TWI826714B - Epoxy resin composition - Google Patents

Abstract

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; the epoxy resin composition can be cured in a short time even under low temperature conditions, thereby giving a cured product having a low glass transition point (T_g) and high pull strength. Since the epoxy resin composition of the present invention gives a cured product having a low T_g and high pull strength after curing, it is very useful as an adhesive, a sealing material, a dam agent, etc. for semiconductor devices and electronic components.

Description

Epoxy resin composition

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

Currently, for the purpose of maintaining reliability, adhesives and sealants containing curable resin compositions, especially epoxy resin compositions, are often used in the assembly and installation of electronic components used in semiconductor devices, such as semiconductor wafers. wait. Especially in the case of semiconductor devices containing parts that degrade under high temperature conditions, the manufacturing steps must be performed under low temperature conditions. Therefore, the adhesives and sealing materials used to manufacture such devices are required to exhibit sufficient hardening properties even under low temperature conditions. In terms of production costs, these are also required to be hardened in a short time.

The epoxy resin composition (hereinafter sometimes referred to simply as "curable composition") used in such adhesives and sealing materials for electronic parts generally contains an epoxy resin and a hardener. Epoxy resins include various polyfunctional epoxy resins (epoxy resins having two or more epoxy groups). The hardener is a compound containing two or more functional groups that react with epoxy groups in the epoxy resin. Among such curable compositions, it is known that those using a thiol-based curing agent as a curing agent can be cured appropriately in a short time even under low temperature conditions such as 0°C to -20°C. Thiol hardeners contain 2 or more mercaptans Based compounds, that is, polyfunctional thiol compounds. An example of such a curable composition is disclosed in Patent Document 1.

Epoxy resin compositions can form hardened products with various properties depending on their composition. This point depends on the purpose of use of the curable composition, etc., and a higher glass transition point (T _g ) may not be preferable. For example, this curable composition is used to join two parts made of different materials.

If the temperature around an assembly in which two parts made of different materials are joined to each other with an adhesive changes, thermal stress will occur in these parts due to the thermal expansion coefficient of the material. This thermal stress is uneven due to different thermal expansion coefficients and cannot offset each other, causing deformation of the assembly. The stress caused by this deformation especially acts on the joint part of the parts, that is, the hardened material of the adhesive, and may cause cracks in the hardened material depending on the situation. Such cracks are particularly likely to occur when the hardened material is brittle and lacks flexibility. Therefore, the adhesive used to join parts made of different materials needs to be flexible (low elastic coefficient) to the extent that it can accompany the deformation of the assembly caused by the thermal expansion of the parts after hardening. Therefore, the _Tg of the hardened material is required to be appropriately low.

[Prior technical literature]

[Patent Document]

[Patent Document 1] International Publication No. 2012/093510

However, the present inventors discovered that the epoxy resin composition described in Patent Document 1 has a sufficiently low Tg and excellent low-temperature curability, but has a problem of low tensile strength. Although electronic parts are required to be resistant to drops and impacts, in order to improve resistance to drops and impacts, it is desirable to increase the tensile strength of the adhesive.

The present invention was completed in view of the above-mentioned problems, and the object of the present invention is to provide an epoxy resin composition that can be cured in a short time even under low-temperature conditions, and can form a low glass transition point (T _g ), stretchable A high-strength hardened product and a sealing material containing the epoxy resin composition are provided. Another object of the present invention is to provide a cured product obtained by curing the above-mentioned epoxy resin composition or sealing material. Another object of the present invention is to provide an electronic component including the hardened material.

Under such circumstances, the inventors of the present invention have devoted themselves to detailed research in order to develop a curable composition that can be cured in a short time even under low-temperature conditions and can form a cured material with low T _g and high tensile strength. . As a result, they unexpectedly found that, in addition to a thiol-based hardener and an epoxy resin, a crosslinking density adjuster containing an aromatic monofunctional epoxy resin was used as a component of the curable composition. When the physical property values of the formed hardened material are adjusted to a predetermined range, the tensile strength of the obtained hardened material becomes high, that is, it has excellent drop impact resistance. Based on the above new insights, the present invention was further completed.

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

1. An epoxy resin composition, comprising the following components (A) to (D):

(A) Thiol-based hardener, including at least one multifunctional thiol compound having three or more thiol groups;

(B) At least 1 type of multifunctional epoxy resin;

(C) Cross-linking density adjuster, including at least 1 aromatic monofunctional epoxy resin; and

(D) Hardening catalyst;

And it can form a hardened product whose loss modulus (E") reaches the maximum temperature when the loss modulus (E") is maximum at 20°C or above and 55 range below ℃.

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

3. The epoxy resin composition as described in the preceding 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 any one of the preceding items 1 to 3, wherein component (C) contains an aromatic monofunctional epoxy resin.

5. A sealing material containing the epoxy resin composition as described in any one of the preceding items 1 to 4.

6. A hardened product obtained by hardening the epoxy resin composition as described in any one of the preceding paragraphs 1 to 4 or the sealing material as described in the preceding paragraph 5.

7. An electronic component including the hardened material described in item 6 above.

Figure 1 is a graph showing the relationship between the corrected tensile strength and the peak temperature (maximum value) of E".

The present invention will be described in detail below.

The epoxy resin composition (curable composition) of the present invention, as described above, contains a thiol-based curing agent (component (A)), a polyfunctional epoxy resin (component (B)), and a crosslinking density adjuster. (Component (C)) and curing catalyst (Component (D)) are essential components. These components (A) to (D) will be described below.

