable from the viewpoint of superior room temperature curability.

In addition, the condensate (D) of the mercapto group-containing silane compound is preferably from 500 to 5,000 in terms of weight average molecular weight from the viewpoint of excellent adhesiveness and higher glass transition temperature of the cured product. 500 to 2,000 is more preferable.
In addition, in this-application specification, a weight average molecular weight is a polystyrene conversion value by GCP (gel permeation column chromatography).

In addition, the condensate (D) of the mercapto group-containing silane compound is preferably from 100 to 500 g / eq in terms of the thiolation amount from the viewpoint that the adhesiveness is excellent and the glass transition temperature of the cured product becomes higher. 100 to 300 g / eq is more preferable.
An organic compound (B) can be used individually or in combination of 2 types or more, respectively.

  The amount of the mercapto group that the organic compound (B) has is 0.000 to the epoxy group that the epoxy resin (A) has, from the viewpoint that it is excellent in room temperature curability, has a higher glass transition temperature, and is excellent in adhesiveness. It is preferably 1 to 0.5 equivalent, and more preferably 0.2 to 0.4 equivalent.

The benzoxazine compound (C) will be described below.
The benzoxazine compound (C) contained in the liquid epoxy resin composition for an encapsulant of the present invention is a compound represented by the following formula (1).
In the formula, each R ¹ is independently a hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group may have a substituent, and R ¹ may be the same or different, n is an integer of 0-4 each independently.

The benzoxazine compound (C) is a condensed polycyclic compound in which an oxazine ring is condensed with a benzene ring as shown in the formula (1). The benzoxazine compound (C) has two benzoxazine rings.
In the formula (1), the nitrogen atoms of the two benzoxazine rings are in the central direction of the benzoxazine compound (C) with each other [the direction in which the methylene group is bonded to two phenylene groups in the formula (1)]. A benzoxazine ring is arranged so as to face each other. The same thing can be said about the benzene ring of the benzoxazine ring. In the formula (1), the benzoxazine ring is arranged so that both benzene rings of the benzoxazine ring are located outside the benzoxazine compound (C). Yes.

The hydrocarbon group having 1 to 10 carbon atoms has the same meaning as described above.
The substituents that the hydrocarbon group can have are as defined above.
Each n is independently an integer of 0 to 4, and is preferably 0, 1 or 2 and more preferably 0 from the viewpoint that the glass transition temperature becomes higher and the adhesiveness is more excellent.

Examples of the benzoxazine compound (C) include a compound represented by the following formula (4) and Pd type benzoxazine (trade name Pd type benzoxazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.).

Of these, the compound represented by the formula (4) and the Pd-type benzoxazine are preferable from the viewpoint that the glass transition temperature becomes higher and the adhesiveness is more excellent.
The benzoxazine compounds (C) can be used alone or in combination of two or more.

The amount of the epoxy resin (A) is less than 90% by mass of the total amount of the epoxy resin (A) and the benzoxazine compound (C) from the viewpoint that the glass transition temperature becomes high and the adhesiveness is excellent.
When the amount of the epoxy resin (A) is less than 90% by mass of the total amount of the epoxy resin (A) and the benzoxazine compound (C), the benzoxazine compound (C) is an amount exceeding 10% by mass.
Further, the amount of the epoxy resin (A) and the benzoxazine compound (C) is such that the ratio of the benzoxazine compound (C) to the epoxy resin (A) from the viewpoint that the glass transition temperature becomes higher and the adhesiveness is superior ( The benzoxazine compound (C) / epoxy resin (A)) is preferably in a mass ratio of more than 10 / less than 90 to 80/20, and more preferably 20/80 to 80/20.

The sealing liquid epoxy resin composition of the present invention can further contain a curing agent. Further, examples of the curing agent that can be contained include those that can be used for epoxy resins. As a hardening | curing agent, a phenol resin, an amine compound, and an acid anhydride are mentioned, for example.
The phenol resin is not particularly limited as long as it has two or more phenolic hydroxy groups in one molecule. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. Phenols and / or novolak type phenol resins and phenols obtained by condensation or cocondensation of naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and the like and compounds having an aldehyde group such as formaldehyde in the presence of an acidic catalyst And / or phenol / aralkyl resins synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, aralkyl-type phenol resins such as naphthol / aralkyl resins, and dicyclopentadiene modification Examples include phenol resin, cyclopentadiene-modified phenol resin, terpene-modified phenol resin, polycyclic aromatic ring-modified phenol resin, triphenolmethane type phenol resin, bisphenol A, bisphenol F, bisphenol S, thiodiphenol, naphthalenediol. Moreover, a phenol resin can be used as an allylated product.

The amine compound is preferably a polyamine compound having two or more nitrogen atoms.
Examples of the polyamine compound include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, latent curing agents, and special amines.

