TW202116849A - 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 epoxy resin composition, and an electronic component containing the cured product.

At present, for the assembly and installation of electronic parts used in semiconductor devices, such as semiconductor chips, for the purpose of maintaining reliability, etc., adhesives and sealing materials containing curable resin compositions, especially epoxy resin compositions, are often used Wait. Especially in the case of semiconductor devices including parts that deteriorate under high temperature conditions, all manufacturing steps must be performed under low temperature conditions. Therefore, adhesives and sealing materials used to manufacture such devices are required to exhibit sufficient curability even under low temperature conditions. As far as the production cost is concerned, it is also required to harden in a short time.

The epoxy resin composition used in such adhesives and sealing materials for electronic parts (hereinafter sometimes simply referred to as "curable composition") generally contains 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 epoxy groups in the epoxy resin. Among such curable compositions, it is known that a thiol-based curing agent is used as a curing agent, which can be cured moderately in a short time even under low temperature conditions such as 0°C to -20°C. The mercaptan hardener contains more than 2 mercaptans -Based compounds, that is, multifunctional thiol compounds. As an example of such a curable composition, what is disclosed in Patent Document 1 can be cited.

The epoxy resin composition system can form a cured product with various characteristics according to its composition. This point depends on the purpose of use of the curable composition, etc. It is not preferable to have a high glass transition point (T _g ). For example, when using this curable composition, two parts made of different materials are joined together.

If the temperature around an assembly formed by joining two parts made of different materials to each other with an adhesive changes, thermal stress will occur in these parts due to the thermal expansion coefficient of the materials. This thermal stress is uneven due to the difference in thermal expansion coefficients, and cannot cancel each other out, resulting in deformation of the assembly. The stress that occurs with this deformation, especially on the joints of the parts, that is, the hardened material of the adhesive, may cause cracks in the hardened material as the case may be. 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 flexibility (low elasticity coefficient) to the extent that it can follow the deformation of the assembly caused by the thermal expansion of the parts after hardening. _{Therefore, the T g of the} cured product is required to be moderately low.

[Prior Technical Literature]

[Patent Literature]

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

However, the present inventors found 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 the drop shock resistance is required for electronic parts, in order to improve the drop shock resistance, it is desirable to increase the tensile strength of the adhesive.

The present invention was completed in view of the above-mentioned problems. 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 ) and stretch A hardened product with high strength 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 epoxy resin composition or sealing material. Another object of the present invention is to provide an electronic component containing the hardened product.

Under such circumstances, the inventors of the present invention intend to develop a _{curable composition that can be cured in a short time even under low temperature conditions to form a cured product with low T g} and high tensile strength, and they have devoted themselves to detailed research. . As a result, it was unexpectedly discovered that, in addition to thiol-based curing agents and epoxy resins, crosslinking density modifiers containing aromatic monofunctional epoxy resins were used as components of the curable composition. By adjusting the physical properties of the formed cured product to a predetermined range, the tensile strength of the resulting cured product will increase, that is, it will have excellent drop impact resistance. Based on the above new findings, the present invention has been completed.

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

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

(A) A thiol-based hardener, including at least one multifunctional thiol compound having 3 or more thiol groups;

(B) At least one multifunctional epoxy resin;

(C) A crosslinking density modifier, including at least one aromatic monofunctional epoxy resin; and

(D) Hardening catalyst;

And it can form a hardened product. The hardened product has a frequency of 10 Hz, a heating rate of 3°C/min, and a DMA measurement by the stretching method. The temperature at which the loss modulus (E") is maximum is 20°C or more, 55 The range below ℃.

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

3. The epoxy resin composition according to 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 the component (C) contains an aromatic monofunctional epoxy resin.

5. A sealing material comprising the epoxy resin composition as described in any one of 1 to 4 above.

6. A cured product obtained by curing the epoxy resin composition as described in any one of 1 to 4 above or the sealing material as described in 5 above.

