KR102129331B1 - Epoxy resin composition - Google Patents

Abstract

The present invention is cured in a short time even under low temperature conditions, an epoxy resin composition that provides a cured product having a low glass transition point (T _g ) and high pull strength, a sealing material containing the same, a cured product obtained by curing it, and a cured product thereof It relates to an electronic component comprising a. Since the epoxy resin composition of the present invention provides a cured product having a low T _g and a high pull strength after curing, it is very useful as an adhesive for semiconductor devices, electronic components, sealing materials, dam agents, and the like.

Description

Epoxy resin composition

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

Currently, in the assembly or mounting of electronic components used in semiconductor devices, for example, semiconductor chips, for the purpose of maintaining reliability, curable resin compositions, particularly adhesives containing epoxy resin compositions, sealing materials, and the like are often used. In particular, in the case of a semiconductor device including a component deteriorated under high temperature conditions, all of its manufacturing steps need to be performed under low temperature conditions. Therefore, it is required that adhesives and sealants used in the manufacture of such devices exhibit sufficient curability even under low temperature conditions. At the same time, it is also required to cure in a short time in terms of production cost.

The epoxy resin composition (hereinafter sometimes simply referred to as a "curable composition") used for such an electronic component adhesive or sealing material generally includes an epoxy resin and a curing agent. The epoxy resin includes various polyfunctional epoxy resins (epoxy resins having two or more epoxy groups). The curing agent includes a compound having two or more functional groups that react with an epoxy group in the epoxy resin. Among these curable compositions, it is known that the use of a thiol-based curing agent as a curing agent suitably cures in a short time even under low temperature conditions of 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. As an example of such a curable composition, what is disclosed in patent document 1 is mentioned.

The epoxy resin composition provides a cured product having various properties depending on its composition. In this respect, depending on the purpose of use of the curable composition, etc., it is sometimes not desirable that the glass transition point (T _g ) is high. For example, using this curable composition, two parts each made of a different material are joined.

When two parts made of different materials are bonded to each other with an adhesive and the ambient temperature of the assembly changes, thermal stress is generated in the parts according to the coefficient of thermal expansion of the material. This thermal stress does not cancel out because it is not uniform according to the difference in the coefficient of thermal expansion, and causes deformation of the granulated product. The stress accompanying this deformation acts particularly 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 particularly likely to occur when the cured product is brittle and lacks flexibility. Therefore, the adhesive for joining parts made of different materials requires flexibility (low modulus of elasticity) sufficient to follow the deformation of the assembly due to thermal expansion of the parts after curing. For that purpose, it is required that the cured T _g is properly low.

International Publication No. 2012/093510

However, the inventors have found that the epoxy resin composition described in Patent Document 1 described above has a problem that the T _g is sufficiently low to exhibit excellent low-temperature curing properties, but the pull strength is low. In some cases, drop impact resistance is required for electronic components. In order to increase the drop impact resistance, it is desirable to improve the adhesive strength of the adhesive.

The present invention has been made in light of the above problems, and an object of the present invention is to provide a cured product having a low glass transition point (T _g ) and a high pull strength by curing in a short time even under low temperature conditions. It is to provide a sealing material containing it. Another object of the present invention is to provide a cured product obtained by curing the epoxy resin composition or the sealing material. Another object of the present invention is to provide an electronic component including the cured product.

Under these circumstances, the present inventors conducted a thorough study to develop a curable composition that cured in a short period of time even under low temperature conditions to provide a cured product having a low T _g and a high pull strength. As a result, surprisingly, as a component of the curable composition, in addition to a thiol-based curing agent and an epoxy resin, a crosslinking density modifier containing an aromatic monofunctional epoxy resin is used so that the physical property value of the cured product provided by the curable composition is within a predetermined range. By adjusting, it was found that the pool strength of the obtained cured product is increased, that is, the drop resistance is excellent. Based on the above new findings, the present invention has been accomplished.

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

1. As an epoxy resin composition, the following components (A) to (D):

(A) a thiol-based curing agent comprising at least one polyfunctional thiol compound having three or more thiol groups;

(B) at least one polyfunctional epoxy resin;

(C) a crosslinking density modifier comprising at least one aromatic monofunctional epoxy resin; And

(D) curing catalyst

Including,

Frequency 10 Hz, heating rate 3 ℃ / min, in the DMA measurement by the tensile method,

An epoxy resin composition that provides a cured product having a temperature at which the loss modulus (E") is maximized in a range of 20°C to 55°C.

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

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

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

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

6. Hardened|cured material obtained by hardening|curing the epoxy resin composition as described in any one of the above-mentioned 1-4, or the sealing material as described in the above-mentioned 5.