  The aromatic polyamine curing agent is not particularly limited as long as an amino group and / or an imino group are bonded to the aromatic ring. For example, benzyldimethylamine, dimethylaminomethylphenol, trisdimethylaminomethylphenol, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-1, 1,4 -Tertiary amines such as diazabicyclo [2.2.2] octane; N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-diisopropylethylenediamine, N, N'-dimethyl-1 , 3-propanediamine, N, N′-diethyl-1,3-propanediamine, N, N′-diisopropyl-1,3-propanediamine, N, N′-dimethyl-1,6-hexanediamine, N, Secondary amines such as N'-diethyl-1,6-hexanediamine; 3,3'-diaminodiph Nylsulfone (3,3'-DDS), diaminodiphenylsulfone such as 4,4'-diaminodiphenylsulfone (4,4'-DDS), diaminodiphenyl ether (DADPE), bisaniline, benzyldimethylaniline, 3,3'- Dichloro-4,4'-diaminodiphenylmethane (MOCA), 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'- Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-tolylenediamine, 2, 4-tolylenediamine, 2, - tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, methylthio diamine include primary amines such as diethyl toluene diamine.

  The latent curing agent is not particularly limited as long as it generates an amine compound by heat or the like, and the generated amine compound functions as a curing agent for the epoxy resin (A) or the organic compound (B). Examples thereof include organic acid dihydrazide, dicyandiamide, amine imide, tertiary amine salt, imidazole salt, Lewis acid, Bronsted acid, oxazolidine compound, and ketimine compound.

  The acid anhydride is not particularly limited as long as it is a compound having a carboxylic acid anhydride group. Examples include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hymic anhydride, succinic anhydride, trimellitic anhydride, and pyromellitic anhydride.

Among these, from the viewpoint of excellent cured product properties, tertiary amines are preferable, and 2,4,6-tris (dimethylaminomethyl) phenol is more preferable.
A hardening | curing agent can be used individually or in combination of 2 or more types, respectively.

  The amount of the curing agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the epoxy resin (A) and the organic compound (B) from the viewpoint of excellent room temperature curability. More preferably, it is 5-5 mass parts.

In the liquid epoxy resin composition for an encapsulant of the present invention, the heating temperature in the post-cure can be lowered, and from the viewpoint of excellent room temperature curability at the time of pre-curing, it further contains an imidazole compound as a polymerization catalyst. Is preferred. Examples of the polymerization catalyst include those that can be used for epoxy resins.
The imidazole compound is not particularly limited as long as it is a compound having an imidazole ring. For example, N-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl-4 -Methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1' )) Ethyl-s-triazine, 2,4- Amino-6 (2'-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine isocyanuric acid Adduct, 2: 3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole Various imidazoles such as 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and these imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid , Salts with polyvalent carboxylic acids such as maleic acid and succinic acid It is below.

Of these, N-methylimidazole is preferable from the viewpoint of excellent curability.
The imidazole compounds can be used alone or in combination of two or more.

From the viewpoint of excellent curability, the amount of the imidazole compound is preferably 0.5 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin (A). More preferred.
When manufacturing the liquid epoxy resin composition for sealing agents of this invention as a 2 liquid type which has a main ingredient and a hardening | curing agent, it is preferable to add an imidazole compound to the hardening | curing agent side from a viewpoint that it is excellent in storage stability.

The liquid epoxy resin composition for sealing of the present invention can further contain a flux agent in order to impart a flux function.
The fluxing agent is not particularly limited. For example, a conventionally well-known thing is mentioned. Specific examples thereof include hydrohalic acid amine salts. As a flux agent, from the viewpoint of electrical characteristics, for example, a compound having a phenolic hydroxyl group and a carboxyl group such as hydroxybenzoic acid, an acid anhydride containing a carboxyxyl group such as trimellitic acid, abitienic acid, adipic acid, ascorbic acid, Preference is given to organic acids such as citric acid, 2-furancarboxylic acid and malic acid, and compounds containing two or more alcoholic hydroxyl groups per molecule.

The amount of the fluxing agent is not particularly limited as long as the flux function is exhibited, and is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass in the total amount of the sealing liquid epoxy resin composition.
When the amount of the fluxing agent is 0.5% by mass or more, the wettability of the solder is sufficient and the connection resistance tends to be low.
Moreover, when the amount of the fluxing agent is 10% by mass or less, voids tend not to be generated.

The liquid epoxy resin composition for sealing of the invention can further contain a filler as necessary.
The filler is used for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, and is not particularly limited as long as it is generally used in a liquid epoxy resin composition for sealing. . For example, fused silica, crystalline silica, fumed silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, barium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, fosterite, steer Examples thereof include powders such as tight, spinel, mullite, and titania, or spherical fillers and inorganic fillers such as glass fibers.
The fillers can be used alone or in combination of two or more.
Of these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity.
In addition, the shape of the filler is preferably a spherical shape because high filling can be achieved.
In the case of imparting thixotropy to the liquid epoxy resin composition for sealing, a small amount of ultrafine silica can be added according to the thixotropy ratio.

