JP2021036020A - Epoxy resin composition - Google Patents

Abstract

To provide an epoxy resin composition which is cured in a short time even under low temperature conditions and has a reduced curing end temperature in a DSC chart while maintaining a pot life, and to provide a sealing material containing the same.SOLUTION: There is provided an epoxy resin composition including the following components (A) to (F): (A) at least one thiol-based curing agent containing a polyfunctional thiol compound having three or more thiol groups; (B) at least one polyfunctional epoxy resin; (C) a crosslinking density regulator comprising at least one monofunctional epoxy resin; (D) a curing catalyst; (E) a silica filler having an average particle size of 0.1 μm or more and 5.0 μm or less; and (F) triphenylsilanol.SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin composition, a sealing material containing the epoxy resin composition, a cured product obtained by curing the epoxy resin composition, and an electronic component containing the cured product.

Currently, for assembling and mounting electronic components used in semiconductor devices, for example, semiconductor chips, curable resin compositions, particularly adhesives and encapsulants containing epoxy resin compositions, are used for the purpose of maintaining reliability. Often used. In particular, in the case of a semiconductor device including parts that deteriorate under high temperature conditions, it is necessary to carry out all the manufacturing processes under low temperature conditions. Therefore, the adhesives and encapsulants used in the manufacture of such devices are required to exhibit sufficient curability even under low temperature conditions. At the same time, they are also required to cure in a short time in terms of production cost.

Epoxy resin compositions used in such adhesives and encapsulants for electronic components (hereinafter, may be simply referred to as "curable compositions") generally include epoxy resins and curing agents. Epoxy resins include various polyfunctional epoxy resins (epoxy resins having two or more epoxy groups). The curing agent contains a compound having two or more functional groups that react with the epoxy group in the epoxy resin. Among such curable compositions, those using a thiol-based curing agent as a curing agent are known to cure in a moderately short time even under low temperature conditions such as 0 ° C. to −20 ° C. The thiol-based curing agent includes a compound having two or more thiol groups, that is, a polyfunctional thiol compound. Examples of such a curable composition include those disclosed in Patent Document 1 or 2.

The epoxy resin composition gives a cured product having various properties depending on the composition. In this regard, it may not be preferable that _{the glass transition point (T g} ) is high depending on the purpose of use of the curable composition and the like. For example, this curable composition is used to join two parts, each made of a different material.

When the temperature around the assembly, which consists of two parts made of different materials joined together with an adhesive, changes, each of these parts is subjected to thermal stress according to the coefficient of thermal expansion of that material. .. This thermal stress is not uniform due to the difference in the coefficient of thermal expansion and is not offset, resulting in deformation of the assembly. The stress associated with this deformation particularly acts on the joints of the parts, that is, the cured product of the adhesive, and in some cases, cracks or the like are generated in the cured product. Such cracks are likely to occur, especially when the cured product is brittle and inflexible. Therefore, the adhesive for joining parts made of different materials needs to have sufficient flexibility (low elastic modulus) to follow the deformation of the assembly due to the thermal expansion of the parts after curing. For that purpose, it is required that _{the T g of the cured product is appropriately low.}

Patent Document 3, and cured in a short period of time even under low temperature conditions, the epoxy resin composition gives a low cured product T _g is described.

Japanese Unexamined Patent Publication No. 6-211969 Japanese Unexamined Patent Publication No. 6-21970 International Publication No. 2012/093510

However, the epoxy resin compositions described in Patent Documents 1 and 2 described above have a problem that the viscosity cannot be said to be sufficiently low for applications in electronic components. On the other hand, the epoxy resin composition described in Patent Document 3, although provide low cured product T _g, there is a shear strength problem of low of the cured product.

As an example of means for improving the mechanical strength of the cured product obtained by curing the curable resin composition, the addition of an appropriate filler (for example, silica filler) to the curable resin composition can be mentioned. The addition of the filler is also useful in terms of improving the thermal cycle resistance of the cured product. However, the application means may be limited due to the increase in viscosity of the curable resin composition accompanying the addition of the filler.

With the recent miniaturization of electronic components and modules, curable resin compositions are often applied to minute regions, and jet dispensers are often used for this purpose. For application by a jet dispenser, it is necessary that the viscosity of the curable resin composition is low to some extent, and in order to cope with a narrow gap, it is required to secure fluidity by reducing the viscosity. However, the curable resin composition whose viscosity has been increased by the addition of the filler has a problem that it is difficult to apply it by a jet dispenser and a desired fluidity cannot be obtained in a narrow gap.
In addition to these, it may be required to lower the curing end temperature in the DSC chart while maintaining the pot life of the curable resin composition.

The present invention has been made in view of the above problems, and an object of the present invention is that the viscosity is low, the curing end temperature in the DSC chart is lowered while maintaining the pot life, and the curing end temperature is lowered under low temperature conditions. However, it is an object of the present invention to provide an epoxy resin composition which cures in a short time _{and gives a cured product having a low glass transition point (T g) after curing and excellent shear strength, and a sealing material containing the same.} Another object of the present invention is to provide a cured product obtained by curing the epoxy resin composition or a sealing material. Yet another object of the present invention is to provide an electronic component containing the cured product.

Under such circumstances, the present inventors, cured in a short time even at low temperature, T _g is not less only after hardening, in order to develop a curable composition which gives a cured product having excellent shear strength , Diligently researched. As a result, surprisingly, as a component of the curable composition, a cross-linking density modifier containing a monofunctional epoxy resin was used in addition to a thiol-based curing agent and an epoxy resin, and the number (amount) of the thiol group and the epoxy group contained therein was used. and by those which satisfy the predetermined relationship, the initial T _g of the cured product obtained was found to be a reasonably low. The present inventors have also found that the addition of a specific filler can improve the share strength of the obtained cured product without excessively increasing the viscosity of the curable composition. Furthermore, the present inventors have found that by adding triphenylsilanol to the curable composition, the curing end temperature in the DSC chart can be lowered while maintaining the pot life. Based on the above new findings, the present invention has been completed.

That is, the present invention includes, but is not limited to, the following inventions.

1. 1. An epoxy resin composition having the following components (A) to (F):
(A) A thiol-based curing agent containing at least one polyfunctional thiol compound having three or more thiol groups;
(B) At least one polyfunctional epoxy resin;
(C) Crosslink density modifier (D) curing catalyst containing at least one monofunctional epoxy resin;
(E) Silica filler having an average particle size of 0.1 μm or more and 5.0 μm or less; and (F) Triphenylsilanol.
The ratio of the total epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalents for the component (A) ([epoxy functional group equivalents] / [thiol functional group equivalents]) is 0. .70 or more, 1.10 or less,
The amount (mol) of the component (C) is 25 to 70% of the total of the amount (mol) of the component (B) and the amount (mol) of the component (C).
An epoxy resin composition having a viscosity at 30 ° C. of 10 mPa · s or more and 2000 mPa · s or less.

2. The epoxy resin composition according to item 1 above, wherein the content of the component (E) is 15 to 50% by mass with respect to the total weight of the epoxy resin composition.

3. 3. The epoxy resin composition according to the above item 1 or 2, wherein the component (C) contains an aromatic monofunctional epoxy resin.

