JP2021036021A - Epoxy resin composition - Google Patents

Abstract

To provide an epoxy resin composition that is cured in a short time even under low-temperature conditions to yield a cured product having a low glass transition point (Tg) and a high pull strength; a sealing material containing the same; a cured product obtained by curing the composition; and an electronic component including the cured product.SOLUTION: As a component of the curable composition, a crosslinking density regulator containing an aromatic monofunctional epoxy resin in addition to a thiol-based curing agent and an epoxy resin is used, and the physical properties values of a cured product provided by the curable composition are adjusted so as to be within a predetermined range.SELECTED DRAWING: Figure 1

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.

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.}

International Publication No. 2012/093510

However, the epoxy resin composition described in Patent Document 1 described above, while indicating low temperature curability T _g and excellent low enough, the present inventors that the pull strength is a problem that low found. Electronic components may be required to have drop impact resistance, but in order to improve drop impact resistance, it is desirable to improve the pull strength of the adhesive.
The present invention has been made in view of the above problems, and an object of the present invention is to cure in a short time even under low temperature conditions, have a low glass transition point (T _g ), and have high pull strength. It is an object of the present invention to provide an epoxy resin composition for giving a substance, 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, in order to develop a curable composition which provides a pull-high strength cured product, intensive I did some research. As a result, surprisingly, a cross-linking density modifier containing an aromatic monofunctional epoxy resin was used as a component of the curable composition in addition to the thiol-based curing agent and the epoxy resin, and the physical properties of the cured product given by this curable composition were used. It has been found that by adjusting the value so as to be within a predetermined range, the pull strength of the obtained cured product is increased, that is, the drop impact resistance is excellent. 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 (D):
(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) A crosslink density modifier containing at least one aromatic monofunctional epoxy resin; and (D) a curing catalyst.
In the DMA measurement by the tension method at a frequency of 10 Hz and a heating rate of 3 ° C./min.
An epoxy resin composition that gives a cured product in which the temperature at which the loss elastic modulus (E ") is maximized is in the range of 20 ° C. or higher and 55 ° C. or lower.

2. The epoxy resin composition according to item 1 above, wherein the molar ratio (B) / (A) of the component (B) to the component (A) is 1.15 or more and 1.45 or less.

3. 3. The epoxy resin composition according to the above item 1 or 2, wherein the molar ratio (C) / (A) of the component (C) to the component (A) is 0.55 or more and 1.65 or less.

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

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

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

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

It is a graph which shows the relationship between the calibration pull strength and the peak temperature (maximum value) of E ".

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)). )) And the curing catalyst (component (D)) are included as essential components. These components (A) to (D) 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 set the temperature at which E ”is maximized in a desired range, 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 are used. The total amount of the above is preferably 10% by mass or more and 55% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and further preferably 25% by mass or more and 50% by 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 the temperature at which E ”is maximized in a desired range, the epoxy resin composition has an aromatic epoxy resin (monofunctional and polyfunctional aromatic epoxy resin) and a glycoluril skeleton or an isocyanul skeleton. The total amount of the trifunctional thiol compound or the tetrafunctional thiol compound is preferably 45% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 80% by mass or less, and 50% by mass or more and 75% by mass or less. It is more preferably less than or equal to%.

(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 aromatic 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 more preferable that the component (C) is substantially an aromatic monofunctional epoxy resin.

Examples of the aromatic monofunctional epoxy resin 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 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, it gives the 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. _{The present inventors have disclosed in Patent Document 1 a composition in which the change in T g} is small after the heat resistance test, but thereafter, in such a composition, a moisture resistance reliability test (particularly under an environment of 85 ° C. and 85%). After the test, it was found that 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.} In some embodiments of the invention, therefore, the ratio of the sum of the epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalents for the component (A) ([epoxy functional group equivalent]). / [Tiol functional group equivalent]) is preferably 0.70 or more and 1.10 or less, more preferably 0.75 or more and 1.10 or less, and 0.80 or more and 1.05 or less. It is particularly preferable to have. In such a curable composition, 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 cured product of such curable compositions give, 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.

In some embodiments of the invention, the ratio of the sum of the 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]. When the functional group equivalent]) is 0.70 or more and 1.10 or less, 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 to a certain extent or more. Therefore, 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.

If desired, the curable composition of the present invention may contain any component other than the above components (A) to (D), 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 (D). Is more preferable, and 0.1 to 20 parts by mass is further preferable.

-Filler A filler can be added to the epoxy resin composition of the present invention if desired. When the epoxy resin composition of the present invention is used as a one-component adhesive, the addition of a filler to the epoxy resin composition improves the moisture resistance and thermal cycle resistance of the bonded portion, particularly the thermal cycle resistance. The addition of the 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.