When the liquid epoxy resin composition for sealing of the present invention contains an inorganic filler, the liquid epoxy resin composition for sealant of the present invention increases the affinity between the resin component and the inorganic filler and is inorganic. In order to improve the dispersibility of the filler, a coupling agent can be further contained as necessary.
Examples of the coupling agent include silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane; coupling agents such as titanium compounds, aluminum chelates, and aluminum / zirconium compounds. .
Specific examples thereof include, for example, vinyl silane such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane; γ-methacryloxypropyltrimethoxysilane. (Meth) acryl silanes such as γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, epoxy silane such as γ-glycidoxypropylmethyldimethoxysilane; γ-mercaptopropyltrimethoxysilane, mercaptosilane such as γ-mercaptopropylmethyldimethoxysilane; Pyrtriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxy Silane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N-β- (N- Aminosilanes such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, N- (dimethoxymethylsilylisopropyl) ethylenediamine; alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane; A halogenated silane such as chloropropyltrimethoxysilane; a disilane-based coupling agent such as hexamethyldisilane; isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) ) Titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyro) Phosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridode Examples thereof include titanate coupling agents such as silbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis (dioctyl phosphite) titanate.
The silane coupling agents can be used alone or in combination of two or more.

The amount of the coupling agent is preferably 0.05 to 5% by weight and more preferably 0.1 to 2.5% by weight with respect to the inorganic filler.
When the amount of the silane coupling agent is 0.05% by weight or more, the effect of improving the dispersibility of the filler is excellent.
Moreover, when the amount of the silane coupling agent is 5% by weight or less, voids tend not to be generated in the cured product.

The liquid epoxy resin composition for sealing of the present invention can further contain an ion trapping agent as necessary from the viewpoint of improving the moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC.
There is no restriction | limiting in particular as an ion trap agent, For example, a conventionally well-known thing is mentioned. Specific examples include hydrotalcites and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth.

Especially, the hydrotalcite shown by the following compositional formula (I) is mentioned as one of the preferable aspects.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (I)
(In the formula, 0 <X ≦ 0.5, and m is a positive number.)
An ion trap agent can be used individually or in combination of 2 types or more, respectively.
The amount of the ion trapping agent is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, and is preferably 0.1 to 5% by mass, and 0.1 to 1% by mass with respect to the epoxy resin (A). % Is more preferable.

The liquid epoxy resin composition for sealing of the present invention can further contain a flame retardant as necessary.
As the flame retardant, conventionally known ones can be used, and examples thereof include brominated epoxy resins, antimony trioxide, non-halogen, and non-antimony flame retardants.
Specifically, for example, red phosphorus coated with a thermosetting resin such as red phosphorus, phenolic resin, etc., phosphorus compounds such as phosphate ester, triphenylphosphine oxide, melamine, melamine derivatives, melamine modified phenolic resin, triazine Compounds having a ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, metal complex compounds such as dicyclopentadienyl iron, zinc oxide, zinc stannate, zinc borate, Examples include zinc compounds such as zinc molybdate, metal oxides such as iron oxide and molybdenum oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and composite metal hydroxides represented by the following composition formula (II). It is done.
p (M ¹ _a O _b ) · q (M ² _c O _d ) · r (M ³ _c O _d ) · mH ₂ O (II)
(Here, M ¹ , M ² and M ³ represent different metal elements, a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number.)

M ¹ , M ² and M ^{3 in the} composition formula (II) are not particularly limited as long as they are different metal elements.
From the viewpoint of flame retardancy, M ¹ is selected from metal elements belonging to the third period metal element, group IIA alkaline earth metal element, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA M ² is preferably selected from IIIB-IIB group transition metal elements, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is iron. More preferably, it is selected from cobalt, nickel, copper and zinc.
From the viewpoint of fluidity, it is preferable that M ¹ is magnesium, M ² is zinc or nickel, and r = 0.
The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1.
Commercially available products include, for example, M ¹ in composition formula (II), magnesium, M ² is zinc, p is 7, q is 3, m is 10, a, b, c, and d are 1, r May be magnesium hydroxide / zinc solid solution composite metal hydroxide (product name: Echo Mug Z-10, manufactured by Tateho Chemical Co., Ltd.).
In addition, the classification of metal elements is a long-period type periodic rate table in which the typical element is the A subgroup and the transition element is the B subgroup (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987) (Reduced plate 30th printing).
A flame retardant can be used individually or in combination of 2 or more types, respectively.