4. A sealing material containing the epoxy resin composition according to any one of items 1 to 3 above.

5. The epoxy resin composition according to any one of items 1 to 3 above, or a cured product obtained by curing the sealing material according to item 4 above.

6. An electronic component containing the cured product according to item 5 above.

It is a graph which shows the DSC measurement result of an epoxy resin composition.

Hereinafter, the present invention will be described in detail.

As described above, the epoxy resin composition (curable composition) of the present invention includes a thiol-based curing agent (component (A)), a polyfunctional epoxy resin (component (B)), and a cross-linking density adjusting agent (component (C)). )), Curing catalyst (component (D)), silica filler (component (E)) and triphenylsilanol (component (F)) are included as essential components. These components (A) to (F) will be described below.
In this specification, following the convention in the field of epoxy resin, a name including the term "resin" which usually refers to a polymer (particularly a synthetic polymer) with respect to the components constituting the epoxy resin composition before curing. May be used even though the component is not a polymer.

(1) Thiol-based curing agent (component (A))
The thiol-based curing agent (component (A)) used in the present invention contains 3 thiol groups that react with the epoxy groups in the polyfunctional epoxy resin (component (B)) and the cross-linking density adjusting agent (component (C)) described later. It contains at least one polyfunctional thiol compound having one or more. The component (A) preferably contains a trifunctional and / or tetrafunctional thiol compound. The thiol equivalent is preferably 90 to 150 g / eq, more preferably 90 to 140 g / eq, and even more preferably 90 to 130 g / eq. The trifunctional and tetrafunctional thiol compounds are thiol compounds having 3 and 4 thiol groups, respectively.

In a certain aspect of the present invention, the polyfunctional thiol compound includes a non-hydrolyzable polyfunctional thiol compound which does not have a hydrolyzable partial structure such as an ester bond from the viewpoint of improving the moisture resistance of the cured product. It is preferable to use the component (A). The non-hydrolyzable polyfunctional thiol compound is unlikely to be hydrolyzed even in a high temperature and high humidity environment.
In another aspect of the invention, component (A) comprises a thiol compound having an ester bond in the molecule and a thiol compound having no ester bond in the molecule. Further, in view of the low T _g of the component (A) preferably contains a free thiol resins urea bond.

Examples of hydrolyzable polyfunctional thiol compounds include trimethylpropanthrides (3-mercaptopropionate) (SC Organic Chemistry Co., Ltd .: TMMP), tris-[(3-mercaptopropionyloxy) -ethyl]-. Isocyanurate (manufactured by SC Organic Chemistry Co., Ltd .: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemistry Co., Ltd .: PEMP), tetraethylene glycol bis (3-mercaptopropionate) (SC organic) Chemical Co., Ltd .: EGFP-4), Dipentaerythritol Hexakis (3-mercaptopropionate) (SC Organic Chemical Co., Ltd .: DPMP), Pentaerythritol tetrakis (3-mercaptobutyrate) (Showa Denko Co., Ltd.) : Karenz MT (registered trademark) PE1), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ( Made by Showa Denko Co., Ltd .: Karenz MT (registered trademark) NR1) and the like can be mentioned.

A preferred non-hydrolyzable polyfunctional thiol compound that can be used in the present invention is the following formula (1):

(During the ceremony,
R ¹ and R ² are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenyl group.
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of a mercaptomethyl group, a mercaptoethyl group and a mercaptopropyl group).
It is a compound represented by. Examples of the compound represented by the formula (1) include 1,3,4,6-tetrax (2-mercaptoethyl) glycoluryl (trade name: TS-G, manufactured by Shikoku Kasei Kogyo Co., Ltd.), (1, 3,4,6-Tetrax (3-mercaptopropyl) glycoluryl (trade name: C3 TS-G, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 1,3,4,6-tetrakis (mercaptomethyl) glycoluryl, 1, 3,4,6-tetrakis (mercaptomethyl) -3a-methylglycoluryl, 1,3,4,6-tetrakis (2-mercaptoethyl) -3a-methylglycoluryl, 1,3,4,6-tetrakis ( 3-Mercaptopropyl) -3a-Methyl glycol uryl, 1,3,4,6-tetrakis (mercaptomethyl) -3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis (2-mercaptoethyl)- 3a, 6a-Dimethylglycollyl, 1,3,4,6-tetrakis (3-mercaptopropyl) -3a, 6a-dimethylglycoluryl, 1,3,4,6-tetrakis (mercaptomethyl) -3a, 6a- Diphenyl glycol uryl, 1,3,4,6-tetrakis (2-mercaptoethyl) -3a, 6a-diphenyl glycol uryl, 1,3,4,6-tetrakis (3-mercaptopropyl) -3a, 6a-diphenyl glycol Uril and the like are included. These may be used alone or in combination of two or more. Of these, 1,3,4,6-tetrakis (2-mercaptoethyl) glycol uryl may be used. And 1,3,4,6-tetrakis (3-mercaptopropyl) glycoluryl are particularly preferred.

Other preferred non-hydrolyzable polyfunctional thiol compounds that can be used in the present invention include the following formula (2):
(R ⁸ ) _m- A- (R ^7- SH) _n (2)
(During the ceremony,
A is a residue of a multivalent alcohol having n + m hydroxyl groups, and contains n + m oxygen atoms derived from the hydroxyl groups.
Each R ⁷ is independently an alkylene group having 1 to 10 carbon atoms.
Each R ⁸ is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
m is an integer greater than or equal to 0 and
n is an integer greater than or equal to 3
Each of the R ⁷ and R ⁸ is bonded to the A via the oxygen atom).
It is a compound represented by. Two or more compounds represented by the formula (2) may be used in combination. Examples of the compound represented by the formula (2) include pentaerythritol tripropanethiol (trade name: PEPT, manufactured by SC Organic Chemistry), pentaerythritol tetrapropanethiol and the like. Of these, pentaerythritol tripropanethiol is particularly preferable.