7. An electronic component comprising the cured product according to the preceding item 6.

1 is a graph showing the relationship between the calibration pool intensity 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)), a crosslinking density modifier (component (C)), and a curing catalyst. (Component (D)) is included as an essential component. These components (A) to (D) will be described below.

In addition, in this specification, according to the customary practice in the field of epoxy resins, for the components constituting the epoxy resin composition before curing, the name usually includes the term "resin" indicating a polymer (especially a synthetic polymer). It is sometimes 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 has three or more thiol groups that react with an epoxy group in a polyfunctional epoxy resin (component (B)) or a crosslinking density regulator (component (C)), which will be described later. And at least one polyfunctional thiol compound. It is preferable that component (A) contains a trifunctional and/or a 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. In addition, the trifunctional and tetrafunctional thiol compounds are thiol compounds having three and four thiol groups, respectively.

In one aspect of the present invention, the polyfunctional thiol compound is a component containing a non-hydrolyzable polyfunctional thiol compound that 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 preferred to use A). The non-hydrolyzable polyfunctional thiol compound is less likely to undergo hydrolysis even under a high temperature and high humidity environment.

In another aspect of the present invention, component (A) includes 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 Chemistry, component (A), it is preferable to contain a thiol resin, there is no coupling element.

Examples of the hydrolyzable polyfunctional thiol compound include trimethylolpropane tris (3-mercaptopropionate) (SC Yuki Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl ]-Isocyanurate (manufactured by SC Yuki Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (SC Yuki Chemical Co., Ltd.: PEMP), tetraethylene glycol bis (3-mercaptopropionate) (SC Yuki Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (SC Yuki Chemical Co., Ltd.: DPMP ), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd.: Carens 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.: Carens MT (registered trademark) NR1) and the like.

Preferred non-hydrolyzable polyfunctional thiol compounds that can be used in the present invention are the following formula (1):

(In the formula,

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 mercaptomethyl group, mercaptoethyl group and mercaptopropyl group)

It is a compound represented by. Examples of the compound represented by formula (1) include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (trade name: TS-G, manufactured by Shikoku Chemical Co., Ltd.), (1, 3,4,6-tetrakis(3-mercaptopropyl) glycoluril (trade name: C3 TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), 1,3,4,6-tetrakis(mercaptomethyl) glycol Uryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1, 3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3, 4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1, 3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril, etc. These may be used alone or in combination of two or more. Of these, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril are particularly preferred.

Other preferred non-hydrolyzable polyfunctional thiol compounds that can be used in the present invention are the following formula (2):

(R ⁸ ) _m -A-(R ⁷ -SH) _n (2)

(In the formula,

A is a residue of a polyhydric alcohol having n+m hydroxyl groups, and includes n+m oxygen atoms derived from the hydroxyl group,

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 of 0 or more,

n is an integer of 3 or more,

R ⁷ and R ⁸ are each bonded to the A through the oxygen atom)

It is a compound represented by. You may use combining 2 or more types of compounds represented by Formula (2). Examples of the compound represented by formula (2) include pentaerythritol tripropanethiol (trade name: PEPT, manufactured by SC Yuki Chemical Co., Ltd.), pentaerythritol tetrapropanthiol, and the like. Of these, pentaerythritol tripropanethiol is particularly preferred.

As the non-hydrolyzable polyfunctional thiol compound, a polythiol compound having a trifunctional or higher function having two or more sulfide bonds in the molecule can also be used. Examples of the thiol compound include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3- Mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tri Thiadecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiadecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 -Trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3 -Tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane , 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7 -Dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1, 6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl) 3,7-dithianonane, 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(mercaptomethyl Thio)-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-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimer Capto-2,5,7,10,12,15-hexathiahexadecane, 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-dithiaheptylthio]-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-dithianilthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2, 4,6,10-tetrathiaundecan, 3-[2-(1,3-dithiethanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4 ,6,10-tetrathiadecane, 9-[2-(1,3-dithiethanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto -2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-diethienyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio )-1,17-dimercapto-2,4,6,10,12,16-hexathioheptadecane and other aliphatic polythiol compounds; 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianilthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianilthio]-1 ,3-Dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethyl Thio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-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-dithiethane, 2-[3,4-bis(mer Captomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio) )-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3-bis(mercaptomethylthio)methyl-5, 6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiethane, 4-{1-[2-(1,3 -Dithitanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3- And polythiol compounds having a cyclic structure such as dithiolane.

(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 polyfunctional epoxy resin. Therefore, the epoxy resin conventionally used can be used as component (B). As described above, the polyfunctional epoxy resin refers to an epoxy resin having two or more epoxy groups. In one aspect of the present invention, component (B) includes a bifunctional epoxy resin.

The polyfunctional epoxy resin is largely divided into an aliphatic polyfunctional epoxy resin and an aromatic polyfunctional epoxy resin.