  The sealing liquid epoxy resin composition of the present invention further includes, for example, dyes, pigments, colorants such as carbon black, diluents, leveling agents, antifoaming agents, silicone oils, silicone resins, liquid rubbers, rubber powders, An additive such as a stress relaxation agent such as a thermoplastic resin can be contained as necessary.

  The liquid epoxy resin composition for sealing of the present invention is not particularly limited for its production, and can be produced using any technique. As a general method, for example, a method of dispersing and kneading with a three-roller, a rough machine or the like can be mentioned.

The liquid epoxy resin composition for a sealant of the present invention can be produced as a one-component or two-component composition. From the viewpoint of excellent storage stability, it is mentioned as one of preferred embodiments that it is produced as a two-component composition.
When the liquid epoxy resin composition for a sealant of the present invention is produced as a two-component composition having a main agent and a curing agent, an epoxy resin (A), an organic compound (B), and a benzoxazine compound are formed on the main agent side. (C) and a silane coupling agent and a filler as required, and a curing agent, an imidazole compound, and a silane coupling agent and a filler as required can be added to the curing agent side.

The composition of this invention can be used as a composition for sealing agents with respect to electronic materials such as elements and substrates.
Examples of the substrate to which the sealing liquid epoxy resin composition of the present invention can be applied include support members such as lead frames, wired tape carriers, wiring boards, glass, and silicon wafers.
Examples of the element to which the liquid epoxy resin composition for sealing agent of the present invention can be applied include active elements such as semiconductor chips, transistors, diodes, and thyristors; passive elements such as capacitors, resistors, and coils. Can be mentioned.

As an electronic component device obtained by sealing an element and / or a bonding area with the liquid epoxy resin composition for sealing of the present invention, for example, a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, etc. On the support member (substrate), active elements such as semiconductor chips, transistors, diodes, thyristors, etc., and passive elements such as capacitors, resistors, coils, etc. are mounted, and the necessary parts are liquid epoxy for sealing of the present invention. Examples thereof include an electronic component device obtained by sealing with a resin composition.
As such an electronic component device, specifically, for example, a semiconductor element is fixed on a lead frame, and a terminal portion and a lead portion of an element such as a bonding pad are connected by wire bonding or bump, and then the sealing of the present invention is performed. PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-Lead Package), which is sealed using a liquid epoxy resin composition for stopping. ), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package) and other general resin-encapsulated ICs, and semiconductor chips connected to tape carriers by bumps , TCP (Tape Carrier Package) sealed with the liquid epoxy resin composition for sealing of the present invention, semiconductor chip, transistor connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module in which active elements such as diodes and thyristors and / or passive elements such as capacitors, resistors and coils are encapsulated with the liquid epoxy resin composition for encapsulation of the present invention, hybrid IC, multi A liquid epoxy resin composition for sealing of the present invention after mounting a semiconductor chip on an interposer substrate on which terminals for connecting a chip module and a mother board are formed, and connecting the wiring formed on the semiconductor chip and the interposer substrate by bumps or wire bonding Semiconductor chips with objects One side sealing packages such as BGA (Ball Grid Array), CSP (Multi Size Package), MCP (Multi Chip Package), flip chip, etc. are provided.

  The liquid epoxy resin composition for an encapsulant of the present invention can be used as an underfill agent for encapsulating an electronic component device and an underfill agent used in an underfill material prior system.

Especially, the liquid epoxy resin composition for sealing of this invention is suitable for the electronic component apparatus using the underfill material used in order to improve reliability, such as a flip chip and CSP.
Moreover, the liquid epoxy resin composition for sealing of this invention is suitable for the electronic component apparatus manufactured by an underfill material advance system.

  Examples of a method for applying and sealing an element and / or a bonding area using the liquid epoxy resin composition for sealing of the present invention include a dispense method, a casting method, a printing method, and the like.

After the liquid epoxy resin composition for a sealant of the present invention is applied to an electronic component device, the electronic component device is placed at room temperature (20 to 25 ° C.) for 1 to 3 hours, and then the liquid for a sealant of the present invention is placed. The epoxy resin composition can be cured (precured) at room temperature to bond the electronic component device.
Then, after curing at room temperature, the electronic component device is further placed in a heating device such as an oven, and is heated for 1 to 3 hours under conditions of 150 to 180 ° C. to be cured (post-cure). The liquid epoxy resin composition can be used as a sealing body having a high glass transition temperature and excellent adhesiveness, and the electronic component device can be completely sealed.
In addition, the liquid epoxy resin composition for sealing agents of the present invention can be heat-cured immediately after application to an electronic component device.

  The liquid epoxy resin composition for a sealant of the present invention is cured at room temperature for 3 hours under conditions of 23 ° C., and then cured by curing for 1 hour under conditions of 150 ° C. after curing at room temperature (post cure). The glass transition temperature of the cured product obtained is preferably 140 ° C. or higher, and preferably 150 ° C. or higher, from the viewpoint of excellent heat resistance.