As the non-hydrolyzable polyfunctional thiol compound, a trifunctional or higher polythiol compound having two or more sulfide bonds in the molecule can also be used. Examples of such thiol compounds include 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, and 1,2,3-tris (3-mercapto). Bupropylthio) Propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7- Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiawndecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiawndecane, tetrakis (mercaptomethylthiomethyl) Methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercapto) Methylthio) ethane, 1,1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ) Etanthiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptan, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonan, 3-mercaptomethylthio- 1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonan, tris (2,2-bis (mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4) , 4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis (mercaptomethylthio) -1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3, 5,9,11,15,17-hexakis (mercaptomethylthio) -1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9- (2,2-bis (mercaptomethylthio) ) Ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1,11-dimercapto-2,5,7, 10-Tetrathiane undecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2,5,7,10,12,15-hexatiahexadecan, 8- [bis (Mercaptomethylthio) Methyl] -3,4,12,13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis [3 , 5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio] -1,3-dithiane, 4- [3,5-bis (mercaptomethylthio) -7-mercapto-2,6- Dithiane heptylthio] -6-mercaptomethylthio-1,3-dithiane, 1,1-bis [4- (6-mercaptomethylthio) -1,3-dithianilthio] -1,3-bis (mercaptomethylthio) propane, 1- [4- (6-mercaptomethylthio) -1,3-dithianylthio] -3- [2,2-bis (mercaptomethylthio) ethyl] -7,9-bis (mercaptomethylthio) -2,4,6 10-Tetrathiane undecane, 3- [2- (1,3-dithietanyl)] methyl-7,9-bis (mercaptomethylthio) -1,11-dimercapto-2,4,6,10-tetrathiandecan, 9 -[2- (1,3-dithiotanyl)] methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane , 3- [2- (1,3-dithianetanyl)] methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,4,6,10,12,16-hexatia Aliphatic polythiol compounds such as heptadecane; 4,6-bis [4- (6-mercaptomethylthio) -1,3-dithianylthio] -6- [4- (6-mercaptomethylthio) -1,3-dithianylthio]- 1,3-Dithiane, 4- [3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiandecyl] -5-mercaptomethylthio-1,3- Dithiolane, 4,5-bis [3,4-bis (mercaptomethylthio) -6-mercapto- 2,5-Dithietane hexylthio] -1,3-dithiolane, 4- [3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio] -5-mercaptomethylthio-1, 3-Dithiolane, 4- [3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl] -5-mercaptomethylthio-1,3- Dithiolane, 2- {bis [3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio] methyl} -1,3-dithietane, 2- [3,4-bis (mercaptomethylthio) ) -6-Mercapto-2,5-dithiahexylthio] mercaptomethylthiomethyl-1,3-dithietane, 2- [3,4,5,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5 7,10-Tetrathiaundecylthio] mercaptomethylthiomethyl-1,3-dithietane, 2- [3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4 7-Trithiaoctyl] mercaptomethylthiomethyl-1,3-dithietane, 4- {1- [2- (1,3-dithietane)]-3-mercapto-2-thiapropylthio} -5- [1,2 −Bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio] -1,3-dithiolane and other polythiol compounds having a cyclic structure can be mentioned.

(2) Epoxy resin (component (B))
The epoxy resin (component (B)) used in the present invention is not particularly limited as long as it contains at least one type of polyfunctional epoxy resin. Therefore, a conventionally used epoxy resin can be used as the component (B). As described above, the polyfunctional epoxy resin refers to an epoxy resin having two or more epoxy groups. In some aspects of the invention, component (B) comprises a bifunctional epoxy resin.
Polyfunctional epoxy resins are roughly classified into aliphatic polyfunctional epoxy resins and aromatic polyfunctional epoxy resins.

An example of an aliphatic polyfunctional epoxy resin is
-(Poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, poly Diepoxy resins such as tetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether;
-Triepoxy resins such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether;
-Alicyclic epoxy resins such as vinyl (3,4-cyclohexene) dioxide, 2- (3,4-epoxycyclohexyl) -5,1-spiro- (3,4-epoxycyclohexyl) -m-dioxane;
-Glysidylamine type epoxy resin such as tetraglycidylbis (aminomethyl) cyclohexane;
Hydant-in type epoxy resins such as -1,3-diglycidyl-5-methyl-5-ethylhydantin; and -1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldi Examples thereof include, but are not limited to, epoxy resins having a silicone skeleton such as siloxane.

In the above example, the "cyclohexane-type diglycidyl ether" means that two glycidyl groups are bonded to a divalent saturated hydrocarbon group having one cyclohexane ring as a parent structure via an ether bond. It means a compound having a structure. The "dicyclopentadiene-type diglycidyl ether" is a compound having a structure in which two glycidyl groups are bonded to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a parent structure via an ether bond. means. The aliphatic polyfunctional epoxy resin preferably has an epoxy equivalent of 90 to 450 g / eq. Further, as the cyclohexane type diglycidyl ether, cyclohexanedimethanol diglycidyl ether is particularly preferable.

In some aspects of the invention, component (B) comprises an aliphatic polyfunctional epoxy resin. When an aliphatic polyfunctional epoxy resin is used as the component (B), the component (A) to be combined preferably contains a trifunctional thiol compound or a tetrafunctional thiol compound having a glycoluril skeleton or an isocyanul skeleton. The ratio of the epoxy functional group equivalent of the aliphatic polyfunctional epoxy resin to the thiol compound having a glycoluril skeleton or isocyanul skeleton ([epoxy functional group equivalent] / [thiol functional group equivalent]) is 0.40 to 0.85. Is preferable.
In some aspects of the invention, component (A) comprises a trifunctional thiol compound or a tetrafunctional thiol compound having a glycoluril skeleton or an isocyanul skeleton. When a trifunctional thiol compound or a tetrafunctional thiol compound having a glycoluril skeleton or an isocyanul skeleton is used as the component (A), an epoxy resin having a cyclohexane type diglycidyl ether or a silicone skeleton is used as the component (B). Is preferable. In particular, it is preferable to use 1,4-cyclohexanedimethanol diglycidyl ether or 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane.
Further, in an aspect of the present invention, the component (A) does not have a glycoluril skeleton or an isocyanul skeleton, and is a trifunctional thiol compound or a tetrafunctional thiol compound (specifically, a polyether skeleton, a polysulfide skeleton, or a polyester). It contains a trifunctional thiol compound or a tetrafunctional thiol compound having a skeleton). In _{order to keep T g} in a desired range, the total amount of the aliphatic polyfunctional epoxy resin and the trifunctional thiol compound or the tetrafunctional thiol compound having no glycoluril skeleton or isocyanul skeleton in the epoxy resin composition is 20. It is preferably mass% or more and 55 mass% or less, and more preferably 20 mass% or more and 50 mass% or less.

The aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin having a structure containing an aromatic ring such as a benzene ring. Many of the epoxy resins that have been frequently used in the past, such as bisphenol A type epoxy resins, are of this type. An example of an aromatic polyfunctional epoxy resin is
-Bisphenol A type epoxy resin;
-P-Glysidyloxyphenyldimethyltrisbisphenol A Branched polyfunctional bisphenol A type epoxy resin such as diglycidyl ether;
-Bisphenol F type epoxy resin;
− Novolac type epoxy resin;
-Tetrabromobisphenol A type epoxy resin;
-Fluorene type epoxy resin;
-Biphenyl aralkyl epoxy resin;
Diepoxy resins such as -1,4-phenyldimethanol diglycidyl ether;
Biphenyl type epoxy resins such as -3,3', 5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl;
Glysidylamine-type epoxy resins such as −diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; and −naphthalene ring-containing epoxy resins are limited thereto. It is not something that is done. From the viewpoint of compatibility with the thiol compound, it is more preferable that the component (B) contains an aromatic polyfunctional epoxy resin rather than an aliphatic polyfunctional epoxy resin. As the aromatic polyfunctional epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin and glycidylamine type epoxy resin are preferable, and those having an epoxy equivalent of 90 to 200 g / eq are particularly preferable, and an epoxy equivalent is 110. Most preferably, it is ~ 190 g / eq.
When an aromatic polyfunctional epoxy resin is used as the component (B), the component (A) to be combined may be a trifunctional thiol compound or a tetrafunctional thiol compound having a polyether skeleton, a polysulfide skeleton, or a polyester skeleton. preferable. The ratio of the epoxy functional group equivalent of the aromatic polyfunctional epoxy resin to the thiol compound having a polyether skeleton, a polysulfide skeleton, or a polyester skeleton ([epoxy functional group equivalent] / [thiol functional group equivalent]) is 0.30. It is preferably ~ 1.10. When a trifunctional thiol compound or a tetrafunctional thiol compound having a polyether skeleton, a polysulfide skeleton, or a polyester skeleton is used as the component (A), the component (B) is a bisphenol A type epoxy resin or a bisphenol F type. It is preferable to use at least one of the epoxy resin and the naphthalene ring-containing epoxy resin.
Further, in order to set T _g in a desired range, a trifunctional thiol compound having an aromatic epoxy resin (monofunctional and polyfunctional aromatic epoxy resin) and a glycoluril skeleton or an isocyanul skeleton in the epoxy resin composition. Alternatively, the total amount of the tetrafunctional thiol compound is preferably 45% by mass or more and 80% by mass or less, and more preferably 50% by mass or more and 80% by mass or less.