Examples of the aliphatic polyfunctional epoxy resin,

-(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, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene Diepoxy resins such as type diglycidyl ether;

-Triepoxy resins such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether;

Alicyclic epoxy such as -vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane Suzy;

-Glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane;

Hydantoin type epoxy resins such as -1,3-diglycidyl-5-methyl-5-ethyl hydantoin; And

Epoxy resin having a silicone skeleton such as -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane

And the like, but are not limited to these.

In the above example, "cyclohexane-type diglycidyl ether" means a compound having a structure in which two glycidyl groups are bonded to a divalent saturated hydrocarbon group having one cyclohexane ring as a parent structure through ether bonding, respectively. Means "Dicyclopentadiene type diglycidyl ether" means a compound having two glycidyl groups bonded to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a parent structure through ether bonding. . It is preferable that the aliphatic polyfunctional epoxy resin has an epoxy equivalent of 90 to 450 g/eq. Moreover, as cyclohexane type diglycidyl ether, cyclohexane dimethanol diglycidyl ether is especially preferable.

In one aspect of the present invention, component (B) includes an aliphatic polyfunctional epoxy resin. When an aliphatic polyfunctional epoxy resin is used as the component (B), it is preferable that the component (A) to be combined contains a trifunctional thiol compound or a tetrafunctional thiol compound having a glycoluril skeleton or an isocyanuric skeleton. It is preferable that the ratio ([epoxy functional group equivalent]/[thiol functional group equivalent]) of the epoxy functional group equivalent to the aliphatic polyfunctional epoxy resin to the thiol compound having a glycoluril skeleton or an isocyanuric skeleton is 0.40 to 0.85.

In one aspect of the present invention, component (A) includes a trifunctional thiol compound or a tetrafunctional thiol compound having a glycoluril skeleton or an isocyanur skeleton. When a trifunctional thiol compound or a tetrafunctional thiol compound having a glycoluril skeleton or an isocyanuric skeleton is used as the component (A), the component (B) has a cyclohexane type diglycidyl ether or a silicone skeleton. It is preferred to use an epoxy resin. In particular, it is preferable to use 1,4-cyclohexanedimethanol diglycidyl ether or 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane.

In addition, in one aspect of the present invention, the component (A) does not have a glycoluril skeleton or an isocyanur skeleton, and a trifunctional thiol compound or a tetrafunctional thiol compound (specifically, a polyether skeleton, a polysulfide skeleton, Or a trifunctional thiol compound or a tetrafunctional thiol compound) having a polyester skeleton. In order to set the temperature at which E" is maximized to a desired range, the trifunctional thiol compound or the tetrafunctional thiol compound which does not have an aliphatic polyfunctional epoxy resin and a glycoluril skeleton or an isocyanur skeleton in the epoxy resin composition. The total amount 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 even more 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. There are many types of epoxy resins conventionally used, such as bisphenol A-type epoxy resins. Examples of the aromatic polyfunctional epoxy resin,

-Bisphenol A type epoxy resin;

branched polyfunctional bisphenol A type epoxy resins such as -p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether;

-Bisphenol F-type epoxy resin;

-Novolac-type epoxy resins;

-Tetrabromobisphenol type A 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;

Glycidylamine-type epoxy resins such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; And

-Epoxy resin containing naphthalene ring

And the like, but are not limited to these. 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 preferred, and among them, the epoxy equivalent of 90 to 200 g/eq is particularly preferable, and the epoxy equivalent is Most preferably, it is 110 to 190 g/eq.

When an aromatic polyfunctional epoxy resin is used as the component (B), the component (A) to be combined is a trifunctional thiol compound or a tetrafunctional thiol compound having a polyether skeleton, a polysulfide skeleton, or a polyester skeleton. desirable. The ratio of the epoxy functional group equivalent to 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 to 1.10 It is preferred. Moreover, when using a trifunctional thiol compound or a tetrafunctional thiol compound which has a polyether skeleton, a polysulfide skeleton, or a polyester skeleton as component (A), as component (B), bisphenol A type epoxy resin, It is preferable to use at least one of a bisphenol F-type epoxy resin and a naphthalene ring-containing epoxy resin.

In addition, in order to set the temperature at which E" is maximized to a desired range, an aromatic epoxy resin (monofunctional and polyfunctional aromatic epoxy resin) in the epoxy resin composition and a glycoluril skeleton or an isocyanur skeleton are provided. 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 even more preferably 50% by mass or more and 75% by mass or less. .