7. An electronic component comprising the hardened product as described in paragraph 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 mercaptan-based curing agent (component (A)), a multifunctional epoxy resin (component (B)), and a cross-linking density regulator (Component (C)) and hardening catalyst (Component (D)) are essential components. The following describes these components (A) to (D).

In addition, in this specification, in accordance with the conventions in the field of epoxy resins, as regards the components constituting the epoxy resin composition before curing, although the components are not polymers, they may be used in general. (Especially synthetic polymers) the name of the term "resin".

(1) Mercaptan hardener (component (A))

The thiol curing agent (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 combined with the polyfunctional epoxy resin ( The epoxy group in the component (B)) or the crosslinking density modifier (component (C)) reacts. The component (A) preferably contains a trifunctional and/or tetrafunctional thiol compound. The mercaptan equivalent is preferably 90 to 150 g/eq, more preferably 90 to 140 g/eq, particularly preferably 90 to 130 g/eq. In addition, trifunctional and tetrafunctional thiol compounds refer to thiol 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 hydrolyzable ester bonds or the like and contains non-hydrolyzable polyfunctional Component (A) of thiol compound. The non-hydrolyzable multifunctional thiol compound is not easily hydrolyzed even in a high temperature and humidity environment.

In another aspect of the present invention, the component (A) includes a thiol compound having an ester bond in the molecule and a thiol compound having no ester bond in the molecule. In addition, from _{the viewpoint of low T g} , it is preferable that the component (A) 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 hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropane) (Oxyoxy)-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), dineopentaerythritol hexa(3-mercaptopropionate) (SC Organic Chemical Co., Ltd.) Production: DPMP), neopentyl erythritol tetrakis (3-mercaptobutyrate) (Showa Denko Co., Ltd. production: Karenz MT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl) 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 carbons, or a phenyl group, and R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of mercaptomethyl and mercapto Selected from the group consisting of ethyl and mercaptopropyl). Examples of the compound represented by formula (1) include 1,3,4,6-tetra(2-mercaptoethyl)acetylene carbamide (trade name: TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), (1 ,3,4,6-Tetra(3-mercaptopropyl)acetylene carbamide (trade name: C3 TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), 1,3,4,6-tetra(mercaptomethyl) Acetylene carbamide, 1,3,4,6-tetra(mercaptomethyl)-3a-methyl acetylene carbamide, 1,3,4,6-tetra(2-mercaptoethyl)-3a-methyl acetylene carbamide, 1 ,3,4,6-Tetra(3-mercaptopropyl)-3a-methylacetylene carbamide, 1,3,4,6-tetra(mercaptomethyl)-3a,6a-dimethylacetylene carbamide, 1, 3,4,6-Tetra(2-mercaptoethyl)-3a,6a-dimethylacetylene carbamide, 1,3,4,6-tetra(3-mercaptopropyl)-3a,6a-dimethylacetylene Urea, 1,3,4,6-tetra(mercaptomethyl)-3a,6a-diphenylacetylene carbamide, 1,3,4,6-tetra(2-mercaptoethyl)-3a,6a-diphenyl Acetylacetylene carbamide, 1,3,4,6-tetra(3-mercaptopropyl)-3a,6a-diphenylacetylene carbamide, etc. These may be used alone, or two or more of them may be mixed for use. Among the others, particularly preferred are 1,3,4,6-tetrakis(2-mercaptoethyl)acetylene carbamide and 1,3,4,6-tetrakis(3-mercaptopropyl)acetylene carbamide.

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, and contains n+m oxygen atoms derived from the aforementioned hydroxyl groups,

R ^{7 is} each independently an alkylene group having 1 to 10 carbons,

R ^{8 is} each independently a hydrogen atom or an alkyl group having 1 to 10 carbons,

m is an integer above 0,

n is an integer greater than 3,

The R ⁷ and R ⁸ are each bonded to A via the oxygen atom). The compound represented by formula (2) may be used in combination of two or more kinds. Examples of the compound represented by the formula (2) include neopentyl erythritol tripropyl mercaptan (trade name: PEPT, manufactured by SC organic chemistry), neopentyl erythritol tetrapropyl mercaptan, and the like. Among these, neopentylerythritol tripropyl mercaptan is particularly preferred.