(3) Crosslink density adjuster (component (C))
The cross-linking density adjusting agent (component (C)) used in the present invention is not particularly limited as long as it contains at least one monofunctional epoxy resin. The monofunctional epoxy resin is an epoxy resin having one epoxy group, and has been conventionally used as a reactive diluent for adjusting the viscosity of an epoxy resin composition. Monofunctional epoxy resins are roughly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the component (C) preferably has an epoxy equivalent of 180 to 400 g / eq. In the present invention, the component (C) preferably contains an aromatic monofunctional epoxy resin from the viewpoint of viscosity and low volatility. Further, it is preferable that the component (C) is substantially an aromatic monofunctional epoxy resin.

Examples of the aromatic monofunctional epoxy resin that can be contained in the component (C) include phenylglycidyl ether, cresylglycidyl ether, ps-butylphenylglycidyl ether, styrene oxide, p-tert-butylphenylglycidyl ether, o. -Phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide and the like can be mentioned, but the present invention is not limited thereto. Of these, p-tert-butylphenylglycidyl ether and phenylglycidyl ether are preferable, and p-tert-butylphenylglycidyl ether is particularly preferable. Examples of aliphatic monofunctional epoxy resins are n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4. -(2-Methyloxylanyl) -1-methylcyclohexane, 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane, neodecanoic acid glycidyl ester and the like. However, it is not limited to these.

(4) Curing catalyst (component (D))
The curing catalyst (component (D)) used in the present invention is not particularly limited as long as it is a curing catalyst of an epoxy resin (component (B)), and known ones can be used. The component (D) is preferably a latent curing catalyst. A latent curing catalyst is a compound that is inactive at room temperature, is activated by heating, and functions as a curing catalyst. For example, an imidazole compound that is solid at room temperature; reaction formation of an amine compound and an epoxy compound. Solid dispersion type amine adduct system latent curing catalyst such as substance (amine-epoxyadduct system); reaction product of amine compound and isocyanate compound or urea compound (urea type adduct system) and the like can be mentioned. By using the component (D), the epoxy resin composition of the present invention can be cured in a short time even under low temperature conditions.

Typical examples of commercially available latent curing catalysts are "Amicure PN-23" (trade name of Ajinomoto Fine Techno Co., Ltd.) and "Amicure PN-40" as amine-epoxyadduct type (amineadduct type). (Product name of Ajinomoto Fine Techno Co., Ltd.), "Amicure PN-50" (Product name of Ajinomoto Fine Techno Co., Ltd.), "Hardener X-3661S" (Product name of ACR Co., Ltd.), "Hardner" "X-3670S" (trade name of ACR Co., Ltd.), "Novacure HX-3742" (trade name of Asahi Kasei Co., Ltd.), "Novacure HX-3721" (trade name of Asahi Kasei Co., Ltd.), "Novacure HXA9322HP" (Product name of Asahi Kasei Co., Ltd.), "Novacure HXA3922HP" (Product name of Asahi Kasei Co., Ltd.), "Novacure HXA3932HP" (Product name of Asahi Kasei Co., Ltd.), "Novacure HXA5945HP" (Product name of Asahi Kasei Co., Ltd.), " "Novacure HXA9382HP" (trade name of Asahi Kasei Co., Ltd.), "Fujicure FXR1121" (trade name of T & K TOKA Co., Ltd.), etc., and "Fujicure FXE-1000" (T & K TOKA Co., Ltd.) as a urea type adduct system. ) Product name), "Fuji Cure FXR-1030" (T & K TOKA Co., Ltd. product name), etc., but are not limited to these. The component (D) may be used alone or in combination of two or more. As the component (D), a solid-dispersed amine adduct-based latent curing catalyst is preferable from the viewpoint of pot life and curability.

Some component (D) is provided in the form of a dispersion liquid dispersed in a polyfunctional epoxy resin. When using the component (D) in such a form, it should be noted that the amount of the polyfunctional epoxy resin in which it is dispersed is also included in the amount of the component (B) in the epoxy resin composition of the present invention. Should be. The component (D) is preferably contained in the epoxy resin composition in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass.

In the epoxy resin composition of the present invention, the number (amount) of thiol groups of the component (A) and the number (amount) of epoxy groups of the components (B) and (C) satisfy a predetermined relationship. Moreover, it is necessary that the amount (mol) of the component (B) and the amount (mol) of the component (C) satisfy a predetermined relationship. In particular,
(I) The ratio of the total epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalents for the component (A) ([epoxy functional group equivalents] / [thiol functional group equivalents]). Is 0.70 or more and 1.10 or less,
(Ii) The amount (mol) of the component (C) is 25 to 70% of the total of the amount (mol) of the component (B) and the amount (mol) of the component (C).

The thiol functional group equivalent means the total number of thiol groups of the thiol compound contained in the component or composition of interest, and the mass (g) of the thiol compound contained in the component or composition of interest is the thiol of the thiol compound. The quotient divided by the equivalent (if multiple thiol compounds are included, the sum of such quotients for each thiol compound). The thiol equivalent can be determined by the iodine titration method. This method is widely known and is disclosed, for example, in paragraph 0079 of Japanese Patent Application Laid-Open No. 2012-153794. If the thiol equivalent cannot be determined by this method, it may be calculated as a quotient obtained by dividing the molecular weight of the thiol compound by the number of thiol groups in one molecule of the thiol compound.

On the other hand, the epoxy functional group equivalent means the total number of epoxy groups of the epoxy resin (the components (B) and (C)) contained in the same component or composition, and the epoxy resin contained in the component or composition of interest. Is the quotient (g) divided by the epoxy equivalent of the epoxy resin (if a plurality of epoxy resins are included, the sum of such quotients for each epoxy resin). Epoxy equivalents can be determined by the method described in JIS K7236. If the epoxy equivalent cannot be determined by this method, it may be calculated as a quotient obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule of the epoxy resin.