In the present invention, the glass transition temperature was measured under the following measurement conditions using a dynamic viscoelasticity measuring device (DMA).
<Measurement conditions>
Measurement temperature: room temperature to 220 ° C
・ Temperature increase rate: 5 ° C./min ・ Measurement frequency: 1 Hz, strain: 0.01%
As a result of the measurement, the temperature at the peak top of the obtained loss rigidity (G ″) was defined as the glass transition temperature.

The encapsulated electronic material of the present invention will be described below.
The encapsulated electronic material of the present invention is
It is the sealed electronic material obtained by sealing an electronic material using the liquid epoxy resin composition for sealing agents of this invention.

The composition used in the sealed electronic material of the present invention is not particularly limited as long as it is a liquid epoxy resin composition for a sealant of the present invention.
The electronic material used in the sealed electronic material of the present invention is not particularly limited. For example, a conventionally well-known thing is mentioned.
The sealed electronic material of the present invention (the sealed electronic material is also referred to as a sealed body) is not particularly limited for its production other than using the liquid epoxy resin composition for a sealant of the present invention. For example, the same thing as the above is mentioned.

In this invention, an electronic material can be used individually or in combination of 2 types or more, respectively. Moreover, an electronic component device can be obtained by combining two or more electronic materials.
When two or more electronic materials are combined and sealed, the combination of electronic components is not particularly limited. For example, the combination of an element and a board | substrate, the combination of an element and an element, and the combination of a board | substrate and a board | substrate are mentioned.

When sealing two or more electronic materials in combination, as a method for sealing the electronic material, for example, a method of sealing the electronic material with an underfill agent after mounting, an underfill agent is placed on the electronic material first, and then separated. There is a method of mounting on an electronic material (underfill agent pre-attachment method).
In the electronic material of the present invention, when two or more electronic materials are sealed, the liquid epoxy resin composition for a sealant is used, for example, as an underfill agent used after mounting or in an underfill material advancement system Can be used as an underfill agent.

Next, the electronic component device of the present invention will be described.
The electronic component device of the present invention is
It is an electronic component device obtained by sealing a board | substrate and an element using the liquid epoxy resin composition for sealing agents of this invention.

The board | substrate and element used for the electronic component apparatus of this invention are not restrict | limited in particular. For example, a conventionally well-known thing is mentioned.
If the composition used for the electronic component apparatus of this invention is a liquid epoxy resin composition for sealing agents of this invention, it will not restrict | limit in particular.

  The electronic component device of the present invention is not particularly limited for its manufacture. For example, the following (1) and (2) are mentioned.

(1) An electronic component for manufacturing an electronic component device sealed by mounting the device on a substrate and then sealing the device and the substrate with the liquid epoxy resin composition for a sealant of the present invention. Device Manufacturing Method In the manufacturing method (1), the liquid epoxy resin composition for a sealant is used as an underfill agent for applying an electronic material after mounting.

(2) After applying the liquid epoxy resin composition for sealant of the present invention to one or both of the element and the substrate, sealing is performed by mounting the element on the substrate and bonding the element to the substrate. An electronic component device manufacturing method for manufacturing a stopped electronic component device may be mentioned.
The manufacturing method of (2) is based on an underfill agent prior method, and in the manufacturing method of (2), the liquid epoxy resin composition for sealant is used as an underfill agent for applying an electronic material before mounting. .

The electronic component device of the present invention will be described below with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
An electronic component device for sealing an element using the liquid epoxy resin composition for a sealant of the present invention as an underfill agent will be described with reference to FIGS.
FIG. 1 is a perspective view schematically showing that the liquid epoxy resin composition for a sealant of the present invention is applied as an underfill agent around an element after the element is mounted on a substrate.
FIG. 2 shows that the liquid epoxy resin composition for an encapsulant of the present invention as an underfill agent penetrates between the element and the substrate, and the underfill agent after curing becomes an encapsulant to form the electronic component device of the present invention. It is a perspective view which shows typically that is obtained.

In FIG. 1, a substrate 100 and an element 130 are connected by an electrode 110 included in the substrate 100 and a solder bump 140 included in the element 130, and the element 130 is mounted on the substrate 100.
The element is not particularly limited. For example, IC packages such as BGA and CSP are listed.
The underfill agent 120 is applied, for example, by applying (not shown) around the element 130 after mounting (not shown). At this time, it is preferable to provide a portion (not shown) where the underfill agent 120 is not applied to a part of the periphery of the element 130 from the viewpoint of preventing generation of bubbles. The underfill agent 120 can be applied along the first to third sides of the element 130 (not shown).