(3) Crosslinking density regulator (component (C))

The crosslinking density regulator (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 the epoxy resin composition. Monofunctional epoxy resins are largely classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the component (C) preferably has an epoxy equivalent weight of 180 to 400 g/eq. In this invention, it is preferable that a component (C) contains an aromatic monofunctional epoxy resin from a viewpoint of viscosity and low volatility. Moreover, it is more preferable that component (C) is substantially an aromatic monofunctional epoxy resin.

Examples of the aromatic monofunctional epoxy resin included in component (C) include phenylglycidyl ether, cresylglycidyl ether, ps-butylphenylglycidyl ether, styrene oxide, and p-tert-butylphenylglycidyl Ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, and the like, but are not limited to these. Of these, p-tert-butylphenylglycidyl ether and phenylglycidyl ether are preferred, and p-tert-butylphenylglycidyl ether is particularly preferred. Examples of the aliphatic monofunctional epoxy resin include n-butylglycidyl ether, 2-ethylhexylglycidyl ether, α-pineneoxide, allylglycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1 ,2-epoxy-4-(2-methyloxyranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, neodecane Acid glycidyl ester, etc. are mentioned, but 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 a known one can be used. It is preferable that component (D) is a latent curing catalyst. The latent curing catalyst is a compound that is inactive at room temperature, activated by heating, and functions as a curing catalyst, for example, an imidazole compound that is solid at room temperature; A solid dispersion type amine adduct-based latent curing catalyst such as a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct); And reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems). 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 products of latent curing catalysts include "Amicure PN-23" (Ajinomoto Finetechno Co., Ltd.) and "Amicure PN-40" (Ajinomoto) as amine-epoxy adducts (amine adducts). Fine Techno Co., Ltd.), ``Amicure PN-50'' (Ajinomoto Fine Techno Co., Ltd.), ``Hardner X-3661S'' (ACR Co., Ltd.), ``Hardner X-3670S'' (ACR Co., Ltd.) Brand name), ``Novacure HX-3742'' (Asahi Kasei Co., Ltd. brand name), ``Novacure HX-3721'' (Asahi Kasei Co., Ltd. brand name), ``Novacure HXA9322HP'' (Asahi Kasei Co., Ltd. brand name), `` Novacure HXA3922HP'' (Asahi Kasei Co., Ltd.), ``Novacure HXA3932HP'' (Asahi Kasei Co., Ltd.), ``Novacure HXA5945HP'' (Asahi Kasei Co., Ltd.), ``Novacure HXA9382HP'' (Asahi Kasei( Note) Product name), ``Fujicure FXR1121'' (T&K TOKA Co., Ltd. product name), and the like, and as an element type adduct system, ``Fujicure FXE-1000'' (T&K TOKA Co., Ltd. product name), ``Fuji Cure FXR-1030” (trade name of T&K TOKA Corporation), and the like, but are not limited to these. Component (D) may be used alone or in combination of two or more. As component (D), from the viewpoint of pot life and curability, a solid dispersion type amine adduct-based latent curing catalyst is preferable.

Moreover, there are those provided in the form of a dispersion liquid dispersed in a polyfunctional epoxy resin in component (D). When using such a component (D), 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.

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 divided by the thiol equivalent of the thiol compound (When plural thiol compounds are included, it is the sum of such shares for each thiol compound). Thiol equivalent weight can be determined by an iodine titration method. This method is well known and is disclosed, for example, in paragraph 0079 of JP 2012-153794 A. When the thiol equivalent cannot be obtained by this method, the molecular weight of the thiol compound may be calculated as the quotient divided 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 (components (B) and (C)) contained in the same component or composition, and the mass (g) of the epoxy resin contained in the component or composition of interest Is the quotient divided by the epoxy equivalent of the epoxy resin (when multiple epoxy resins are included, the sum of those quotients for each epoxy resin). The epoxy equivalent can be determined by the method described in JIS K7236. When the epoxy equivalent cannot be obtained by this method, the molecular weight of the epoxy resin may be calculated as the quotient divided by the number of epoxy groups in one molecule of the epoxy resin.