In addition, in this specification, according to the common practice in the field of epoxy resin, for the components constituting the epoxy resin composition before curing, even though the components are not polymers, the term "polymer" generally means "polymer". (especially synthetic polymers) the name of the term "resin".

(1) Thiol-based hardener (component (A))

The thiol-based hardener (component (A)) used in the present invention contains at least one polyfunctional thiol compound having three or more thiol groups, and the thiol group is related to the polyfunctional epoxy resin (described later). Reaction of the epoxy groups in component (B)) or the crosslink density adjuster (component (C)). Component (A) preferably contains a trifunctional and/or tetrafunctional thiol compound. The thiol equivalent is preferably 90 to 150g/eq, more preferably 90 to 140g/eq, and particularly preferably 90 to 130g/eq. In addition, trifunctional and tetrafunctional thiol compounds refer to thiol group compounds having 3 thiol groups and 4 thiol groups respectively.

In one aspect of the present invention, as the polyfunctional thiol compound, from the viewpoint of improving the moisture resistance of the cured product, it is preferable to use a partial structure that does not have hydrolyzability such as an ester bond and contains a non-hydrolyzable polyfunctional Component (A) of the thiol compound. Non-hydrolyzable multifunctional thiol compounds are not prone to hydrolysis even in high temperature and humid environments.

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. Furthermore, from the viewpoint of lowering _Tg , component (A) preferably contains a thiol resin without a urea bond.

-2,4,6(1H,3H,5H)-三酮(昭和電工股份有限公司製：Karenz MT(註冊商標)NR1)等。 Examples of the hydrolyzable polyfunctional thiol compound include: trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionate) Cyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), neopentylerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP ), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: EGMP-4), dineopenterythritol hexa(3-mercaptopropionate) (SC Organic Chemical Co., Ltd. Manufactured by: DPMP), neopentyritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd.: Karenz MT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethane) base)-1,3,5-three

-2,4,6(1H,3H,5H)-triketone (manufactured by Showa Denko Co., Ltd.: Karenz MT (registered trademark) NR1), etc.

The preferred non-hydrolyzable polyfunctional thiol compound that can be used in the present invention is a compound represented by 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 a mercaptomethyl group, a mercaptomethyl group, and a phenyl group. Select from the group consisting of ethyl and mercaptopropyl). Examples of compounds represented by formula (1) include 1,3,4,6-tetrakis(2-mercaptoethyl)acetyleneurea (trade name: TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), (1 , 3,4,6-tetrakis(3-mercaptopropyl)acetyleneurea (trade name: C3 TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), 1,3,4,6-tetrakis(mercaptomethyl) Acetylene urea, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylacetylene urea, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylacetylene urea, 1 ,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylacetylurea, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylacetylurea, 1, 3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylacetylene urea, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylacetylene Urea, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylacetylene urea, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenyl Acetylene urea, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylacetylene urea, etc. These can be used individually, or two or more types can be mixed and used. This Among others, particularly preferred ones are 1,3,4,6-tetrakis(2-mercaptoethyl)acetylurea and 1,3,4,6-tetrakis(3-mercaptopropyl)acetylurea.

Another preferred non-hydrolyzable polyfunctional thiol compound that can be used in the present invention is a compound represented by the following formula (2):

(R ⁸ ) _m -A-(R ⁷ -SH) _n (2)

(In the formula,

A is the residue of a polyol having n+m hydroxyl groups, containing n+m oxygen atoms derived from the above hydroxyl groups,

R ⁷ is each independently an alkylene group having 1 to 10 carbon atoms,

R ⁸ is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

m is an integer above 0,

n is an integer above 3,

The above-mentioned R ⁷ and R ⁸ are each bonded to the above-mentioned A via the above-mentioned oxygen atom). Two or more types of compounds represented by formula (2) may be used in combination. Examples of the compound represented by formula (2) include neopentyl erythritol tripropyl mercaptan (trade name: PEPT, manufactured by SC Organic Chemicals), neopentyl erythritol tetrapropyl mercaptan, and the like. Among these, neopentylerythritol tripropylmercaptan is particularly preferred.