As the non-hydrolyzable polyfunctional thiol compound, a trifunctional or more polythiol compound having two or more sulfur bonds in the molecule can also be used. Examples of such thiol compound systems 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-dithiooctane, 5,7-dimercaptomethyl-1,11-dimercapto -3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,8-Dimercaptomethyl- 1,11-dimercapto-3,6,9-tri Thioundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3 ,3-Tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 1,1,5,5-tetra(mercaptomethylthio)-3 -Thiopentane, 1,1,6,6-tetra(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-trithiononane Alkyl, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiohexane, 1,1,9,9-tetra(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-tetra(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-hexathianonadecane, 9-(2,2-bis (Mercaptomethylthio)ethyl)-3,5,13,15-Tetra(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathia Heptadecane, 3,4,8,9-tetra(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13 ,14-hexa(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiohexadecane, 8-(bis(mercaptomethylthio)methyl ]-3,4,12,13-tetra(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiopentadecane, 4,6-bis[ 3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithioheptylthio]-1,3-dithiocyclohexane, 4-[3,5-bis(mercapto Thiol)-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-tetrathiaundecane, 9-[2-(1,3-dithiocyclobutyl)]methyl-3,5,13,15-tetra(mercaptomethyl) Thio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithiocyclobutyl)]methyl-7 ,9,13,15-Tetra(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathioheptadecane and other aliphatic polythiol compounds; 4, 6-Bis[4-(6-Mercaptomethylthio)-1,3-dithiocyclohexylthio]-6-[4-(6-mercaptomethylthio)-1,3-disulfide ring already Thio]-1,3-dithiocyclohexane, 4-[3,4,8,9-tetra(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathio One group]-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-Trithiooctyl]-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-tetra(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-trithiooctyl]mercaptomethylthiomethyl-1,3-dithiocyclobutane, 4-{1-[2- (1,3-Dithiocyclobutyl)]-3-mercapto-2-thiopropylthio)-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiobutyl Thio]-1,3-Dicyclopentane and other polythiol compounds having a cyclic structure.

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

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

Examples of aliphatic polyfunctional epoxy resins include:

-Such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 -Hexanediol Diglycidyl Ether, Trimethylolpropane Diglycidyl Base ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentan Diene type diglycidyl ether two epoxy resin;

-Such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, three epoxy resins;

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)-meta-di

Alkane alicyclic epoxy resin;

-Glycidyl amine epoxy resin such as tetraglycidyl bis(aminomethyl)cyclohexane;

-Hydantoin epoxy resin such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and

-Such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane such as epoxy resin with polysiloxane skeleton, but not limited to this Wait.

In the foregoing examples, "cyclohexane type diglycidyl ether" refers to a divalent diglycidyl ether with "two glycidyl groups each bonded through an ether bond to a cyclohexane ring as the parent structure". "Saturated hydrocarbon group" structure compound. "Dicyclopentadiene type diglycidyl ether" refers to a structure having "two glycidyl groups are respectively bonded to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a parent structure through an ether bond" compound of. The aliphatic multifunctional epoxy resin preferably has an epoxy equivalent of 90 to 450 g/eq. In addition, as cyclohexane type diepoxypropyl ether, cyclohexanedimethanol dieplyoxypropyl ether is particularly preferred.

In one aspect of the present invention, the 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 carbamide skeleton or an isocyanurate skeleton. The ratio ([epoxy functional group equivalent]/[thiol functional group equivalent]) of the epoxy functional group equivalent of the aliphatic multifunctional epoxy resin relative to the thiol compound having an acetylene carbamide skeleton or an isocyanurate skeleton Preferably, it is 0.40 to 0.85.