The epoxy resin composition thiol-based curing agent is excessive to the epoxy resin, also as is the case in the curable composition in Patent Document 3, provide an initial T _g less cured product _{(T g} immediately after _curing) .. However, when the thiol-based curing agent is excessive with respect to the epoxy resin in this way, it does not react with the epoxy groups, and more thiol groups remain in the cured product without reacting. Therefore, the cured product epoxy resin composition described in Patent Document 3 provides the initial T _g is too low, the shear strength is lowered. In the present invention, the ratio of the total epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalents for the component (A) ([epoxy functional group equivalents] / [thiol functional group equivalents]). and 0.70 or more, by 1.10 or less, the crosslinking density becomes proper, the initial _{T g} of the cured product becomes possible to 65 ° C. or less 30 ° C. or higher. As a result, the share strength can be increased. Furthermore, the present inventors have disclosed in Patent Document 3 a curable composition that gives a cured product having a small change in _{Tg after a heat resistance test.} In the test (particularly at 85 ° C. for 100 hours in an 85% environment), it was found that after the test, new cross-linking due to excess thiol groups may occur. The progress of this cross-linking is milder than that when the epoxy resin is excessive with respect to the thiol-based curing agent, but it results in an increase in _{T g.} Therefore, in the present invention, the ratio of the total epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalents for the component (A) ([epoxy functional group equivalents] / [thiol functional groups] / [thiol functional groups] The base equivalent]) is 0.70 or more and 1.10 or less, preferably 0.75 or more and 1.10 or less, and more preferably 0.80 or more and 1.05 or less. In the curable composition of the present invention, since the epoxy group contained in the component (C) that reduces the unreacted thiol group is present, most of the unreacted thiol group disappears as a result of the reaction between them. To do. The polyfunctional epoxy resin contained in the component (B) has a function of linking two molecules of the polyfunctional thiol compound contained in the component (A) to extend a polymer chain or form a crosslink between the polymer chains. Has. However, since the monofunctional epoxy resin contained in the component (C) does not have such a function, a new _{reaction that raises the T g of the cured product by the reaction between the components (A) and (C).} It is possible to suppress the occurrence of cross-linking. Therefore, the curable composition is cured to provide the present invention, because a low content of functional groups capable of forming a new cross-linking, even if a long time elapses after curing, a T _g associated with the formation of a new cross-linking Almost no rise is observed.
The cured product provided by the epoxy resin composition of the present invention is, in particular, LCP (liquid crystal polymer), PC (polycarbonate), PBT (polybutylene terephthalate), SUS, alumina, and nickel (including those having a nickel-plated surface). , Exhibits excellent share strength for adherends selected from glass. These may be surface-treated with plasma or the like. As used herein, the term "share strength" typically means the share strength when these adherends are made of these materials.

The ratio of the total epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalent for the component (A) ([epoxy functional group equivalent] / [thiol functional group equivalent]) is 0. When it is .70 or more and 1.10 or less (the relationship (i) is satisfied), both the epoxy group and the thiol group in the same composition are involved in the reaction between the epoxy group and the thiol group. Since the proportion of thiol is more than a certain amount, the characteristics of the obtained cured product are appropriate. If the ratio is less than 0.70, the thiol groups are excessive with respect to the epoxy groups, so that the number of thiol groups remaining in the cured product without reaction increases, and the curing accompanying the reaction between such thiol groups It becomes difficult to suppress the increase in T _{g of an object.} On the other hand, when the above ratio exceeds 1.10, the epoxy group is excessive with respect to the thiol group, so that in addition to the reaction between the epoxy group and the thiol group, the reaction between the excessive epoxy groups (homopolymerization) occurs. proceed. As a result, intermolecular cross-linking is formed in the obtained cured product by both of these reactions, so that the cross-linking density becomes too high and T _g increases. Alternatively, low temperature curing such as 1 hour at 80 ° C. becomes difficult.

The relationship (ii) is that 25 to 70% of all the epoxy resin molecules contained in the epoxy resin composition of the present invention are monofunctional epoxy resin (component (C)) molecules, and the monofunctionality thereof. By reacting with the epoxy resin, the cross-linking points of the component (A) containing the thiol compound having three or more thiol groups are reduced. For example, in the case of a thiol compound having four thiol groups, a bifunctional thiol compound or a trifunctional thiol compound can be used. Means to use as if there were. If the amount ratio exceeds 70%, the amount of the polyfunctional epoxy resin as a cross-linking component is too small, so that the obtained cured product may exhibit properties like a thermoplastic resin such that it melts at a high temperature. is there. On the other hand, if the amount ratio is less than 25%, the amount of the polyfunctional epoxy resin as a cross-linking component is too large, so that the obtained cured product has excessive intermolecular cross-linking due to the reaction of the components (A) and (B). It may be formed and the crosslink density becomes too high, resulting in an excessive increase in _{T g of the cured product.}
The amount (mol) of the component (C) is preferably 30 to 70%, more preferably 33 to 70, with respect to the total of the amount (mol) of the component (B) and the amount (mol) of the component (C). %.
By satisfying the relationship between (i) and (ii), the thiol group of the component (A) that did not react with the component (B) reacts with the component (C), and the unreacted thiol group remaining in the cured product remains. Since the amount is reduced, the characteristics of the obtained cured product become appropriate.

Further, in the present invention, since a certain amount of the component (C) is essential, the viscosity of the epoxy resin composition can be reduced. As described above, since the epoxy resin composition of the present invention is intended to be applied by a jet dispenser, the viscosity at the nozzle tip temperature is high so that the epoxy resin composition can be discharged at high speed from micropores having an inner diameter of several hundred μm. It is preferably low. Further, it is preferable that the epoxy resin composition after discharge has fluidity. Therefore, the viscosity of the epoxy resin composition at 30 ° C. is 2000 mPa · s or less, preferably 1000 mPa · s or less, and more preferably 800 mPa · s or less. From the viewpoint of handling, the viscosity of the epoxy resin composition at 30 ° C. is preferably 10 mPa · s or more, and more preferably 100 mPa · s or more. In some embodiments, the epoxy resin composition of the present invention has a viscosity at 30 ° C. of 10 mPa · s or more and 2000 mPa · s or less, preferably 100 mPa · s or more and 2000 mPa · s or less. In the present invention, the viscosity can be determined according to Japanese Industrial Standard JIS K6833. Specifically, the viscosity at 30 ° C. can be obtained by reading the value 1 minute after the start of measurement at a rotation speed of 1 rpm using an E-type viscometer. There are no particular restrictions on the equipment, rotor, or measurement range used. If the viscosity at 30 ° C. is below the measurement viscosity detection limit of the E-type viscometer at a rotation speed of 1 rpm, it can be obtained by measuring at an appropriate rotation speed such as 2.5 rpm, 5 rpm, or 10 rpm.
It is more preferable that the epoxy resin composition of the present invention has a viscosity at 60 ° C. of 300 mPa · s or less. If the rotation speed is small, the measurement viscosity detection limit of the E-type viscometer is reached. Therefore, the viscosity at 60 ° C. is preferably measured at 50 rpm or an appropriate rotation speed.

(5) Silica filler (component (E))
The epoxy resin composition of the present invention contains a silica filler (component (E)). This improves the thermal resistance of the cured product obtained by curing the epoxy resin composition. The addition of a filler such as a silica filler improves the thermal cycle resistance because the coefficient of linear expansion of the cured product is reduced, that is, the expansion and contraction of the cured product due to the thermal cycle is suppressed.