As the non-hydrolyzable polyfunctional thiol compound, a trifunctional or higher polythiol compound having two or more sulfur 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(mercaptoethylthio)propane. -Tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithioctane, 5,7-dimercaptomethyl-1,11-dimercapto -3,6,9-trisulfoundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trisulfoundecane, 4,8-dimercaptomethyl- 1,11-dimercapto-3,6,9-tris Thioundecane, 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 -Thiopentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiohexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercapto Methylthio-1,7-dimercapto-2,6-dithioheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithionan alkane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiohexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3- Bis(mercaptomethylthio)-1-thiopropyl)3,7-dithiononane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis) (Mercaptomethylthio)-2-thiobutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)- 2-Thiobutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiotridecane, 3,5, 9,11,15,17-hexa(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexasulfonadecane, 9-(2,2-bis (Mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiopenca Heptane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathioundecane, 3,4,8,9,13 ,14-hexa(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexasulfohexadecan, 8-[bis(mercaptomethylthio)methyl [ 3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithioheptylthio]-1,3-dithiocyclohexane, 4-[3,5-bis(mercaptomethyl methylthio)-7-mercapto-2,6-dithioheptylthio]-6-mercaptomethylthio-1,3-dithiocyclohexane, 1,1-bis[4-(6- Mercaptomethylthio)-1,3-dithiocyclohexylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1, 3-Dithiocyclohexylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10- Tetrathioundecane, 3-[2-(1,3-dithiocyclobutyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4, 6,10-tetrathioundecane, 9-[2-(1,3-dithiocyclobutyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17 -Dimercapto-2,6,8,10,12,16-hexathiopentadecane, 3-[2-(1,3-dithiocyclobutyl)]methyl-7,9,13,15- Aliphatic polythiol compounds such as tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathioheptadecane; 4,6-bis[4-( 6-Mercaptomethylthio)-1,3-dithiocyclohexylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithiocyclohexyl methylthio]-1,3-dithiocyclohexane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiodecane Mono]-5-mercaptomethylthio-1,3-dithiocyclopentane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-di Thiohexylthio]-1,3-dithiocyclopentane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]-5-mercapto Methylthio-1,3-dithiocyclopentane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2, 4,7-trithioctyl]-5-mercaptomethylthio-1,3-dithiocyclopentane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto- 2,5-dithiohexylthio]methyl}-1,3-dithiocyclobutane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-disulfide Hexylthio]mercaptomethylthiomethyl-1,3-dithiocyclobutane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5, 7,10-tetrathioundecylthio]mercaptomethylthiomethyl-1,3-dithiocyclobutane, 2-[3-bis(mercaptomethylthio)methyl-5,6- Bis(mercaptomethylthio)-8-mercapto-2,4,7-trithioctyl]mercaptomethylthiomethyl-1,3-dithiocyclobutane, 4-{1-[2- (1,3-dithiocyclobutyl)]-3-mercapto-2-thiopropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiobutanyl Polythiol compounds with cyclic structures such as methylthio]-1,3-diocyclopentane.

(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, conventionally commonly used epoxy resins can be used as component (B). As mentioned above, multifunctional epoxy resin refers to an epoxy resin with two or more epoxy groups. In one aspect of the present invention, component (B) contains a bifunctional epoxy resin.

Multifunctional epoxy resins are roughly divided into aliphatic multifunctional epoxy resins and aromatic multifunctional epoxy resins.

Examples of aliphatic multifunctional epoxy resins include:

-Such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 -Hexylene glycol diepoxypropyl ether, trimethylolpropane diepoxypropyl ether base ether, polytetramethylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type glycol diglycidyl ether, dicyclopentyl ether Diene type diepoxy propyl ether diepoxy resin;

-Triepoxy resins such as trimethylolpropane triepoxypropyl ether and glycerol triepoxypropyl ether;

烷之脂環式環氧樹脂； -Such as vinyl (3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxide

Alkane alicyclic epoxy resin;

-glycidylamine type epoxy resin such as tetraepoxypropylbis(aminomethyl)cyclohexane;

- Hydantoin type epoxy resin such as 1,3-diepoxypropyl-5-methyl-5-ethyl hydantoin; and

-Such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, epoxy resin with polysiloxy skeleton, etc., but not limited to this wait.

Among the aforementioned examples, "cyclohexane type diglycidyl ether" refers to a bivalent epoxy propyl ether having "two epoxypropyl groups bonded to each other through ether bonds and having one cyclohexane ring as the parent structure." A compound with the structure of "saturated hydrocarbon group". "Dicyclopentadiene type diglycidyl ether" refers to a structure with "two epoxypropyl groups bonded to a divalent saturated hydrocarbon group with a dicyclopentadiene skeleton as the parent structure through ether bonds" compound of. Aliphatic multifunctional epoxy resin preferably has an epoxy equivalent weight of 90 to 450g/eq. In addition, as the cyclohexane-type diglycidyl ether, cyclohexanedimethanol diglycidyl ether is particularly preferred.

In one aspect of the present invention, component (B) includes an aliphatic multifunctional epoxy resin. When an aliphatic polyfunctional epoxy resin is used as the component (B), the combinable component (A) preferably contains a trifunctional thiol compound or a tetrafunctional thiol compound having an acetylene urea skeleton or an isocyanurate skeleton. The ratio of the epoxy functional group equivalent of the aliphatic multifunctional epoxy resin to the thiol compound having an acetylene urea skeleton or an isocyanurate skeleton ([epoxy functional group equivalent]/[thiol functional group equivalent]) The optimal range 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 an acetylene urea skeleton or an isocyanurate skeleton. As component (A), use an acetylene urea skeleton or isocyanuride In the case of a trifunctional thiol compound or a tetrafunctional thiol compound having an acid ester skeleton, it is preferable to use an epoxy resin having a cyclohexane type diglycidyl ether or polysiloxy skeleton as component (B). Particularly preferred systems use 1,4-cyclohexanedimethanol diglycidyl ether or 1,3-bis(3-epoxypropoxypropyl)-1,1,3,3-tetramethyldisilicon oxane.

In addition, in one aspect of the present invention, component (A) contains a trifunctional thiol compound or a tetrafunctional thiol compound that does not have an acetylene urea skeleton or an isocyanurate skeleton (specifically, a polyether skeleton). , polythioether skeleton or polyester skeleton trifunctional thiol compound or tetrafunctional thiol compound). In order to set the temperature when E" is maximum into the desired range, the epoxy resin composition contains an aliphatic polyfunctional epoxy resin, a trifunctional thiol compound that does not have an acetylene urea skeleton or an isocyanurate skeleton, or The total amount of the tetrafunctional thiol compound is preferably 10 mass% or more and 55 mass% or less, more preferably 20 mass% or more and 50 mass% or less, and still more preferably 25 mass% or more and 50 mass% or less.

Aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin having a structure containing aromatic rings such as benzene rings. Among the epoxy resins commonly used in the past, there are many multifunctional epoxy resins such as bisphenol A type epoxy resin. Examples of aromatic polyfunctional epoxy resins include:

-Bisphenol A type epoxy resin;

-Branched multifunctional bisphenol A-type epoxy resin such as p-glycidyloxyphenyldimethyltribisphenolA-diglycidylether;

-Bisphenol F epoxy resin;

-Novolak type epoxy resin;

-Tetrabromobisphenol A type epoxy resin;

-Flu type epoxy resin;

-Biphenyl aralkyl epoxy resin;

- Diepoxy resin such as 1,4-phenyl dimethanol diglycidyl ether;

-Biphenyl-type epoxy resin such as 3,3',5,5'-tetramethyl-4,4'-diepoxypropyloxybiphenyl;

-Epoxypropylamine-type epoxy resins such as diepoxypropylaniline, diepoxypropyltoluidine, tripoxypropyl-p-aminophenol, and tetraepoxypropylisoxylylenediamine; and

- Epoxy resins containing naphthalene rings, but not limited to these. From the viewpoint of compatibility with a thiol compound, component (B) preferably contains an aromatic polyfunctional epoxy resin rather than an aliphatic polyfunctional epoxy resin. As aromatic multifunctional epoxy resins, the preferred ones are bisphenol F epoxy resin, bisphenol A epoxy resin and epoxypropylamine epoxy resin, among which the epoxy equivalent weight of 90 to 200g is particularly preferred. /eq, the best ones are those with epoxy equivalents between 110 and 190g/eq.

When an aromatic polyfunctional epoxy resin is used as the component (B), the component (A) that can be combined is preferably a trifunctional thiol compound or a tetrafunctional thiol compound having a polyether skeleton, a polythioether skeleton, or a polyester skeleton. . The ratio of the epoxy functional group equivalent of the aromatic polyfunctional epoxy resin to the thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton ([epoxy functional group equivalent]/[thiol functional group equivalent] ) is preferably 0.30 to 1.10. In addition, when using a trifunctional thiol compound or a tetrafunctional thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton as the component (A), the component (B) is preferably a bisphenol A-type epoxy resin. , at least one of bisphenol F epoxy resin and naphthalene ring-containing epoxy resin.

In addition, in order to set the temperature when E" is the maximum within the desired range, in the epoxy resin composition, aromatic epoxy resins (monofunctional and polyfunctional aromatic epoxy resins), and those having an acetylene urea skeleton or different The total amount of the trifunctional thiol compound or the tetrafunctional thiol compound in the cyanurate skeleton is preferably 45 mass% or more and 90 mass% or less, more preferably 50 mass% or more and 80 mass% or less, and still more preferably 50 mass%. % or more and less than 75% by mass.

(3) Cross-linking density adjuster (component (C))

The crosslinking density adjuster (component (C)) used in the present invention is not particularly limited as long as it contains at least one aromatic monofunctional epoxy resin. Monofunctional epoxy resin is an epoxy resin having one epoxy group and has been used as a reactive diluent to adjust the viscosity of epoxy resin compositions. Monofunctional epoxy resins are roughly divided into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the epoxy equivalent of component (C) is preferably 180 to 400 g/eq. In the present invention, from the viewpoint of viscosity and low volatility, component (C) preferably contains aromatic monofunctional epoxy resin. Furthermore, component (C) is more preferably essentially an aromatic monofunctional epoxy resin.

Examples of the aromatic monofunctional epoxy resin contained as component (C) include phenyl glycidyl ether, tolyl glycidyl ether, and p-second butyl phenyl glycidyl ether. , styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-epoxypropyl phthaloimide, etc. , but not limited to this. Among these, p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tert-butylphenyl glycidyl ether is particularly preferred. Examples of aliphatic monofunctional epoxy resins include: n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl Glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane alkane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, glycidyl neodecanoate, etc., but are not limited to these wait.

(4) Hardening 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 for epoxy resin (the component (B)), and a conventional one can be used. Component (D) is preferably a latent hardening catalyst. The latent curing catalyst is a compound that is activated by heating in an inactive state at room temperature to function as a curing catalyst. Examples thereof include: imidazole compounds that are solid at room temperature; amine compounds and cyclic compounds; Solid dispersion type amine adduct systems such as reaction products of oxygen compounds (amine-epoxy adduct systems) are potentially hardening contacts. media; reaction products of amine compounds and isocyanate compounds or urea compounds (urea type adduct system), etc. By using the above-mentioned component (D), the epoxy resin composition of the present invention can be hardened in a short time even under low-temperature conditions.

As a representative example of commercially available latent curing catalysts, examples of amine-epoxy adduct systems (amine adduct systems) include: "Amicure PN-23" (product of Ajinomoto Fine-Techno Co., Ltd. Name), "Amicure PN-40" (trade name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (trade name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (ACR Co., Ltd. Trade name), "Hardener "Novacure HXA9322HP" (trade name of Asahi Kasei Co., Ltd.), "Novacure HXA3922HP" (trade name of Asahi Kasei Co., Ltd.), "Novacure HXA3932HP" (trade name of Asahi Kasei Co., Ltd.), "Novacure HXA5945HP" (trade 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. Also, examples of urea-type adduct systems include: "Fujicure FXE-1000" ( T&K TOKA Co., Ltd.'s trade name), "Fujicure FXR-1030" (T&K TOKA Co., Ltd.'s trade name), etc., but are not limited to these. Component (D) may be used individually or in combination of 2 or more types. As component (D), from the viewpoint of pot life and curability, a solid-dispersed amine adduct-based latent curing catalyst is preferred.