In one aspect of the present invention, the component (A) contains a trifunctional thiol compound or a tetrafunctional thiol compound having an acetylene carbamide skeleton or an isocyanurate skeleton. Use as component (A) with acetylene carbamide skeleton or isocyanurea In the case of a trifunctional thiol compound or a tetrafunctional thiol compound having an acid ester skeleton, the component (B) is preferably an epoxy resin having a cyclohexane type dieglycidyl ether or a polysiloxane skeleton. Especially preferably, 1,4-cyclohexanedimethanol diglycidyl ether or 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane Oxane.

In addition, in one aspect of the present invention, the component (A) contains a trifunctional thiol compound or a tetrafunctional thiol compound that does not have an acetylene carbamide skeleton or an isocyanurate skeleton (specifically, a polyether skeleton , Trifunctional thiol compound or tetrafunctional thiol compound of polysulfide skeleton or polyester skeleton). In order to set the temperature at which E" is maximum to the desired range, in the epoxy resin composition, 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% by mass or more and 55% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and still 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 including an aromatic ring such as a benzene ring. Bisphenol A type epoxy resins and the like have many such polyfunctional epoxy resins among epoxy resins frequently used in the past. Examples of aromatic polyfunctional epoxy resins include:

-Bisphenol A type epoxy resin;

-Branched multifunctional bisphenol A epoxy resin such as p-glycidoxy phenyl dimethyl tribisphenol A diglycidyl ether;

-Bisphenol F type epoxy resin;

-Novolac type epoxy resin;

-Tetrabromobisphenol A epoxy resin;

-Fu-type epoxy resin;

-Biphenyl aralkyl epoxy resin;

-Two epoxy resins such as 1,4-phenyldimethanol diglycidyl ether;

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

-Glyoxypropyl amine epoxy resin such as diglycidyl aniline, diglycidyl toluidine, triglycidyl p-aminophenol, tetraglycidyl m-xylylene diamine; and

-Epoxy resins containing naphthalene ring, but 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 than an aliphatic polyfunctional epoxy resin. As aromatic polyfunctional epoxy resins, bisphenol F type epoxy resins, bisphenol A type epoxy resins and glycidyl amine type epoxy resins are preferred, among which the epoxy equivalent of 90 to 200 g is particularly preferred. /eq, the best is the epoxy equivalent of 110 to 190g/eq.

When an aromatic polyfunctional epoxy resin is used as the component (B), the combinable component (A) is preferably a trifunctional thiol compound or a tetrafunctional thiol compound having a polyether skeleton, a polysulfide 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, polysulfide skeleton or polyester skeleton ([epoxy functional group equivalent]/[thiol functional group equivalent] ) Is preferably 0.30 to 1.10. In addition, when a trifunctional thiol compound or a tetrafunctional thiol compound having a polyether skeleton, a polysulfide skeleton or a polyester skeleton is used as the component (A), the component (B) is preferably a bisphenol A epoxy resin , At least one of bisphenol F epoxy resin and epoxy resin containing naphthalene ring.

In addition, in order to set the temperature at which E" is maximum to the desired range, in the epoxy resin composition, aromatic epoxy resins (monofunctional and polyfunctional aromatic epoxy resins), and acetylene urea skeletons or different The total amount of the trifunctional thiol compound or the tetrafunctional thiol compound of the cyanurate skeleton 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 still more preferably 50% by mass % Above 75% by mass.

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

The crosslinking density modifier (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 used conventionally as a reactive diluent for adjusting the viscosity of an epoxy resin composition. Monofunctional epoxy resins are roughly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the epoxy equivalent of component (C) is preferably 180 to 400 g/eq. In the present invention, from the viewpoint of viscosity and low volatility, the component (C) preferably contains an aromatic monofunctional epoxy resin. Furthermore, it is more preferable that the component (C) is substantially an aromatic monofunctional epoxy resin.