In the present invention, a silica filler having an average particle size of 5.0 μm or less is used. In the present specification, the average particle size refers to a volume-based median diameter (d ₅₀ ) measured by a laser diffraction method in accordance with ISO-13320 (2009) unless otherwise specified. The average particle size of the silica filler is preferably 4.0 μm or less, more preferably 3.0 μm or less. When the average particle size is more than 5.0 μm, the silica filler tends to settle. Further, coarse particles are likely to be contained, the nozzle of the jet dispenser is worn, and the discharged resin composition is likely to be scattered outside the desired region. The lower limit of the average particle size is not particularly limited. However, if the average particle size is less than 0.1 μm, the viscosity of the epoxy resin composition tends to increase, so that it is preferably 0.1 μm or more, and more preferably 0.2 μm or more. In some embodiments, the average particle size of the silica filler used in the present invention is 0.1 μm or more and 5.0 μm or less, preferably 0.2 μm or more and 3.0 μm or less.

The content of the silica filler in the epoxy resin composition of the present invention is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, and 20 to 20% by mass with respect to the total weight of the epoxy resin composition. It is more preferably 40% by mass. If the content of the silica filler is too low, the thermal cycle resistance becomes insufficient. If the content is too high, the viscosity of the epoxy resin composition becomes too high, making it difficult to apply in a jet dispenser.

The silica filler may be used in combination with other fillers. The other filler is not particularly limited, and various fillers can be used. Specific examples of other fillers include alumina fillers, talc fillers, calcium carbonate fillers, polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, styrene fillers and the like.
Further, in the present invention, the silica filler and other fillers may be surface-treated.

(6) Triphenylsilanol (component (F))
The epoxy resin composition of the present invention has the following formula:

Contains triphenylsilanol (component (F)), which is indicated by.
In some embodiments, the effect of triphenylsilanol contained in the epoxy resin of the present invention can reduce the curing end temperature when curing the epoxy resin composition while maintaining the pot life. This effect can be confirmed, for example, from the shape of the exothermic peak obtained by measuring the epoxy resin composition by differential scanning calorimetry (DSC).

In the above DSC measurement, since there is a correlation between the amount of heat of reaction when the epoxy resin composition is cured and the degree of curing, the degree of curing at a given temperature can be calculated. If the rise of the curve corresponding to the heat generation due to curing (curing start temperature) shifts to a low temperature, the polymerization reaction is relatively likely to occur even in the low temperature range, and the pot life may be shortened. Further, in the present application, as a guideline for the temperature at which the epoxy resin composition is completely cured (curing end temperature), a temperature at which the heat flow first becomes 1/10 of the heat flow at the exothermic peak in a temperature range higher than the exothermic peak temperature is adopted. .. Therefore, when the additive in the epoxy resin composition is added, if the curing start temperature does not shift to the low temperature side so much and the difference between the exothermic peak temperature and the curing end temperature becomes small, the pot life is not shortened. It is expected that the curing will be completed promptly and the reliability of the cured product will be improved.

In the present application, the effect of triphenylsilanol (component (F)) is specifically that when triphenylsilanol is added to the epoxy resin composition, the curing start temperature does not change significantly, but the exothermic peak temperature and the effect end. This can be confirmed by reducing the temperature difference. Further, in the above, the conditions for DSC measurement can be obtained, for example, in the range of room temperature to 130 ° C. and the heating rate of 1 to 50 ° C./min. The preferred rate of temperature rise is 10 ° C./min.
The content of triphenylsilanol in the epoxy resin composition of the present invention is preferably 0.1 to 10% by mass, preferably 0.3 to 7% by mass, based on the total weight of the epoxy resin composition. More preferably, it is more preferably 0.5 to 6% by mass. If the content of triphenylsilanol is too low, the reduction in curing end temperature may be insufficient. If the content is too high, the viscosity of the epoxy resin composition becomes too high, which may make it difficult to apply with a jet dispenser, or the cured product may become brittle.

If desired, the curable composition of the present invention may contain any component other than the above components (A) to (F), for example, those described below, if necessary.

-Stabilizer A stabilizer can be added to the epoxy resin composition of the present invention if desired. Stabilizers can be added to the epoxy resin compositions of the present invention to improve their storage stability and prolong pot life. Various known stabilizers can be used as stabilizers for one-component adhesives containing epoxy resin as the main ingredient, but liquid boric acid ester compounds, aluminum chelates and aluminum chelate are available because of their high effect of improving storage stability. At least one selected from the group consisting of organic acids is preferred.

Examples of liquid borate compounds include 2,2'-oxybis (5,5'-dimethyl-1,3,2-oxabolinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, Tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris ( 2-Ethylhexyloxy) borate, bis (1,4,7,10-tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) ) Borate, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate and the like. Since the liquid boric acid ester compound is liquid at room temperature (25 ° C.), the viscosity of the compound can be kept low, which is preferable. As the aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used.

When a stabilizer is added, the amount added is preferably 0.01 to 30 parts by mass, preferably 0.05 to 25 parts by mass, based on 100 parts by mass of the total amount of the components (A) to (F). Is more preferable, and 0.1 to 20 parts by mass is further preferable.

-Coupling agent A coupling agent can be added to the epoxy resin composition of the present invention if desired. The addition of a coupling agent, particularly a silane coupling agent, is preferable from the viewpoint of improving the adhesive strength. As the coupling agent, various silane coupling agents such as epoxy type, amino type, vinyl type, methacrylic type, acrylic type and mercapto type can be used. Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and 3-triethoxysilyl-N- (1,3-dimethyl-butylidene). Propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 8-glycidoxyoctyl Examples thereof include trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyandiapropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

In the epoxy resin composition of the present invention, the amount of the coupling agent added is 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (F) from the viewpoint of improving the adhesive strength. It is preferably 0.1 to 30 parts by mass, and more preferably 0.1 to 30 parts by mass.

-Other Additives The epoxy resin composition of the present invention contains, if desired, other additives such as carbon black, titanium black, ion trapping agent, leveling agent, and oxidation, as long as the gist of the present invention is not impaired. Inhibitors, antifoaming agents, rocking agents, viscosity modifiers, flame retardants, colorants, solvents and the like can be added. The type and amount of each additive are the same as usual.

The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, the components (A)-(F) and, if desired, other additives are introduced into a suitable mixer simultaneously or separately, and if necessary, mixed by stirring while melting by heating. The epoxy resin composition of the present invention can be obtained by making the composition uniform. The mixer is not particularly limited, but a Raikai machine equipped with a stirring device and a heating device, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. Moreover, you may use these devices in combination as appropriate.

The epoxy resin composition thus obtained is thermosetting, and under the condition of a temperature of 80 ° C., it is preferably cured within 5 hours, and more preferably within 1 hour. Further, it is possible to cure at a high temperature of 150 ° C. for several seconds at a high temperature and in an ultra-short time. When the curable composition of the present invention is used in the manufacture of an image sensor module containing parts that deteriorate under high temperature conditions, the composition is thermoset at a temperature of 60 to 90 ° C. for 30 to 120 minutes, or 120. It is preferably thermoset at a temperature of ~ 200 ° C. for 1 to 300 seconds.