In addition, some components (D) are provided in the form of a dispersion dispersed in a polyfunctional epoxy resin. When using component (D) in this form, attention should be paid to the amount of the polyfunctional epoxy resin dispersed therein and the amount of the above-mentioned component (B) included in the epoxy resin composition of the present invention.

The thiol functional group equivalent refers to the total number of thiol groups of the thiol compound contained in the ingredient or composition of concern, divided by the mass (g) of the thiol compound contained in the ingredient or composition of concern. The quotient obtained by the thiol equivalent (when multiple thiol compounds are included, it is the sum of the quotients calculated in this way for each thiol compound). Thiol equivalents can be determined by iodine titration. This method is widely known, for example, disclosed in paragraph 0079 of Japanese Patent Application Laid-Open No. 2012-153794. When the thiol equivalent cannot be determined by this method, it can also be calculated as a quotient obtained by dividing the molecular weight of the thiol compound by the number of thiol groups in 1 molecule of the thiol compound.

On the other hand, the epoxy functional group equivalent refers to the total number of epoxy groups of the epoxy resin contained in the same component or composition (components (B) and (C)), which is the total number of epoxy groups contained in the component or composition of concern. The quotient obtained by dividing the mass (g) of the epoxy resin by the epoxy equivalent of the epoxy resin (when multiple epoxy resins are included, it is the sum of the quotients calculated in this way for each epoxy resin). The epoxy equivalent can be determined by the method described in JIS K7236. When the epoxy equivalent cannot be determined by this method, it can also be calculated as the quotient obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule of the epoxy resin.

An epoxy resin composition in which the thiol-based hardener is in excess relative to the epoxy resin will form a hardened product with a low initial T _g (T _g immediately after hardening). However, when the thiol-based curing agent is present in an excess relative to the epoxy resin in this way, the number of thiol groups remaining in the cured product in an unreacted state without reacting with the epoxy groups increases. The present inventors disclosed in Patent Document 1 a composition with a small change in T _g after a heat resistance test. However, they later found that this composition had poor performance in a humidity resistance reliability test (especially 85°C, 85% environment for 100 hours). , after the test, new cross-links may occur with each other due to excess thiol groups. The progress of this cross-linking is more stable than when the epoxy resin is in excess of the thiol-based hardener, but it also causes an increase in T _g . In one aspect of the present invention, therefore, the ratio of the sum of the epoxy functional group equivalents of the above-mentioned components (B) and (C) to the thiol functional group equivalents of the above-mentioned component (A) ([epoxy functional group equivalent] /[thiol functional group equivalent]) is preferably from 0.70 to 1.10, more preferably from 0.75 to 1.10, particularly preferably from 0.80 to 1.05. In the curable composition, since there are epoxy groups contained in the component (C) that reduce the unreacted thiol groups, most of the unreacted thiol groups disappear as a result of the reaction between them. The polyfunctional epoxy resin contained in the above component (B) has the ability to connect two molecules of the polyfunctional thiol compound contained in the above component (A) to extend the polymer chain or form a cross-link between the polymer chains. function. However, since the monofunctional epoxy resin contained in the above component (C) does not have such a function, it can suppress the occurrence of new cross-links that cause the T _g of the cured product to increase due to the reaction between the components (A) and (C). Union. Therefore, the cured product formed by this curable composition has a small content of functional groups capable of forming new cross-links. Therefore, even after a long time has passed after curing, almost no increase in T _g due to the formation of new cross-links is observed. .

In one aspect of the present invention, the ratio of the sum of the epoxy functional group equivalents of the above-mentioned components (B) and (C) to the thiol functional group equivalents of the above-mentioned component (A) ([epoxy functional group equivalent]/[ If the thiol functional group equivalent]) is 0.70 or more and 1.10 or less, for both the epoxy group and the thiol group in the composition, the reaction between the epoxy group and the thiol group becomes certain. With the above ratio, the characteristics of the obtained hardened product are ideal. If the above ratio is less than 0.70, there will be an excess of thiol groups relative to the epoxy groups, resulting in an increase in the number of unreacted thiol groups remaining in the hardened product, and it will be difficult to suppress the hardening caused by the reaction between the thiol groups. The T _g of the object rises. On the other hand, when the above ratio exceeds 1.10, there will be an excess of epoxy groups relative to the thiol groups, and in addition to the reaction between the epoxy groups and the thiol groups, the reaction between the excess epoxy groups will also proceed (homopolymerization) . As a result, in the resulting hardened product, intermolecular cross-links are formed due to the reaction between these two parties, so the cross-link density is too high, resulting in an increase in T _g . Or it may make it difficult to harden at low temperatures such as 80°C and 1 hour.

If necessary, the curable composition of the present invention may contain any components other than the above-mentioned components (A) to (D), such as those described below.