Examples of the aromatic monofunctional epoxy resin contained in the component (C) include phenyl glycidyl ether, tolyl glycidyl ether, and p-second butyl phenyl glycidyl ether. , Styrene oxide, p-tertiary butyl phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, etc. , But not limited to this. Among these, p-tertiary butyl phenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tertiary butyl phenyl glycidyl ether is particularly preferred. Examples of aliphatic monofunctional epoxy resins include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, and allyl Glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane Alkyl, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, glycidyl neodecanoate, etc., but 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 of an epoxy resin (the component (B)), and conventional ones can be used. The component (D) is preferably a latent hardening catalyst. As a latent hardening catalyst, a compound that is activated by heating at room temperature to function as a hardening catalyst. Examples include imidazole compounds that are solid at room temperature; amine compounds and cyclic compounds. The reaction products of oxygen compounds (amine-epoxy adducts) and other solid dispersion amine adducts have potential hardening contact Medium; reaction product of amine compound and isocyanate compound or urea compound (urea-type adduct system), etc. By using the above-mentioned component (D), the epoxy resin composition of the present invention can be cured in a short time even under low temperature conditions.

As a representative example of commercially available products of the latent curing catalyst, the amine-epoxy adduct system (amine adduct system) system includes "Amicure PN-23" (product of Ajinomoto Fine-Techno Co., Ltd.) Name), "Amicure PN-40" (Ajinomoto Fine-Techno Co., Ltd. product name), "Amicure PN-50" (Ajinomoto Fine-Techno Co., Ltd. product name), "Hardener X-3661S" (ACR Co., Ltd. Product name), "Hardener X-3670S" (ACR Co., Ltd. product name), "Novacure HX-3742" (Asahi Kasei Co., Ltd. product name), "Novacure HX-3721" (Asahi Kasei Co., Ltd. product name), " "Novacure HXA9322HP" (Asahi Kasei Co., Ltd. product name), "Novacure HXA3922HP" (Asahi Kasei Co., Ltd. product name), "Novacure HXA3932HP" (Asahi Kasei Co., Ltd. product name), "Novacure HXA5945HP" (Asahi Kasei Co., Ltd. product name) , "Novacure HXA9382HP" (product name of Asahi Kasei Co., Ltd.), "Fujicure FXR1121" (product name of T&K TOKA Co., Ltd.), etc. Also, as the urea-type adduct series, such as: "Fujicure FXE-1000" ( T&K TOKA Co., Ltd. trade name), "Fujicure FXR-1030" (T&K TOKA Co., Ltd. trade name), etc., but not limited to these. The component (D) may be used alone or in combination of two or more kinds. As the component (D), from the viewpoint of pot life and curability, a solid dispersion type amine adduct-based latent curing catalyst is preferred.

In addition, the component (D) has a provider in the form of a dispersion liquid dispersed in a polyfunctional epoxy resin. When using the component (D) in this form, it should be noted that the amount of the multifunctional epoxy resin dispersed therein is also included in the amount of the above-mentioned component (B) 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 component or composition of interest, divided by the mass (g) of the thiol compound contained in the component or composition of interest divided by the thiol compound 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). The mercaptan equivalent can be determined by iodine titration. This method has been widely known, for example, it is disclosed in paragraph 0079 of Japanese Patent Laid-Open No. 2012-153794. When the thiol equivalent cannot be obtained by this method, it can also be calculated as the 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 (the components (B) and (C)) contained in the same component or composition, and refers to the component or composition of interest. 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, 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 obtained 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.