In FIG. 2, the underfill agent 220 can penetrate into the gap between the element 230 and the substrate 200 by capillary action.
The electronic component device 270 in which the underfill agent 220 has sufficiently penetrated into the gap between the element 230 and the substrate 200 can be cured at room temperature at room temperature. Thereafter, by heating the electronic component device 270, the underfill agent 220 is heat-cured (post-cured) to form the sealing body 220. The sealing body 220 can seal the element 230 to the substrate 200.
In this manner, an electronic component device 270 having the element 230 encapsulated using the liquid epoxy resin composition for encapsulant of the present invention as the underfill agent 220 is obtained.

An electronic component device for sealing an element using the liquid epoxy resin composition for an encapsulant of the present invention as an underfill agent in an underfill agent pre-adhering system will be described with reference to FIGS.
FIG. 3 is a perspective view schematically showing a substrate and an element to which the liquid epoxy resin composition for a sealant of the present invention is applied as an underfill agent before mounting.
FIG. 4 shows an electronic component device according to the present invention in which an element is mounted on a substrate to which the liquid epoxy resin composition for an encapsulant of the present invention as an underfill agent is applied, and the cured underfill agent becomes a sealed body. It is a perspective view which shows typically what is obtained.

In FIG. 3, the element 330 having the solder bump 340 and the active surface 350 is arranged so that the solder bump 340 and the active surface 350 face the substrate 300 and are aligned with the metallized pattern 310 of the solder bump 340. .
An underfill agent 320 is applied to the substrate 300 in advance.
In FIG. 4, the bumped element 430 is moved (not shown) and connected so as to be in intimate contact with the metallized pattern 410. One preferred embodiment is that the active surface 450 is completely covered by the underfill agent 420. In order to protect the active surface 450, the underfill agent 420 protrudes to the periphery of the element 430 and seals the periphery of the element 430.

In FIG. 4, the electronic component device 470 is heat-cured (post-cured) after room temperature curing or without room temperature curing (not shown), the underfill agent 420 becomes the sealing body 420, and the sealing body 420 is the element 430. Is sealed to the substrate 400.
In addition, in the underfill agent advance system, reflow can be performed at the time of heat curing, which is efficient.
In this way, an electronic component device 470 having an element 430 encapsulated using the liquid epoxy resin composition for encapsulant of the present invention as the underfill agent 420 in the underfill agent advancement system is obtained.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Evaluation About the obtained composition, the adhesive strength (initial stage, water resistance), adhesive strength retention, glass transition temperature, and room temperature curability were tested and evaluated by the following methods. The results are shown in Table 1.
(1) Adhesive strength (initial)
Two adherends (a glass epoxy having a length of 10 mm, a width of 50 mm, and a thickness of 1.6 mm) were prepared, and the entire surface of one of the adherends (hereinafter referred to as “the adherend A”). Then, each composition obtained by uniformly mixing the main agent and the curing agent shown in Table 1 was applied, and the remaining one adherend (hereinafter referred to as “adherence B”) was covered. It overlapped and bonded to the kimono A.
After superposing the adherends A and B as described above for 3 hours under a condition of 23 ° C. (room temperature curing), a treatment of heating at 150 ° C. for 1 hour (post-cure) is performed. A sample in which the adherends A and B were laminated via the composition was obtained. Let the obtained sample be a sample for adhesive strength.
A sample for adhesion strength was attached to a tensile testing machine, a tensile test was performed under the condition of a tensile speed of 1 mm / min, and the adhesive strength was measured. The obtained adhesive strength is defined as adhesive strength (initial).

(2) Adhesive strength (water resistance)
The adhesive strength sample obtained as described above is placed in a pressure cooker tester, placed under conditions of a temperature of 121 ° C. and a humidity of 100% RH for 24 hours, and then the adhesive strength sample is taken out from the pressure cooker tester. It was placed for 1 hour under the condition of ° C.
After 1 hour, the obtained sample for adhesion strength was attached to a tensile tester, a tensile test was performed under the condition of a tensile speed of 1 mm / min, and the adhesive strength was measured. The obtained adhesive strength is defined as adhesive strength (water resistance).

(3) Adhesive strength retention rate Adhesive strength retention rate was calculated by applying the values of adhesive strength (initial) and adhesive strength (water resistance) to the following equations.
Adhesive strength retention (%) = [Adhesive strength (water resistance) / Adhesive strength (initial)] × 100

(4) Glass transition temperature Using the sample for adhesive strength obtained by the method described in Adhesive strength (initial), the glass transition temperature of the cured product obtained by curing the composition is determined by dynamic viscoelasticity. The measurement was performed under the following measurement conditions using a measuring device (DMA).
<Measurement conditions>
Measurement temperature: room temperature to 220 ° C
・ Temperature increase rate: 5 ° C./min ・ Measurement frequency: 1 Hz, strain: 0.01%
As a result of the measurement, the temperature at the peak top of the obtained loss rigidity (G ″) was defined as the glass transition temperature.