‧Stabilizer

If necessary, a stabilizer can be added to the epoxy resin composition of the present invention. In order to improve the storage stability and extend the pot life of the epoxy resin composition of the present invention, a stabilizer can be added. As the stabilizer for the single-liquid adhesive agent using epoxy resin as the main ingredient, various conventional stabilizers can be used. However, in view of the high effect of improving storage stability, it is preferably selected from the group consisting of liquid borate ester compounds, At least one member from the group consisting of aluminum chelate and organic acid.

Examples of liquid borate compounds include: 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), boric acid Trimethyl ester, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, boric acid Trioctyl ester, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane , bis(1,4,7,10-tetraoxadecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxa1decyl) Borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-creyl borate, triethanolamine borate, etc. The liquid borate compound is preferable because it is liquid at normal temperature (25°C) and can keep the viscosity of the formulation low. 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 adding a stabilizer, the amount to be added is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and still more preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of components (A) to (D). parts by mass.

‧Filling agent

If necessary, fillers can be added to the epoxy resin composition of the present invention. When using the epoxy resin composition of the present invention as a one-liquid adhesive, adding a filler to the composition improves the moisture resistance and heat cycle resistance of the bonded part, especially the heat cycle resistance. Improved heat cycle resistance by adding fillers The increase is because the linear expansion coefficient of the hardened material is reduced, which can inhibit the expansion and contraction of the hardened material caused by thermal cycles.

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

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

‧Coupling agent

If necessary, a coupling agent can 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 bonding strength. As the coupling agent, various silane coupling agents such as epoxy type, amine 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-triethoxysilane. Silyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methyl Acrylyloxypropylmethyltrimethoxysilane, 3-acrylyloxypropyltrimethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, etc. These silane coupling agents may be used alone, or two or more types may be used in combination.

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

‧Other additives

If necessary, other additives may be added to the epoxy resin composition of the present invention, such as carbon black, titanium black, ion trapping agent, leveling agent, antioxidant, and defoaming within the scope that does not undermine the gist of the present invention. agents, thixotropic agents, viscosity adjusters, flame retardants, colorants, solvents, etc. The types and amounts of each additive are determined according to general methods.

The epoxy resin composition of the present invention can form a hardened product in a temperature range of 20°C or more and 55°C or less when the loss modulus (E”) is maximum. The loss modulus corresponds to the dynamic elastic modulus of the object expressed as a complex number. The imaginary part of the complex elastic modulus represents the lost energy of viscoelasticity in dynamic behavior. In this specification, unless otherwise noted, the loss modulus means the frequency is 10Hz, the temperature rise rate is 3℃/min, and the strain amplitude is 5.0 μ m, value measured by dynamic viscoelasticity (DMA) by tensile method.

The industry can appropriately adjust the amounts of components (A) to (D) constituting the epoxy resin composition of the present invention until the cured product formed by the composition has a predetermined loss modulus. In addition, the measurement method of the loss modulus is publicly known, and the industry can easily measure the loss modulus using conventional dynamic viscoelasticity measuring devices.

As mentioned above, the temperature of the cured product formed from the epoxy resin composition of the present invention when the loss modulus (E") reaches the maximum is in the range of 20°C or more and 55°C or less. This temperature is not within the above range. For epoxy resin compositions, the tensile strength of the cured product, that is, the drop and impact resistance cannot be fully improved.

The epoxy resin composition of the present invention can form a hardened product in which the temperature when the loss modulus is maximum is preferably in the range of 20°C or more and 50°C or less (more preferably 20°C or more and 45°C or less).

From the viewpoint of making the dynamic viscoelastic properties of the cured material as described above, in the epoxy resin composition of the present invention, the molar number ratio (B)/(A) of the component (B) to the component (A) is preferable. It is above 1.15 and below 1.45.

In addition, for the same reason, in the epoxy resin composition of the present invention, the molar ratio (C)/(A) of component (C) to 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) means that the cross-linking points of the component (A) including a thiol compound having three or more thiol groups are reduced, For example, in the case of a thiol compound having four thiol groups, it is used as a bifunctional thiol compound or a trifunctional thiol compound. When the aforementioned ratio is less than 1.15, there is too little polyfunctional epoxy resin that is a cross-linking component, and the resulting hardened product may have properties like a thermoplastic resin that melts at high temperatures. On the other hand, when the aforementioned ratio exceeds 1.45, the polyfunctional epoxy resin, which is a cross-linking component, becomes too large, and excessive intermolecular formation occurs due to the reaction of components (A) and (B) in the obtained cured product. Cross-linking, there is a concern that the cross-linking density will become too high and the tensile strength will decrease.

The relationship between the molar ratio (C)/(A) of the aforementioned component (C) and the component (A) means that the aforementioned component (A) is relative to the number (amount) of epoxy groups contained in the aforementioned component (C). There is a moderate excess of thiol groups. By satisfying this relationship, it is preferable to obtain a hardened product with an appropriate cross-link density formed by the reaction of components (A) and (B).

By satisfying the relationship between the molar ratio (B)/(A) of component (B) and component (A), and the molar ratio (C)/(A) of component (C) and component (A) , the thiol group of component (A) that has not reacted with component (B) will react with component (C), so that the number of unreacted thiol groups remaining in the cured product is reduced, and the resulting cured product has appropriate characteristics.

The cured product formed by the epoxy resin composition of the present invention is particularly selected from the group consisting of LCP (liquid crystal polymer), PC (polycarbonate), PBT (polybutylene terephthalate), SUS, alumina, Adheres made of nickel (including those whose surface is plated with nickel) exhibit excellent tensile strength. These adherends can be processed by plasma, etc. Perform surface treatment. In this specification, "tensile strength" typically means the tensile strength when the adherends are made of such materials.