Thiol-based curing agent is an excess of epoxy resin composition with respect to the epoxy resin, there is provided an initial T _g (T _g of the cured immediately after) the cured product low. However, when the thiol-based curing agent is excessive with respect to the epoxy resin, the thiol groups remaining in the cured product do not react with the epoxy groups and remain unreacted. Although the present inventors disclosed a composition with a small change in T _g after the heat resistance test in Patent Document 1, after that, in such a composition, in the moisture resistance reliability test (especially 100 hours under an environment of 85° C. and 85%), after the test , It has been found that there is a possibility that new crosslinking by excessive thiol groups may occur. To moderate if progression of the cross-linking are compared with when the epoxy resin is excessive with respect to a thiol-based curing agents, however, results in an increase in the T _g. In one aspect of the present invention, for this reason, the ratio of the sum of the epoxy functional group equivalents to the components (B) and (C) to the thiol functional group equivalents to the component (A) ([Epoxy functional group equivalents]/[ Thiol 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 particularly preferably 0.80 or more and 1.05 or less. In such a curable composition, since the epoxy group contained in the said component (C) reducing its unreacted thiol group exists, as a result of reaction between them, most of unreacted thiol groups are lost. The polyfunctional epoxy resin contained in the component (B) has a function of connecting two molecules of the polyfunctional thiol compound contained in the component (A) to extend the polymer chain or to form crosslinks between the polymer chains. . However, the monofunctional epoxy resin is included in the component (C) that does not have such a function, a new cross-linking occurs to by the reaction between the component (A) and (C), rising to the cured T _g Can be suppressed. Therefore, the cured product of such a curable composition is provided, since there is little amount of the functional group capable of forming a new cross-linked, even if a long time elapses after the curing, the increase of the T _g caused by the formation of a new cross-linking hardly visible.

In one aspect of the present invention, the ratio ([Epoxy Functional Group Equivalent]// Thiol Functional Group Equivalent to the thiol functional group equivalent to component (A)) of the sum of the epoxy functional group equivalents to components (B) and (C) When ]) is 0.70 or more and 1.10 or less, the ratio of the epoxy group and the thiol group in the same composition involved in the reaction between the epoxy group and the thiol group is at a predetermined or higher ratio, so that the properties of the resulting cured product are appropriate. If the above ratio is less than 0.70, since the thiol group is excessive with respect to epoxy groups, unreacted while the thiol group is left in the cured product increases, it becomes difficult to the cured T _g increase caused by the reaction of a thiol such inhibition period. On the other hand, when the above-mentioned ratio is more than 1.10, since the epoxy group is excessive with respect to the thiol group, in addition to the reaction between the epoxy group and the thiol group, the reaction (exclusive polymerization) of the excess epoxy period proceeds. As a result, intermolecular crosslinking by both of these reactions is formed in the resulting cured product, so the crosslinking density becomes too high and T _g rises. Alternatively, low-temperature curing, which is 1 hour at 80°C, becomes difficult.

If desired, the curable composition of the present invention may contain optional components other than the components (A) to (D), for example, those described below.

ㆍStabilizer

If desired, a stabilizer can be added to the epoxy resin composition of the present invention. The stabilizer can be added to the epoxy resin composition of the present invention to improve its storage stability and lengthen the pot life. As a stabilizer for an epoxy resin-based one-component adhesive, various known stabilizers can be used, but from a high effect of improving storage stability, at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and organic acids is preferred. Do.

Examples of the liquid boric acid ester compound include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, and triisopropyl Borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, triocta Decyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1,4, 7-trioxanedecyl) borane, 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), it is preferable because the viscosity of the compound can be suppressed low. As the aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used. As an organic acid, barbituric acid can be used, for example.

When adding a stabilizer, the addition amount thereof is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and more preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of components (A) to (D) It is more preferable.

ㆍFilling agent

If desired, a filler can be added to the epoxy resin composition of the present invention. When the epoxy resin composition of the present invention is used as a one-component adhesive, when a filler is added to it, the moisture resistance and the thermal cycle resistance, particularly the thermal cycle resistance, of the bonded site are improved. The thermal cycle resistance is improved by the addition of the filler because the linear expansion coefficient of the cured product decreases, that is, expansion and contraction of the cured product by the thermal cycle are suppressed.

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

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, and more preferably 5 to 80% by mass in the entire epoxy resin composition. It is more preferable that it is 50 mass %.

ㆍCoupling agent

If desired, a coupling agent may be added to the epoxy resin composition of the present invention. The addition of a coupling agent, especially 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, amino, vinyl, methacrylic, acrylic, and mercapto series can be used. As a specific example of a silane coupling agent, 3-glycidoxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, vinyl trimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-part Thylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltri Methoxysilane, 8-glycidoxyoctyl trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-iso And cyanatopropyl triethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

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

ㆍOther additives

In the epoxy resin composition of the present invention, if desired, other additives, such as carbon black, titanium black, ion trapping agent, leveling agent, antioxidant, antifoaming agent, thixotropic agent, viscosity, within a range not impairing the spirit of the present invention Adjusters, flame retardants, colorants, solvents and the like can be added. The type and amount of each additive are in the usual manner.

The epoxy resin composition of the present invention provides a cured product in which the temperature at which the loss modulus (E") is maximized is in the range of 20°C to 55°C. The loss modulus is the complex elastic modulus in which the dynamic elastic modulus of an object is expressed by a complex number. Corresponds to the imaginary part of and represents the energy lost in viscoelasticity during dynamic behavior In this specification, the loss modulus is a frequency of 10 Hz, a heating rate of 3° C./min, a deformation amplitude of 5.0 μm, unless otherwise specified. It means the value measured by dynamic viscoelasticity measurement (DMA) by tensile method.