The filler is not particularly limited as long as it has the effect of reducing the coefficient of linear expansion, and various fillers can be used. Specific examples of the filler include silica filler, alumina filler, talc filler, calcium carbonate filler, polytetrafluoroethylene (PTFE) filler and the like. Among these, silica filler is preferable because the filling amount can be increased.

When a filler is added, the content of the filler in the epoxy resin composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 65% by mass in the entire epoxy resin composition. It is preferably 5 to 50% by mass, more preferably 5 to 50% by mass.

-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 (D) 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 epoxy resin composition of the present invention gives a cured product in which the temperature at which the loss elastic modulus (E ") is maximized is in the range of 20 ° C. or higher and 55 ° C. or lower. It corresponds to the imaginary part of the complex elastic modulus expressed by a complex number, and indicates the disappearing energy of viscoelasticity during dynamic behavior. In the present specification, the loss elastic modulus has a frequency of 10 Hz and a temperature rise unless otherwise specified. It means a value measured by dynamic viscoelasticity measurement (DMA) at a speed of 3 ° C./min, a strain amplitude of 5.0 μm, and a tensile method.
A person skilled in the art will appropriately adjust the amounts of the components (A) to (D) and the like constituting the epoxy resin composition of the present invention so that the cured product of this composition has a predetermined loss modulus. Can be adjusted. Further, a method for measuring the loss elastic modulus is known, and a person skilled in the art can easily measure the loss elastic modulus using a conventional dynamic viscoelasticity measuring device.

As described above, in the cured product provided by the epoxy resin composition of the present invention, the temperature at which the loss elastic modulus (E ″) is maximized is in the range of 20 ° C. or higher and 55 ° C. or lower. With an epoxy resin composition not within the above range, the pull strength of the cured product, that is, the drop impact resistance is not sufficiently improved.
The epoxy resin composition of the present invention gives a cured product in which the temperature at which the loss elastic modulus is maximized is preferably in the range of 20 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 45 ° C. or lower.

From the viewpoint of making the dynamic viscoelastic property of the cured product as described above, in the epoxy resin composition of the present invention, the molar ratio (B) / (A) of the component (B) to the component (A) is , Preferably 1.15 or more and 1.45 or less.
For the same reason, in the epoxy resin composition of the present invention, the molar ratio (C) / (A) of the component (C) to the component (A) is 0.55 or more and 1.65 or less.
The relationship between the molar number ratio (B) / (A) of the component (B) and the component (A) reduces the cross-linking points of the component (A) containing a thiol compound having three or more thiol groups, for example, a thiol group. If it is a thiol compound having four, it means that it is used as if it were a bifunctional thiol compound or a trifunctional thiol compound. If the ratio is less than 1.15, the amount of the polyfunctional epoxy resin as a cross-linking component is too small, and 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 ratio is more than 1.45, 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 may be too high and the pull strength may be low.
The relationship between the molar ratio (C) / (A) of the component (C) and the component (A) is the thiol of the component (A) with respect to the number (amount) of epoxy groups contained in the component (C). It means that the groups are moderately excessive. Satisfying this relationship is preferable because a cured product having an appropriate density of crosslinks formed by the reaction of the components (A) and (B) can be obtained.
By satisfying the relationship between the molar ratio (B) / (A) of the component (B) and the component (A) and the molar ratio (C) / (A) of the component (C) and the component (A). , The thiol groups of the component (A) that did not react with the component (B) react with the component (C), and the unreacted thiol groups remaining in the cured product are reduced, so that the characteristics of the obtained cured product are appropriate. It becomes.
The cured product provided by the epoxy resin composition of the present invention includes, in particular, LCP (liquid crystal polymer), PC (polycarbonate), PBT (polybutylene terephthalate), SUS, alumina, and nickel (including those having a nickel-plated surface). Demonstrates excellent pull strength for adherends selected from the above. These may be surface-treated with plasma or the like. As used herein, the term "pull strength" typically means pull strength when these adherends are made of these materials.

The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, the components (A)-(D) 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 a range of −20 ° C. to 110 ° C., a frequency of 1 to 10 Hz, a heating rate of 1 to 10 ° C./min, and a strain amplitude of 5.0 μm using a dynamic thermomechanical measuring device (DMA). , Can be obtained by the tensile method. 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.

Examples 1-9, Comparative Examples 1-3
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): Trimethylolpropanetris (3-mercaptopropionate) (trade name: TMMP, manufactured by SC Organic Chemistry Co., Ltd., thiol equivalent: 133)
(A-3): Pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMP, manufactured by SC Organic Chemistry, thiol equivalent: 122)

-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): Dicyclopentadiene type epoxy resin (trade name: EP4088L, manufactured by ADEKA Corporation, epoxy equivalent 165)
(B-4): 1,4-Cyclohexanedimethanol diglycidyl ether (trade name: CDMDG, manufactured by Showa Denko KK, epoxy equivalent: 133)
(B-5): 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-based latent curing catalyst (trade name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation)

The latent curing catalyst (D-1) 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)). (D-1) in Tables 1 and 2 is a mass portion of the dispersion liquid containing the latent curing catalyst. The epoxy resin constituting this dispersion is treated as forming a part of the component (B). Therefore, (B) of "(B) / (A) (molar number ratio)" in Tables 1 and 2 includes the amount of the epoxy resin in (D-1).