The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, ingredients (A) to (D) and other additives as needed are introduced into an appropriate mixer simultaneously or separately, and if necessary, they are melted by heating while stirring and mixing to form a uniform composition. The epoxy resin composition of the present invention can be obtained. This mixer is not particularly limited, and a mill equipped with a stirring device and a heating device, a Henschel mixer, a three-roller mill, a ball mill, a planetary mixer, a bead mill, etc. can be used. Furthermore, these devices can also be used in appropriate combination.

The epoxy resin composition thus obtained is thermosetting, and under the condition of a temperature of 80° C., it hardens preferably within 5 hours, more preferably within 1 hour. In addition, hardening can also be carried out at a high temperature such as 150°C for several seconds and in an ultra-short time. When the curable composition of the present invention is used to manufacture image sensor modules containing parts that deteriorate under high temperature conditions, it is preferable to thermally harden the same composition at a temperature of 60 to 90°C for 30 to 120 minutes. , or heat harden it at a temperature of 120 to 200°C for 1 to 300 seconds.

The epoxy resin composition of the present invention can be cured in a short time even under low-temperature conditions to form a cured product with low _Tg . The cured product of the epoxy resin composition of the present invention has a _Tg of preferably 65°C or lower, more preferably 60°C or lower, and still more preferably 50°C or lower. Furthermore, from the viewpoint of adhesiveness, the _Tg of the cured material is preferably 30°C or higher, more preferably 32°C or higher. In the present invention, T _g can be measured using a dynamic thermomechanical measurement device (DMA) in the range of -20°C to 110°C, frequency 1 to 10Hz, temperature rise rate 1 to 10°C/min, and strain amplitude 5.0 μm, by stretching. Find out through the law. The optimal frequency is 10Hz, and the optimal heating rate is 3℃/min. T _g is calculated from the peak temperature of the loss tangent (tanδ) obtained from the loss modulus (E”) and the 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 for fixing, joining or protecting components constituting the electronic components, a sealing material, a dam agent, or the like. raw material.

The present invention also provides a sealing material containing the epoxy resin composition of the present invention. The sealing material of the present invention is suitable as a filling material for protecting or fixing modules, electronic components, etc., for example.

Furthermore, the present invention also provides a cured product obtained by curing the epoxy resin composition or sealing material of the present invention.

The present invention further provides electronic components including the hardened product of the present invention.

(Example)

The present invention is illustrated below through examples, but the present invention is not limited thereto. In addition, in the following examples, parts and % mean parts by mass and % by mass unless otherwise specified.

Examples 1 to 9, Comparative Examples 1 to 3

According to the preparation shown in Tables 1 to 2, a predetermined amount of each component was mixed using a 3-roll mill, thereby preparing an epoxy resin composition. In Tables 1 to 2, the amount of each component is expressed in parts by mass (unit: g).

‧Mercaptan hardener (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)acetyleneurea (trade name: TS-G, manufactured by Shikoku Chemical Industry Co., Ltd., thiol equivalent: 100)

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

(A-3): Neopenterythritol tetrakis(3-mercaptopropionate) (trade name: PEMP, manufactured by SC Organic Chemicals, thiol equivalent: 122)

‧Epoxy resin (component (B))

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

(B-1): Bisphenol F epoxy resin (trade name: YDF-8170, manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., epoxy equivalent: 159)

(B-2): Bisphenol F epoxy resin/bisphenol A epoxy resin mixture (trade name: EXA-835LV, manufactured by DIC Co., Ltd., epoxy equivalent: 165)

(B-3): Dicyclopentadiene-type epoxy resin (trade name: EP4088L, manufactured by ADEKA Co., Ltd., 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 contract company System, epoxy equivalent: 181)

‧Crosslinking density adjuster (component (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 Co., Ltd., epoxy equivalent: 205)

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

(C-3): 2-ethylhexylglycidyl ether (trade name: Denacol EX121, manufactured by Nagase ChemteX Co., Ltd., epoxy equivalent: 187)

‧Harding catalyst (component (D))

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

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

The above-mentioned latent curing catalyst (D-1) is a latent curing catalyst in the form of fine particles dispersed in an epoxy resin (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin (epoxy equivalent: 170)) is provided in the form of a dispersion (a mixture of latent curing catalyst/bisphenol A-type epoxy resin and bisphenol F-type epoxy resin = 33/67 (mass ratio)). (D-1) in Tables 1 to 2 is the mass part of the dispersion liquid containing the latent curing catalyst. The epoxy resin constituting this dispersion is regarded as a part of component (B). Therefore, (B) of "(B)/(A) (molar ratio)" in Tables 1 to 2 includes the amount of the epoxy resin in (D-1).

‧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 Admatechs Co., Ltd.)

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

In the Examples and Comparative Examples, the characteristics of the cured product obtained by curing the epoxy resin composition were measured in the following manner.

(Preparation of hardened materials)

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 cured products.