Those skilled in the art can adjust the amount of the components (A) to (D) constituting the epoxy resin composition of the present invention as appropriate, so that the cured product provided by the composition has a predetermined loss modulus. In addition, the method for measuring the loss modulus is well known, and a person skilled in the art can easily measure the loss 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 modulus (E") is maximized is in the range of 20°C or more and 55°C or less. In the resin composition, 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 provides a cured product having a temperature at which the loss modulus becomes maximum, preferably in the range of 20°C to 50°C, more preferably 20°C to 45°C.

From the viewpoint that the dynamic viscoelastic properties of the cured product are as described above, in the epoxy resin composition of the present invention, the molar ratio (B)/(A) of component (B) and component (A) is preferably 1.15 or more and 1.45 or less to be.

Further, for the same reason, in the epoxy resin composition of the present invention, the molar ratio (C)/(A) of component (C) and component (A) is 0.55 or more and 1.65 or less.

The relationship between the molar ratio (B)/(A) of the component (B) and the component (A) reduces the crosslinking point of the component (A) containing a thiol compound having three or more thiol groups, for example, thiol If it is a thiol compound having 4 groups, it means that it is used as a bifunctional thiol compound or a trifunctional thiol compound. When the above-mentioned ratio is less than 1.15, since there are too few polyfunctional epoxy resins as crosslinking components, there is a concern that the obtained cured product exhibits properties such as a thermoplastic resin that melts under high temperature. On the other hand, when the above-mentioned ratio is more than 1.45, since there are too many polyfunctional epoxy resins as crosslinking components, intermolecular crosslinking due to the reaction of components (A) and (B) is excessively formed in the resulting cured product, and the crosslinking density becomes too high. , There is a fear that the pull strength becomes small.

The relationship between the molar ratio (C)/(A) of the component (C) and the component (A) is such that the thiol group of the component (A) is appropriate for the number (amount) of the epoxy groups contained in the component (C). It means that it is excessive. By satisfying this relationship, a cured product having an appropriate density of crosslinks formed by the reaction of components (A) and (B) is obtained, and thus is preferable.

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 component (B ) Since the thiol group of the component (A) which has not reacted with the component (C) reacts with less unreacted thiol groups remaining in the cured product, the properties of the obtained cured product are appropriate.

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, nickel (nickel plated on the surface) It exhibits excellent pull strength with respect to an adherend selected from among them. These may be surface treated with plasma or the like. In this specification, "pull strength" typically means the pull strength when these adherends are these materials.

The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, the components (A) to (D) and other additives, if desired, are introduced simultaneously or separately in a suitable mixer, and if necessary, mixed by stirring while being melted by heating to obtain a uniform composition, the present invention The epoxy resin composition can be obtained. The mixer is not particularly limited, and a thyristor equipped with a stirring device and a heating device, a Henschel mixer, three roll mills, a ball mill, a planetary mixer, and a beads mill can be used. Moreover, you may use it combining these apparatus suitably.

The epoxy resin composition thus obtained is thermosetting, and under conditions of a temperature of 80°C, it is preferable to cure within 5 hours, and more preferably within 1 hour. Further, curing at a high temperature and a very short time, which is a few seconds at a temperature of 150°C, is also possible. When the curable composition of the present invention is used in the manufacture of an image sensor module including a component deteriorated under high temperature conditions, the composition is thermally cured at a temperature of 60 to 90°C for 30 to 120 minutes, or 120 to 200°C It is preferable to heat-cure at a temperature of 1 to 300 seconds.

The epoxy resin composition of the present invention cures in a short time even under low temperature conditions, thereby providing a cured product having a low T _g . The cured product of the epoxy resin composition of the present invention preferably has a T _g of 65°C or less, more preferably 60°C or less, and even more preferably 50°C or less. In addition, from the point of view of adhesion, the cured T _g is more preferably not less than, and preferably, less than 32 ℃, 30 ℃. In the present invention, T _g is, using a dynamic thermomechanical measuring device (DMA), a range of -20°C to 110°C, a frequency of 1 to 10Hz, a heating rate of 1 to 10°C/min, a strain amplitude of 5.0 μm, and tension You can get it 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 (tanδ) obtained from the loss modulus (E")/storage modulus (E').

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

In this invention, the sealing material containing the epoxy resin composition of this invention is also provided. The sealing material of this invention is suitable as a fill material for protecting or fixing a module, an electronic component, etc., for example.

Moreover, in this invention, the hardened|cured material obtained by hardening the epoxy resin composition or sealing material of this invention is also provided.