The epoxy resin composition of the present invention cures in a short time even at low temperature, T _g gives low cured product. The cured product of the epoxy resin composition of the present invention _{preferably has a T g} of 65 ° C. or lower, more preferably 60 ° C. or lower, and even more preferably 50 ° C. or lower. Further, from the viewpoint of adhesion, the T _g of the cured product is preferably 30 ° C. or higher, more preferably 32 ° C. or higher. In the present invention, T _g is used in the range of −20 ° C. to 110 ° C., frequency 1 to 10 Hz, heating rate 1 to 10 ° C./min, strain amplitude 5 μm, and tension using a dynamic thermomechanical measuring device (DMA). It can be obtained by law. The preferred frequency is 10 Hz, and the preferred heating rate is 3 ° C./min. T _g is obtained from the peak temperature of the loss tangent (tan δ) obtained from the loss elastic modulus (E ″) / storage elastic modulus (E ′).

The epoxy resin composition of the present invention is, for example, a semiconductor device including various electronic components, an adhesive for fixing, joining or protecting the components constituting the electronic components, a sealing material, a dam agent, or a raw material thereof. Can be used as.

The present invention also provides a sealing material containing the epoxy resin composition of the present invention. The encapsulant of the present invention is suitable as, for example, a fill material for protecting or fixing modules, electronic components, and the like.
Further, in the present invention, a cured product obtained by curing the epoxy resin composition or the encapsulant of the present invention is also provided.
The present invention also provides electronic components containing the cured product of the present invention.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and% by mass unless otherwise specified.

Reference Examples 1 to 14, Examples 15 to 17, Comparative Examples 1 to 5
An epoxy resin composition was prepared by mixing a predetermined amount of each component using a three-roll mill according to the formulation shown in Tables 1 and 2. In Tables 1 and 2, the amount of each component is represented by parts by mass (unit: g).

・ Thiol-based curing agent (component (A))
The compounds used as the component (A) in Examples and Comparative Examples are as follows.
(A-1): 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Shikoku Kasei Kogyo Co., Ltd., thiol equivalent: 100)
(A-2): Pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMP, manufactured by SC Organic Chemistry Co., Ltd., thiol equivalent: 122)
(A-3): Trimethylolpropanetris (3-mercaptopropionate) (trade name: TMMP, manufactured by SC Organic Chemistry Co., Ltd., thiol equivalent: 133)

-Epoxy resin (component (B))
The compounds used as the component (B) in Examples and Comparative Examples are as follows.
(B-1): Bisphenol F type epoxy resin (trade name: YDF-8170, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent: 159)
(B-2): Bisphenol F type epoxy resin / bisphenol A type epoxy resin mixture (trade name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165)
(B-3): 1,4-Cyclohexanedimethanol diglycidyl ether (trade name: CDMDG, manufactured by Showa Denko KK, epoxy equivalent: 133)
(B-4): 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane (trade name: TSL9906, manufactured by Momentive Performance Materials Japan LLC, Epoxy equivalent: 181)

-Crosslink density modifier (component (C))
The compounds used as the component (C) in Examples and Comparative Examples are as follows.
(C-1): p-tert-butylphenylglycidyl ether (trade name: ED509S, manufactured by ADEKA Corporation, epoxy equivalent: 205)
(C-2): Phenylglycidyl ether (trade name: Denacol EX141, manufactured by Nagase ChemteX Corporation, epoxy equivalent: 151)
(C-3): 2-Ethylhexyl glycidyl ether (trade name: Denacol EX121, manufactured by Nagase ChemteX Corporation, epoxy equivalent: 187)

-Curing catalyst (component (D))
The compounds used as the component (D) in Examples and Comparative Examples are as follows.
(D-1) Amine-Epoxy Adduct System Latent Curing Catalyst 1 (Product Name: Fuji Cure FXR1121, manufactured by T & K TOKA Co., Ltd.)
(D-2) Amine-Epoxy Adduct System Latent Curing Catalyst 2 (Product Name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation)

The latent curing catalyst (D-2) is a dispersion in which fine-grained latent curing catalyst is dispersed in an epoxy resin (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (epoxy equivalent: 170)). It is provided in the form of a liquid (latent curing catalyst / mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin = 33/67 (mass ratio)). Tables 1 and 2 (D-2) are parts by mass of the dispersion containing the latent curing catalyst. The epoxy resin constituting this dispersion is treated as forming a part of the component (B). Therefore, in Tables 1 and 2, "(B) / (A) (functional group equivalent ratio)", "{(B) + (C)} / (A) (functional group equivalent ratio)", "(C) / The amount of the epoxy resin in (D-2) is included in (B) of "{(B) + (C)} (molar number ratio)".

-Silica filler (component (E))
The compounds used as the component (E) in Examples and Comparative Examples are as follows.
(E-1) Silica filler 1 (trade name: SE2300, average particle size 0.6 μm, manufactured by Admatex Co., Ltd.)
(E-2) Silica filler 2 (trade name: SO-E5, average particle size 2.0 μm, manufactured by Admatex Co., Ltd.)
(E'-1): Silica filler 1'(trade name: FB-7SDX, average particle size 5.5 μm, manufactured by Denka Co., Ltd.)

(F): Triphenylsilanol (trade name: TSL8161D, manufactured by Momentive Performance Materials Japan LLC)

In Examples and Comparative Examples, the properties of the epoxy resin composition and the cured product were measured as follows.
<Viscosity of curable composition>
Viscosity of epoxy resin composition using E-type viscometer manufactured by Toki Sangyo Co., Ltd. (model number: TVE-22H, rotor name: 1 ° 34'x R24) (set to an appropriate measurement range (H, R or U)) (Unit: mPa · s) was read within 1 hour from the preparation at 30 ° C. at a rotor rotation speed of 1 rpm and 1 minute after the start of measurement. The results are shown in Tables 1 and 2. When measured at a rotor rotation speed of 1 rpm, if the viscosity is less than 640 mPa · s, it is out of the measurement range. Therefore, Tables 1 and 2 describe “<640” indicating that the viscosity is at least less than 640 mPa · s. .. The viscosity needs to be 2000 mPa · s or less.

(Preparation of cured product)
The resin compositions of Reference Examples 1 to 14, Examples 15 to 17, and Comparative Examples 1 to 5 were each heated at 80 ° C. for 120 minutes to obtain a cured product.

<Glass transition temperature of cured product (T _g )>
It was measured according to Japanese Industrial Standard JIS C6481. Specifically, first, a Teflon (registered trademark) sheet was attached to the surface of a glass plate having a thickness of 3 mm, and a spacer (heat resistant tape) was laminated on the Teflon (registered trademark) sheet so that the film thickness when cured was 400 ± 150 μm. Things) were placed in two places. Next, a resin composition is applied between the spacers, sandwiched between other glass plates with a Teflon (registered trademark) sheet on the surface so as not to entrap air bubbles, and cured at 80 ° C. for 120 minutes to obtain a cured product. It was. Finally, this cured product was peeled off from a glass plate to which a Teflon (registered trademark) sheet was attached, and then cut to a predetermined size (10 mm × 40 mm) with a cutter to obtain a test piece. The cut end was smoothed with sandpaper. Using a dynamic thermomechanical measuring device (DMA) (DMS6100 manufactured by Hitachi High-Tech Science Corporation), this cured product was subjected to a range of -20 ° C to 110 ° C, a frequency of 10 Hz, a heating rate of 3 ° C / min, and a strain amplitude of 5 μm. , The initial T _g was measured by the tensile method. T _g was determined from the peak temperature of tan δ determined from E'' / E'.