・ Other ingredients (ingredient (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.)

In Examples and Comparative Examples, the characteristics of the cured product obtained by curing the epoxy resin composition were measured as follows.
(Preparation of cured product)
The resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were each heated at 80 ° C. for 120 minutes to obtain a cured product.

<Resilient modulus of cured product (E ")>
The measurement method _{of T g} of Japanese Industrial Standard JIS C6481 was used. 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) (manufactured by Seiko Instruments), 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 5.0 μm. The loss elastic modulus (E ") of the cured product was measured by the tensile method, and the temperature (° C.) at which E" was maximized was determined. The results are shown in Tables 1 and 2.

<Measured pull strength and calibration pull strength of cured product>
Spacers (heat-resistant tape with a thickness of 150 μm) were arranged at two locations on an alumina plate having a length of 20 mm, a width of 20 mm, and a thickness of 1.6 mm. Next, 1 mg of the resin composition was applied between the spacers. A thick plate (2.5 g) treated with 9 mm □ square bright nickel plating was placed on the spacer so as to be in contact with the applied resin composition. Then, the test piece was obtained by heat-curing at 80 ° C. for 120 minutes. A nut is attached to the upper part of the thick plate of this test piece using a moisture-curable adhesive, and left for 12 hours to prevent peeling between the thick plate and the nut when measuring the pull strength. And the nut were sufficiently joined. After that, after fixing the alumina plate to a precision load measuring instrument (manufactured by Aiko Engineering, model number: 1605HTP) so that the adhesive surface is horizontal, pass a string through the nut ring, attach this string to the jig, and attach it to the jig at 23 ° C. In, a pulling load was applied at a speed of 12 mm / min in the vertical direction. The measured pull strength was defined as the value obtained by dividing the maximum load applied until the alumina plate and the thick plate were separated by the adhesive area between the alumina plate and the thick plate (N = 6). The unit is N / mm ² . Further, from this actually measured pull strength, the calibration pull strength was obtained using the following formula derived from the comparison of Examples 1 and 2. The unit is N / mm ² . The results are shown in Tables 1 and 2.
Calibration pull strength = Measured pull strength / ((100-component (E) content (wt%) x 1.2) / 100)

The epoxy resin composition of the present invention can be used by adding the component (E) (filler) as needed, but as can be seen from the comparison between Examples 1 and 2, the component (E) (filler) As the content increases, the measured pull strength of the cured product tends to decrease. The calibration pull strength is a pull strength that offsets the influence of such a component (E).

As is clear from Tables 1 and 2, the pull strength after curing (particularly the calibration pull strength) was a satisfactory value in any of Examples 1 to 9.
On the other hand, in Comparative Examples 1 and 2 in which the temperature at which the E "of the cured product was maximized was not within the predetermined range and Comparative Example 3 in which the component (C) was not included, the pull strength after curing was insufficient. As can be seen from Comparative Example 3, in the epoxy resin composition having no predetermined composition, the pull strength after curing is not sufficiently improved even if the temperature at which the cured product E ”is maximized is in the predetermined range. ..
The relationship between the calibration pull strength in Tables 1 and 2 and the peak temperature (maximum value) of E ”is shown in FIG. 1. In FIG. 1, the thiol functional group equivalent of the component (A) is shown from the relationship between the straight lines of I and II. It can be seen that the pull strength increases as the epoxy functional group equivalent of the component (C) with respect to the component (C) increases.

The epoxy resin composition of the present invention 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. Further, since this cured product exhibits high pull strength, an electronic component having excellent drop impact resistance can be easily manufactured by using the epoxy resin composition of the present invention. 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 (7)

An epoxy resin composition having the following components (A) to (D):
(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) A crosslink density modifier containing at least one aromatic monofunctional epoxy resin; and (D) a curing catalyst.
In the DMA measurement by the tension method at a frequency of 10 Hz and a heating rate of 3 ° C./min.
An epoxy resin composition that gives a cured product in which the temperature at which the loss elastic modulus (E ") is maximized is in the range of 20 ° C. or higher and 55 ° C. or lower. The epoxy resin composition according to claim 1, wherein the molar ratio (B) / (A) of the component (B) to the component (A) is 1.15 or more and 1.45 or less. The epoxy resin composition according to claim 1 or 2, wherein the molar ratio (C) / (A) of the component (C) to the component (A) is 0.55 or more and 1.65 or less. The epoxy resin composition according to claims 1 to 3, 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 4. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4 or the encapsulant according to claim 5. An electronic component containing the cured product according to claim 6.