Thiol-based epoxy resin curing agent relative excess epoxy resin composition, the formation of an initial T _g (cured immediately after T _g) lower cured. However, when the thiol-based curing agent is excessive to the epoxy resin in this way, the thiol group remaining in the cured product in an unreacted state without reacting with the epoxy group increases. The inventors of the present invention disclosed in Patent Document 1 _{a composition with a small change in T g} after a heat resistance test, but later found that the composition was tested in a humidity resistance reliability test (especially at 85°C and 85% for 100 hours) After the test, the excess thiol groups may generate new cross-links with each other. The progress of this cross-linking is more stable than when the epoxy resin is in excess of the mercaptan-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 equivalent of the above-mentioned component (A) ([epoxy functional group equivalent] /[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 the curable composition, since the epoxy group contained in the component (C) that reduces the unreacted thiol group is present, most of the unreacted thiol group disappears as a result of these reactions. The polyfunctional epoxy resin contained in the aforementioned component (B) has the ability to link two molecules of the polyfunctional thiol compound contained in the aforementioned component (A) to extend the polymer chain or to form cross-links 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 exchanges that cause the T g of the} cured product to increase due to the reaction between the components (A) and (C). United. Therefore, the cured product formed by the curable composition has a small content of functional groups that can form new crosslinks, so even after a long period of time after curing, the increase in T _{g due to the formation of new crosslinks is hardly confirmed.} .

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 equivalent of the above-mentioned component (A) ([epoxy functional group equivalent]/[ When the equivalent of thiol functional group]) is 0.70 or more and 1.10 or less, for both epoxy groups and thiol groups in the composition, the one related to the reaction between epoxy groups and thiol groups becomes certain The above ratio, therefore, the characteristics of the obtained hardened product are ideal. If the above ratio is less than 0.70, the thiol group is excessive to the epoxy group, resulting in unreacted, i.e., more thiol groups remaining in the hardened substance, and it is difficult to suppress the hardening caused by the reaction between the thiol groups. The T _{g of the material} rises. On the other hand, when the above ratio exceeds 1.10, the epoxy group is excessive to the thiol group, and in addition to the reaction between the epoxy group and the thiol group, the reaction between the excess epoxy group (homopolymerization) also proceeds. . As a result, in the resulting cured product, intermolecular cross-links are formed due to the reaction of these two parties, so the cross-link density is too high, which leads to an increase _{in T g.} Or it may cause difficulty in hardening at a low temperature of 80°C for 1 hour.

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

‧stabilizer

In the epoxy resin composition of the present invention, if necessary, a stabilizer can be added. In order to improve the storage stability and extend the pot life of the epoxy resin composition of the present invention, a stabilizer may be added. As the stabilizer of the single-component adhesive with epoxy resin as the main agent, various conventional stabilizers can be used. However, in view of the high effect of improving storage stability, it is preferably selected from liquid borate compounds, At least one of 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, tri-dodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane , Double (1,4,7,10-tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) Borane, tribenzyl borate, triphenyl borate, tri-o-cresyl borate, tri-m-cresyl borate, triethanolamine borate, etc. Since the liquid borate compound is liquid at normal temperature (25°C), the viscosity of the formulation can be suppressed to be low, which is preferable. As the aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used.

When the stabilizer is added, the amount 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, relative to 100 parts by mass of the total amount of components (A) to (D) Mass parts.

‧Filling agent

In the epoxy resin composition of the present invention, a filler can be added if necessary. When the epoxy resin composition of the present invention is used as a one-component adhesive, if a filler is added to it, the moisture resistance and heat cycle resistance, especially the heat cycle resistance, of the part to be bonded are improved. The heat cycle resistance is improved by adding fillers The rise is because the coefficient of linear expansion of the hardened material is reduced, which can inhibit the expansion and contraction of the hardened material due to thermal cycling.

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

In the case of adding a filler, 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 still more preferably, in the entire epoxy resin composition It is 5 to 50% by mass.

‧Coupling agent

In the epoxy resin composition of the present invention, if necessary, a coupling agent can be added. 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-based, amino-based, vinyl-based, methacryl-based, acrylic-based, and mercapto-based coupling agents can be used. Specific examples of the silane coupling agent include: 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxy Silyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methyl Allyloxypropylmethyltrimethoxysilane, 3-propenoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, etc. These silane coupling agents may be used alone, or two or more of them may be used in combination.

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

‧Other additives

If necessary, the epoxy resin composition of the present invention can also be added with other additives, such as carbon black, titanium black, ion scavengers, leveling agents, antioxidants, and defoamers, within the scope that does not impair the gist of the present invention. Agents, thixotropic agents, viscosity modifiers, flame retardants, colorants, solvents, etc. The type and amount of each additive are in accordance with the general method.