In the present invention, an electronic component including the cured product of the present invention is also provided.

<Example>

Hereinafter, the present invention will be described by examples, but the present invention is not limited to these. In addition, in the following examples, parts and% represent parts by mass and mass% unless otherwise stated.

Examples 1 to 9 and Comparative Examples 1 to 3

According to the formulations shown in Tables 1 to 2, an epoxy resin composition was prepared by mixing each component in a predetermined amount using three roll mills. In Tables 1 to 2, the amount of each component is expressed in parts by mass (unit: g).

ㆍThiol curing agent (component (A))

In Examples and Comparative Examples, the compounds used as component (A) are as follows.

(A-1): 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (trade name: TS-G, manufactured by Shikoku Chemical Co., Ltd., thiol equivalent: 100)

(A-2): Trimethylolpropane tris (3-mercaptopropionate) (trade name: TMMP, manufactured by SC Yuki Chemical Co., Ltd., thiol equivalent weight: 133)

(A-3): Pentaerythritol tetrakis (3-mercaptopropionate) (brand name: PEMP, SC Yuki Chemicals, thiol equivalent: 122)

ㆍEpoxy resin (component (B))

In Examples and Comparative Examples, the compounds used as component (B) are as follows.

(B-1): Bisphenol F-type epoxy resin (trade name: YDF-8170, manufactured by Shinnitetsu Sumkin Co., Ltd., 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, Epoxy equivalent 165)

(B-4): 1,4-cyclohexanedimethanol diglycidyl ether (trade name: CDMDG, manufactured by Showa Denko Co., Ltd., epoxy equivalent: 133)

(B-5): 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane (trade name: TSL9906, Momentive Performance Materials, Japan Kodo Chemical Co., Ltd., Epoxy equivalent: 181)

ㆍCrosslinking density regulator (ingredient (C))

In Examples and Comparative Examples, the compounds used as component (C) are as follows.

(C-1): p-tert-butylphenyl glycidyl ether (trade name: ED509S, manufactured by ADEKA, Epoxy equivalent: 205)

(C-2): Phenylglycidyl ether (trade name: Denacol EX141, manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent: 151)

(C-3): 2-ethylhexyl glycidyl ether (trade name: Denacol EX121, manufactured by Nagase Chemtex, Epoxy equivalent: 187)

ㆍCuring catalyst (component (D))

In Examples and Comparative Examples, the compounds used as component (D) are as follows.

(D-1) Amine-epoxy adduct-based latent curing catalyst (trade name: Novacure HXA9322HP, manufactured by Asahi Kasei Co., Ltd.)

The latent curing catalyst (D-1) is a dispersion (potential) in which a particulate latent curing catalyst is dispersed in an epoxy resin (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin (epoxy equivalent: 170)) Sex curing catalyst/bisphenol type A epoxy resin and mixture of bisphenol F type epoxy resin=33/67 (mass ratio)). (D-1) in Tables 1 to 2 are parts by mass of the dispersion liquid containing the latent curing catalyst. The epoxy resin constituting this dispersion is treated as forming part of component (B). Therefore, the amount of the epoxy resin in (D-1) is contained in (B) of "(B)/(A) (molar ratio)" in Tables 1 to 2.

・Other ingredients (ingredient (E))

In Examples and Comparative Examples, the compounds used as component (E) are as follows.

(E-1): Silica filler 1 (trade name: SE2300, average particle diameter 0.6 µm, manufactured by Admatex Co., Ltd.)

(E-2): Silica filler 2 (trade name: SO-E5, average particle diameter 2.0 µm, manufactured by Admatex Co., Ltd.)

In Examples and Comparative Examples, the properties of the cured product obtained by curing the epoxy resin composition were measured as follows.

(Production of light cargo)

Cured products were obtained by heating the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 at 80°C for 120 minutes, respectively.

<Loss modulus of hardening (E")>

It carried out using the measuring method of T _g of 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 thereon two spacers (overlapping with heat-resistant tape) so that the film thickness when cured was 400±150 µm. Placed in. Subsequently, a resin composition was applied between the spacers, and sandwiched between separate glass plates with a Teflon (registered trademark) sheet on the surface to prevent air bubbles from rolling, and cured at 80°C for 120 minutes to obtain a cured product. Finally, after peeling this cured product from the glass plate with the Teflon (registered trademark) sheet, it was cut out to a predetermined dimension (10 mm x 40 mm) with a cutter to obtain a test piece. Further, the cut-out portion was smoothed with sandpaper. By using a dynamic thermomechanical measuring device (DMA) (manufactured by Seiko Instruments Inc.), this cured product is in a range of -20°C to 110°C, a frequency of 10 Hz, a heating rate of 3°C/min, a strain amplitude of 5.0 µm, and a tensile method. The loss modulus (E") of the cured product was measured, and the temperature (°C) at which E" was maximized was determined. The results are shown in Tables 1 to 2.