(5) Room temperature curability Two PET films (1 cm in length and 1 cm in width) were prepared, and the entire surface of one of the PET films (hereinafter referred to as “PET film A”) is shown in Table 1. Each composition obtained by uniformly mixing the main agent and the curing agent shown is applied, and the remaining one PET film (hereinafter referred to as “PET film B”) is overlapped and bonded to the PET film A. It was.
The PET films A and B overlapped as described above were placed at 23 ° C., and the time until curing was measured.

2. Manufacture of composition (1) Manufacture of condensate (D) of mercapto group-containing silane compound 3-mercaptopropyltrimethoxysilane (trade name KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) 196 g, water 18 g, dibutyltin laurate 0 In the presence of 0.5 g, the mixture was stirred at room temperature in a nitrogen atmosphere for 15 hours, and after the completion of the reaction, methyl alcohol produced by the reaction was removed to obtain a condensate of a mercapto group-containing silane compound. Let the obtained condensate be an organic compound (B1).

(2) Production of Composition A composition was produced by using the components shown in Table 1 in the amounts (unit: parts by mass) shown in the same table.
In Table 1, the amount of the organic compound (B) is described in terms of the mercapto group equivalent to the epoxy group of the epoxy resin (A).
Further, the amount of the filler 1 is described as the weight percent of the filler 1 in the main agent, and the amount of the filler 2 is described as the weight percent of the filler 2 in the curing agent.
As the main agent, benzoxazine compound (C) was added to epoxy resin (A), and benzoxazine compound (C) was dissolved in epoxy resin (A) at 80 ° C. over 2 hours. After dissolution, heating is stopped and the mixture is placed at room temperature to bring the temperature of the mixture to about the same as room temperature. Then, the organic compound (B) is added to the mixture, and these are rotated at a rotational speed of 2 per minute using a defoaming stirrer. The mixture was stirred for 2 minutes under the condition of 1,000,000 times, and the main component components shown in Table 1 other than the epoxy resin (A), organic compound (B) and benzoxazine compound (C) were added thereto. A homogeneous main agent was obtained by stirring.
The curing agent was a uniform curing agent obtained by stirring the components shown in Table 1 with a defoaming stirrer.

Each component shown in Table 1 is as follows.
Epoxy resin (A1): triglycidyl-p aminophenol (trade name MY-0510, manufactured by Huntsman Advanced Materials)
Epoxy resin (A2): Bis-F type epoxy resin (trade name YDF-170, manufactured by Tohto Kasei Co., Ltd.)
Organic compound (B1): manufactured as described above Thiol compound: Dipentaerythritol hexa-3-mercaptopropionate (DPMP, manufactured by Sakai Chemical Co., Ltd.)
Benzoxazine compound (C1): a compound represented by the following formula (4) (trade name: benzoxazine Pd, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Benzoxazine compound 2: Compound represented by the following formula (5) (trade name Bis-S benzoxazine, manufactured by Konishi Chemical Industries)
Silane coupling agent 1: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (trade name KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)
Filler 1: Silica filler (trade name UF-103A, manufactured by Tokuyama Corporation)
Curing agent 1: 2,4,6-tris (dimethylaminomethyl) phenol (trade name DMP-30, manufactured by Seiko Chemical Co., Ltd.)
・ Imidazole: N-methylimidazole (manufactured by Kanto Chemical Co., Inc.)
Silane coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane (trade name KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.)
Filler 2: Fumed silica (trade name RY200S, manufactured by Nippon Aerosil Co., Ltd.)

As is clear from the results shown in Table 1, Comparative Examples 1 to 3, in which the amount of the epoxy resin (A) is 90% by mass or more of the total amount of the epoxy resin (A) and the benzoxazine compound (C), Adhesive strength (initial), adhesive strength (water resistance) and adhesive strength retention were poor, glass transition temperature was low, and room temperature curability was poor.
The comparative example 4 which does not contain an organic compound (B) was inferior to room temperature curability.
Comparative Example 5 containing a benzoxazine compound other than the benzoxazine compound (C) represented by the formula (1) is inferior to Example 1 in adhesive strength (initial, water resistance) and adhesive strength retention. The glass transition temperature was low.
Comparative Example 6 containing a benzoxazine compound other than the benzoxazine compound (C) represented by the formula (1) was inferior in adhesive strength (water resistance) and adhesive strength retention, and had a low glass transition temperature.
Comparative Example 7 containing a thiol compound other than the organic compound (B) was inferior in adhesive strength (initial, water resistance) and adhesive strength retention, and had a low glass transition temperature.
On the other hand, Examples 1-4 can be cured at room temperature, have a short room temperature curing time and excellent room temperature curability, and have an adhesive strength (initial and after water resistance test) and a retention rate of adhesive strength after the water resistance test. High adhesiveness, high glass transition temperature, excellent heat resistance, can be cured with high glass transition temperature and excellent adhesion by curing under low temperature and short post-curing conditions, Low viscosity and excellent workability.