The epoxy resin composition of the present invention can form a cured product with a maximum loss modulus (E") at a temperature in the range of 20°C or more and 55°C or less. The loss modulus corresponds to the dynamic elastic modulus of an object expressed in plural The imaginary part of the complex modulus of elasticity represents the disappearing energy of viscoelasticity in dynamic behavior. In this specification, unless otherwise specified, the loss modulus means a frequency of 10 Hz, a heating rate of 3°C/min, and a strain amplitude of 5.0 μm , the value measured by the dynamic viscoelasticity measurement (DMA) in the stretching method.

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

As described above, the temperature of the cured product formed of the epoxy resin composition of the present invention at such a maximum loss modulus (E") is in the range of 20°C or more and 55°C or less. The temperature is not within the above range. In the epoxy resin composition, the tensile strength of the cured product, that is, the drop shock resistance cannot be sufficiently improved.

The epoxy resin composition of the present invention can form a cured product with a temperature in the range of 20°C or higher and 50°C or lower (more preferably 20°C or higher and 45°C or lower) at a maximum loss modulus.

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

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

The aforementioned relationship between the molar ratio (B)/(A) of the component (B) and the component (A) means that the crosslinking point of the component (A) including the thiol compound having 3 or more thiol groups is reduced, For example, if it is a thiol compound having 4 thiol groups, it is used to become a bifunctional thiol compound or a trifunctional thiol compound. When the aforementioned ratio is less than 1.15, the multifunctional epoxy resin that is a cross-linking component will become too small, and the resulting hardened product may show the properties of a thermoplastic resin that melts at high temperatures. On the other hand, when the aforementioned ratio exceeds 1.45, the multifunctional epoxy resin which is a cross-linking component will become too much, and the resulting hardened product will cause excessive intermolecular formation due to the reaction of components (A) and (B). Cross-linking, there are doubts 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 component (A) means that the aforementioned component (A) is relative to the number (amount) of epoxy groups contained in the aforementioned component (C) The thiol group is the case of moderate excess. By satisfying this relationship, a cured product having an appropriate crosslink density formed by the reaction of the components (A) and (B) can be obtained, which is preferable.

By satisfying the aforementioned 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 the component (A) that has not reacted with the component (B) will react with the component (C), so that the remaining unreacted thiol group in the hardened product is reduced, and the characteristics of the obtained hardened product become appropriate.

The cured product formed by the epoxy resin composition of the present invention is particularly suitable for selected from LCP (liquid crystal polymer), PC (polycarbonate), PBT (polybutylene terephthalate), SUS, alumina, The adherend of nickel (including the surface plated with nickel) exhibits excellent tensile strength. These adherends can be made of plasma, etc. Perform surface treatment. In this specification, "tensile strength" typically means the tensile strength when the adherends are made of the same material.

The manufacturing method of the epoxy resin composition of this invention is not specifically limited. For example, the components (A) to (D) and other additives according to the needs are introduced into an appropriate mixer at the same time 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 an attritor equipped with a stirring device and a heating device, a Henschel mixer, a 3-roll mill, a ball mill, a planetary mixer, a bead mill, etc. can be used. Moreover, these devices can also be used in combination as appropriate.

The epoxy resin composition thus obtained is thermosetting, and it is preferably cured within 5 hours under the condition of a temperature of 80°C, and more preferably cured within 1 hour. In addition, it can be cured at a high temperature of 150°C for a few seconds in an ultra-short time. When the curable composition of the present invention is used to manufacture image sensor modules including parts that deteriorate under high temperature conditions, it is preferable to heat the same composition at a temperature of 60 to 90°C for 30 to 120 minutes , Or heat curing 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 a low _Tg. The cured product of the epoxy resin composition of the present invention _{preferably has a T g} of 65°C or lower, more preferably 60°C or lower, and still more preferably 50°C or lower. In addition, from the viewpoint of adhesion, the T _{g of the} cured product is preferably 30°C or higher, and more preferably 32°C or higher. In the present invention, T _g can use a dynamic thermomechanical measuring device (DMA), in the range of -20°C to 110°C, a frequency of 1 to 10 Hz, a heating rate of 1 to 10°C/min, and a strain amplitude of 5.0 μm. Find out by law. The preferred frequency is 10 Hz, and the preferred heating rate is 3°C/min. T _g is calculated from the peak temperature of the loss tangent (tanδ) obtained from the loss modulus (E") and the stored modulus (E').