<Measured pool strength and corrected pool strength of hardened products>

Spacers (150 µm-thick heat-resistant tape) were placed in two places on an alumina plate having a length of 20 mm × 20 mm × 1.6 mm in thickness. Subsequently, 1 mg of the resin composition was applied between the spacers. On a spacer, a thick plate (2.5 g) treated with 9 mm square glossy nickel plating was placed on the spacer so as to contact the applied resin composition. Then, it heat-cured at 80 degreeC for 120 minutes, and obtained the test body. A nut was attached to the upper portion of the back plate of the test body using a moisture-curable adhesive, and the plate and the nut were sufficiently joined by standing for 12 hours to prevent peeling between the plate and the nut when measuring the pull strength. After that, the alumina plate was fixed to a precision load meter (manufactured by Aiko Engineering, Model No.: 1605HTP) so that the adhesive surface was horizontal, and then passed through a string on the wheel of the nut, and this string was installed on a jig, and at 23°C. , A tensile load was applied at a rate of 12 mm/min in the vertical direction. The maximum load applied until the alumina plate and the thick plate were divided, and the value divided by the adhesive area between the alumina plate and the thick plate was taken as the actual pull strength (N=6). The unit is N/mm 2. In addition, the corrected pool strength was obtained from the measured pool strength 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 to 2.

Corrected pool strength = actual pool strength/((100-component (E) content (wt%)×1.2)/100)

The epoxy resin composition of the present invention can be used by adding component (E) (filler) as necessary, but as can be seen from the comparison of Examples 1 and 2, the content of component (E) (filler) increases. The measured pool strength of the lower surface cured product tends to decrease. The above-mentioned corrected pull strength is a pull strength that offsets the influence of this component (E).

As is evident from Tables 1 to 2, in any of Examples 1 to 9, the pull strength after curing (particularly the corrected pull strength) was a satisfactory value.

On the other hand, in Comparative Examples 1 to 2 in which the temperature at which E" of the cured product became the maximum was not in a predetermined range and Comparative Example 3 not containing component (C), the pull strength after curing was insufficient. As can be seen, in an epoxy resin composition that does not have a predetermined composition, even if the temperature at which E" of the cured product is maximized is within a predetermined range, the pull strength after curing is not sufficiently improved.

The relationship between the calibration pool strength of Tables 1 to 2 and the peak temperature (maximum value) of E" is shown in Fig. 1. In Fig. 1, from the relationship between the straight lines of I and II, the equivalent of the thiol functional group equivalent of component (A) It can be seen that as the epoxy functional group equivalent of component (C) increases, the pull strength increases.

The epoxy resin composition of the present invention is cured in a short time even under low temperature conditions to provide a cured product. This cured product exhibits low T _g and has moderate flexibility and flexibility. In addition, since this cured product exhibits high pull strength, by using the epoxy resin composition of the present invention, it is possible to easily manufacture an electronic component having excellent drop impact resistance. Therefore, the epoxy resin composition of the present invention is particularly useful as a semiconductor device or an electronic component adhesive, a sealing material, a dam agent, or the like, which is assembled by joining a plurality of parts made of different materials.

Claims (7)

As an epoxy resin composition, the following components (A) to (D):
(A) a thiol-based curing agent comprising at least one polyfunctional thiol compound having three or more thiol groups;
(B) at least one bifunctional epoxy resin;
(C) a crosslinking density modifier comprising at least one aromatic monofunctional epoxy resin; And
(D) curing catalyst
Including,
The mole ratio (B)/(A) of component (B) and component (A) is 1.15 or more and 1.45 or less,
Frequency 10 Hz, heating rate 3 ℃ / min, in the DMA measurement by the tensile method,
An epoxy resin composition that provides a cured product having a temperature at which the loss modulus (E") is maximized in a range of 20°C to 55°C. The epoxy resin composition according to claim 1, wherein component (A) comprises a trifunctional or tetrafunctional thiol compound. The ratio ([epoxy functional group equivalent]/[thiol functional group equivalent]) to the thiol functional group equivalent to component (A) of the sum of the epoxy functional group equivalents to components (B) and (C) is 0.70. The epoxy resin composition is 1-10 or more. The epoxy resin composition according to any one of claims 1 to 3, wherein the molar ratio (C)/(A) of the component (C) and the component (A) is 0.55 or more and 1.65 or less. A sealing material comprising the epoxy resin composition according to claim 1. A cured product obtained by curing the epoxy resin composition according to claim 1 or the sealing material according to claim 5. An electronic component comprising the cured product according to claim 6.

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