Conventionally, a compound represented by the formula (5) has been proposed as a benzoxazine compound contained in a liquid epoxy resin composition for a sealant.
However, the present inventor has found that when the composition containing the benzoxazine compound represented by the formula (5) is post-cured under the condition of 150 ° C., the obtained cured product has a low glass transition temperature.
Moreover, it discovered that the hardened | cured material of the epoxy resin composition containing the oxazine compound which has the monocyclic oxazine proposed conventionally cannot express a high glass transition temperature by the postcure at 150 degreeC.
In contrast, the inventor of the present application has two benzoxazine rings in which the oxazine ring is condensed with the benzene ring, as in the benzoxazine compound (C) represented by the formula (1). The direction in which the nitrogen atoms of the two benzoxazine rings are more central to the benzoxazine compound than the benzene ring of the benzoxazine ring (the direction in which the methylene group is at the center of the benzoxazine compound (C). In this case, the benzoxazine compound (C), the epoxy resin (A), and the organic compound (B) are contained in an amount of the epoxy resin (A). The composition containing less than 90% by mass of the total amount of the epoxy resin (A) and the benzoxazine compound (C) at 150 ° C. under heating conditions In case of post-curing, the cured product obtained, even though the heating conditions are 0.99 ° C. and cold, it was found that the glass transition temperature of the cured product is very high.

  Thus, the glass transition temperature of the hardened | cured material obtained from the liquid epoxy resin composition for sealing agents of this invention becomes high although the temperature conditions in a postcure are as low as 150 degreeC.

FIG. 1 is a perspective view schematically showing that the liquid epoxy resin composition for a sealant of the present invention is applied as an underfill agent around an element after the element is mounted on a substrate. FIG. 2 shows that the liquid epoxy resin composition for an encapsulant of the present invention as an underfill agent penetrates between the element and the substrate, and the underfill agent after curing becomes an encapsulant to form the electronic component device of the present invention. It is a perspective view which shows typically that is obtained. It is a perspective view which shows typically the board | substrate to which the liquid epoxy resin composition for sealing agents of this invention is applied as an underfill agent before mounting, and an element. FIG. 4 shows that the electronic component device of the present invention is obtained by mounting an element as an underfill agent on a substrate to which the liquid epoxy resin composition for a sealant of the present invention is applied, and the cured underfill agent becomes a sealed body. It is a perspective view showing typically what is done.

Explanation of symbols

100, 200, 300, 400 Substrate 110, 210 Electrode 310, 410 Metallized pattern 120, 220, 320, 420 Underfill agent (later sealed)
130, 230, 330, 430 Element 140, 240, 340, 440 Solder bump 270, 470 Electronic component device 350, 450 Active surface

Claims (7)

An epoxy resin (A) having three or more epoxy groups in one molecule;
An organic compound (B) having two or more mercapto groups in one molecule;
A benzoxazine compound (C) represented by the following formula ( 4 ),
A liquid epoxy resin composition for a sealant, wherein the amount of the epoxy resin (A) is less than 90% by mass of the total amount of the epoxy resin (A) and the benzoxazine compound (C), and the organic compound A liquid epoxy resin composition for a sealant, wherein (B) is a condensate (D) of a mercapto group-containing silane compound.
The liquid epoxy resin composition for sealing agents according to claim 1, wherein the epoxy resin (A) is represented by the following formula (2).

(In the formula, each R ² is independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may have a substituent, and R ² may be the same or different. , N is an integer from 0 to 4.) The amount of mercapto group which the said organic compound (B) has is 0.1-0.5 equivalent with respect to the epoxy group which the said epoxy resin (A) has, For the sealing agent of Claim 1 or 2 Liquid epoxy resin composition. The sealed electronic material obtained by sealing an electronic material using the liquid epoxy resin composition for sealing agents in any one of Claims 1-3 . The electronic component apparatus obtained by sealing a board | substrate and an element using the liquid epoxy resin composition for sealing agents in any one of Claims 1-3 . After mounting an element on a board | substrate, the said component and the said board | substrate were sealed by sealing with the liquid epoxy resin composition for sealing agents in any one of Claims 1-3. A method for manufacturing an electronic component device. After apply | coating the liquid epoxy resin composition for sealing agents in any one of Claims 1-3 to one or both of an element and a board | substrate, the said element is mounted in the said board | substrate and the said element is set to the said board | substrate. An electronic component device manufacturing method for manufacturing an electronic component device sealed by bonding.