<Loss modulus of hardened material (E”)>

The measurement was performed in accordance with the T _g measurement method of Japanese Industrial Standard JIS C6481. Specifically, first, a Teflon (registered trademark) sheet was affixed to the surface of a glass plate with a thickness of 3 mm, and spacers (overlaid with heat-resistant tape) were placed at two places so that the film thickness when cured became 400±150 μm. adult). Next, the resin composition was applied between the spacers, sandwiched between another glass plate with a Teflon (registered trademark) sheet attached to the surface so as not to mix air bubbles, and cured at 80° C. for 120 minutes to obtain a cured product. Finally, the hardened material was peeled off from the glass plate on which the Teflon (registered trademark) sheet was attached, and then cut into a predetermined size (10 mm × 40 mm) with a cutter to obtain a test piece. Also, smooth the cuts with sandpaper. For this hardened product, a dynamic thermomechanical measuring device (DMA) (manufactured by Seiko Instruments) was used, and the tensile method was carried out in the range of -20°C to 110°C at a frequency of 10 Hz, a temperature rise rate of 3°C/min, a strain amplitude of 5.0 μm, and a temperature rise rate of 3°C/min. Measure the loss modulus (E") of the hardened material and find the temperature (°C) at which E" reaches the maximum. The results are shown in Tables 1 to 2.

〈Actual tensile strength and corrected tensile strength of hardened materials〉

On an alumina plate having a length of 20 mm, a width of 20 mm, and a thickness of 1.6 mm, spacers (heat-resistant tape with a thickness of 150 μm) were arranged at two places. Next, 1 mg of the resin composition was applied between the spacers. The spacer was covered with a 9 mm square bright nickel plated thick plate (2.5 g) so as to be in contact with the coated resin composition. Then, the test body was obtained by heating and hardening at 80° C. for 120 minutes. A moisture-hardening adhesive was used to attach the nut to the upper part of the thick plate of the test body. In order to avoid peeling between the thick plate and the nut when measuring the tensile strength, the thick plate and the nut were left for 12 hours to fully Engagement. Then, after fixing the alumina plate to a precision load measuring instrument (manufactured by Aikoh Engineering, model: 1605HTP) so that the joint surface becomes horizontal, a rope is passed through the hole of the nut, and the rope is attached to the jig, and the temperature is maintained at 23°C Apply tensile load in the vertical direction at a speed of 12mm/min. The maximum load applied before separation of the alumina plate and the thick plate was divided by the bonding area between the alumina plate and the thick plate, and the value obtained was regarded as the measured tensile strength (N=6). The unit is N/mm ² . In addition, the corrected tensile strength was calculated from the measured tensile 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 tensile strength = measured tensile 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 needed. However, it can be seen from the comparison between Examples 1 and 2 that when the content of component (E) (filler) increases, the actual measurement of the cured product Tensile strength tends to decrease. The above-mentioned corrected tensile strength is the tensile strength after offsetting the influence of the component (E).

[Table 1]

[Table 2]

As is clear from Tables 1 to 2, in any of Examples 1 to 9, the tensile strength after hardening (especially the corrected tensile strength) is a satisfactory value.

On the other hand, in Comparative Examples 1 and 2 in which the temperature when E" of the cured product is maximum is not within the predetermined range, and in Comparative Example 3 that does not contain the component (C), the tensile strength after curing is insufficient. From the Comparative Example 3 It can be seen that there is no For an epoxy resin composition with a predetermined composition, even if the temperature of the cured product when E" is maximum is within a predetermined range, the tensile strength after curing is not sufficiently improved.

The relationship between the corrected tensile strength in Tables 1 to 2 and the peak temperature (maximum value) of E" is shown in Figure 1. In Figure 1, it can be seen from the straight line relationship between I and II that the sulfur content of component (A) is Alcohol functional group equivalent, if the epoxy functional group equivalent of component (C) is more, the tensile strength will be higher.

(Industrial availability)

The epoxy resin composition of the present invention can be cured in a short time to form a cured product even under low temperature conditions. This hardened material shows low T _g and has moderate softness and flexibility. In addition, since the cured product exhibits high tensile strength, electronic components with excellent drop and impact resistance can be easily produced 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, sealing material, dam agent, etc. for semiconductor devices and electronic components in which a plurality of components are assembled and assembled using different materials.

Claims (8)

An epoxy resin composition comprising the following components (A) to (D): (A) a thiol-based hardener, including at least one multifunctional thiol compound having three or more thiol groups; (B) At least 1 kind of bifunctional epoxy resin; (C) cross-linking density adjuster, including at least 1 kind of aromatic monofunctional epoxy resin; and (D) hardening catalyst; wherein, component (B) and component (A) The molar ratio (B)/(A) is 1.15 or more and 1.45 or less, and a hardened product can be formed. In the DMA measurement by the tensile method at a frequency of 10 Hz, a temperature rise rate of 3°C/min, The temperature when the loss modulus (E”) is maximum is in the range of 20°C or more and 55°C or less. The epoxy resin composition according to claim 1, wherein component (A) contains a trifunctional or tetrafunctional thiol compound. The epoxy resin composition according to claim 1 or 2, wherein the ratio of the sum of the epoxy functional group equivalents of components (B) and (C) to the thiol functional group equivalents of component (A) ([cyclo Oxygen functional group equivalent]/[thiol functional group equivalent]) is 0.70 or more and 1.10 or less. The epoxy resin composition according to claim 1 or 2, wherein the molar ratio (C)/(A) of component (C) to component (A) is 0.55 or more and 1.65 or less. The epoxy resin composition according to claim 1 or 2, wherein component (C) is an aromatic monofunctional epoxy resin. A sealing material comprising the epoxy resin composition as described in any one of claims 1 to 5. A hardened product obtained by hardening the epoxy resin composition according to any one of claims 1 to 5 or the sealing material according to claim 6. An electronic component including the hardened material described in claim 7.

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