<Share strength of cured product>
The resin composition was applied on a SUS plate to a size of φ2 mm and a thickness of 125 μm by stencil printing, and an alumina chip having a thickness of 3.2 mm × 1.6 mm × 0.45 mm was placed on the applied resin composition. A test piece was prepared by laminating and curing the resin composition under a light load. The curing conditions at this time were 80 ° C. and 120 minutes in a blower dryer. The alumina chip on the SUS plate was pierced from the side surface with a bond tester (manufactured by Dage, series 4000) at 23 ° C., and the stress (N) when the alumina chip was peeled off was measured. This measurement was performed on seven test pieces, and the average value of the obtained stresses was calculated. This average value is shown in Tables 1 and 2 as the share strength (unit: N / Chip) of the cured product. The share strength is preferably 50 N / Chip or more, and more preferably 80 N / Chip or more.

<Presence or absence of coarse particles in the curable composition>
Relatively large particles (coarse) detected in the curable composition using a grind gauge (model: No. 527 particle size measuring instrument [small size], groove depth 0 to 50 μm, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) The particle size of the grains) was measured. The results are shown in Tables 1 and 2. A curable composition in which coarse particles having a particle size of 15 μm or more were detected was evaluated as x.

<Confirmation of curability>
DSC measurement of the resin compositions of Reference Example 9 and Examples 15 to 17 was performed. The DSC measurement was performed using a differential scanning calorimetry device (DSC 204 F1 Phoenix (registered trademark)) (manufactured by NETZSCH) in the range of room temperature to 150 ° C. and a heating rate of 10 ° C./min. The results are shown in Table 3 and FIG.

In Tables 1 and 2, the functional group equivalent ratios ((B) + (C)) / (A), (B) / (A) and (C) / (A) are the components (A), (B) and It is a value calculated from the mass of (C) and the corresponding thiol equivalent (or epoxy equivalent). These functional group equivalent ratios are more accurate than the functional group equivalent ratios obtained from the thiol functional group equivalents (or epoxy functional group equivalents) of the fractionated components (A), (B) and (C) in the table. Is.

As is clear from Tables 1 and 2, the curable compositions of Reference Examples 1 to 14 and Examples 15 to 17 have a low viscosity of 2000 mPa · s or less, and are adhesives and the like for application to minute regions by a jet dispenser. It gives a cured product that is suitable for use and exhibits high shear strength.
Further, as is clear from Table 3 and FIG. 1, Examples 15 to 17 containing the component (F) have a heat generation peak temperature based on curing and this heat generation as compared with Reference Example 9 not containing the component (F). Since the difference from the temperature at which the heat flow first becomes 1/10 of the heat flow at the exothermic peak (curing end temperature) in the higher temperature region than the peak temperature is small, the reliability of the cured product is improved. Furthermore, in Examples 15 to 17 containing the component (F), the curing start temperature (rising of the curve corresponding to heat generation) is almost shifted to a lower temperature than in Reference Example 9 not containing the component (F). It can also be seen that the pot life is not shortened.
On the other hand, the curable composition of Comparative Example 1 using a silica filler having an average particle size of 5.0 μm or more gives a cured product having a low viscosity and a sufficient shear strength, but has coarse particles. However, it is not suitable for application with a jet dispenser.
The curable composition of Comparative Example 2 in which the ratio of the total epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalents for the component (A) was less than 0.70 has a high viscosity. In addition, the cured product provided by this product showed excellent shear strength numerically, but showed thermoplasticity, and it was considered difficult to use it at 70 ° C. or higher.
The curable composition of Comparative Example 3 in which the ratio of the total epoxy functional group equivalents for components (B) and (C) to the thiol functional group equivalents for component (A) is greater than 1.10. The cured product was brittle, _{and a test piece for T g} measurement could not be prepared. Therefore, the shear strength was not measured.
The curable composition of Comparative Example 4 in which the amount (mol) of the component (C) is less than 25% of the total of the amount (mol) of the component (B) and the amount (mol) of the component (C) has a viscosity. It is expensive and not suitable for application with a jet dispenser.
In Comparative Example 5 in which the amount (mol) of the component (C) is more than 70% of the total of the amount (mol) of the component (B) and the amount (mol) of the component (C), the cured product provided by the component (C) is brittle. A test piece for T _g measurement could not be prepared. Therefore, the shear strength was not measured.
As described above, it is difficult to apply any of Comparative Examples 1 to 5 as an adhesive or the like for application to a minute region by a jet dispenser.

The epoxy resin composition of the present invention has a lower curing end temperature on the DSC chart while maintaining the pot life, and cures in a short time even under low temperature conditions to give a cured product. The cured product showed a low T _g, has appropriate flexibility and flexibility. Therefore, this cured product can follow the deformation due to thermal expansion of the parts in the assembly formed by joining a plurality of parts made of different materials. Moreover, this cured product has excellent share strength. Further, the epoxy resin composition of the present invention exhibits a low viscosity even though a silica filler is added to improve the shear strength, and is suitable for application to a minute region by a jet dispenser or the like. Therefore, the epoxy resin composition of the present invention is particularly useful as an adhesive, a sealing material, a dam agent, or the like for semiconductor devices and electronic parts that are assembled by joining a plurality of parts made of different materials.

Claims (6)

An epoxy resin composition having the following components (A) to (F):
(A) A thiol-based curing agent containing at least one polyfunctional thiol compound having three or more thiol groups;
(B) At least one polyfunctional epoxy resin;
(C) Crosslink density modifier (D) curing catalyst containing at least one monofunctional epoxy resin;
(E) Silica filler having an average particle size of 0.1 μm or more and 5.0 μm or less; and (F) Triphenylsilanol.
The ratio of the total epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalents for the component (A) ([epoxy functional group equivalents] / [thiol functional group equivalents]) is 0. .70 or more, 1.10 or less,
The amount (mol) of the component (C) is 25 to 70% of the total of the amount (mol) of the component (B) and the amount (mol) of the component (C).
An epoxy resin composition having a viscosity at 30 ° C. of 10 mPa · s or more and 2000 mPa · s or less. The epoxy resin composition according to claim 1, wherein the content of the component (E) is 15 to 50% by mass with respect to the total weight of the epoxy resin composition. The epoxy resin composition according to claim 1 or 2, wherein the component (C) contains an aromatic monofunctional epoxy resin. A sealing material containing the epoxy resin composition according to any one of claims 1 to 3. The epoxy resin composition according to any one of claims 1 to 3, or a cured product obtained by curing the sealing material according to claim 4. An electronic component containing the cured product according to claim 5.