The epoxy resin composition of the present invention can be used, for example, as a semiconductor device containing various electronic parts, an adhesive for fixing, joining, or protecting the parts constituting the electronic parts, 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 parts, etc., for example.

In addition, 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 an electronic component including the hardened product of the present invention.

(Example)

The following examples illustrate the present invention, but the present invention is not limited to these. In addition, in the following examples, parts and% represent parts by mass and% by mass unless otherwise specified.

Examples 1 to 9, Comparative Examples 1 to 3

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

‧Thiol hardener (component (A))

In the examples and comparative examples, the compounds used as the component (A) are as follows.

(A-1): 1,3,4,6-Tetra(2-mercaptoethyl)acetylene carbamide (trade name: TS-G, manufactured by Shikoku Chemical Industry Co., Ltd., mercaptan equivalent: 100)

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

(A-3): Neopentylerythritol tetrakis (3-mercaptopropionate) (trade name: PEMP, manufactured by SC organic chemistry, mercaptan equivalent: 122)

‧Epoxy resin (component (B))

In the Examples and Comparative Examples, the compounds used as the 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 type epoxy resin/bisphenol A type epoxy resin mixture (trade name: EXA-835LV, manufactured by DIC Co., Ltd., epoxy equivalent: 165)

(B-3): Dicyclopentadiene 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 regulator (ingredient (C))

In the Examples and Comparative Examples, the compounds used as the 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): Phenyl glycidyl 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 Co., Ltd., epoxy equivalent: 187)

‧Hardening catalyst (component (D))

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

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

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

‧Other ingredients (ingredient (E))

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

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

(E-2): Silica filler 2 (trade name: SO-E5, average particle size 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.

(Production of hardened material)

The resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were heated at 80°C for 120 minutes to obtain hardened products.

<Loss modulus of hardened material (E")>

The measurement was performed in _{accordance with the T g} measurement method of Japanese Industrial Standards JIS C6481. Specifically, first, a Teflon (registered trademark) sheet is attached to the surface of a glass plate with a thickness of 3mm, and spacers (with heat-resistant adhesive tape overlaid on it) are placed on it so that the film thickness at the time of curing becomes 400±150μm. Winner). Next, the resin composition was applied between the spacers, and the Teflon (registered trademark) sheet was sandwiched between another glass plate with a Teflon (registered trademark) sheet attached to the surface so as not to mix in air bubbles, and cured at 80°C for 120 minutes to obtain a cured product. Finally, after peeling the cured product from the glass plate with the Teflon (registered trademark) sheet attached, it was cut into a predetermined size (10 mm×40 mm) with a cutter to obtain a test piece. In addition, use sandpaper to smooth the cut. For this hardened product, a dynamic thermomechanical measuring device (DMA) (manufactured by Seiko Instruments) was used at a frequency of 10 Hz, a heating rate of 3° C/min, a strain amplitude of 5.0 μm, and a stretching method in the range of -20°C to 110°C. The loss modulus (E") of the cured product is measured, and the temperature (°C) at which E" is the maximum is determined. The results are shown in Tables 1 to 2.

<Measured tensile strength and corrected tensile strength of hardened material>

On an alumina board with a length of 20 mm × a width of 20 mm × 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. A 9 mm square thick plate (2.5 g) treated with bright nickel plating was covered on the spacer so as to be in contact with the coated resin composition. Then, it was heat-cured at 80°C for 120 minutes to obtain a test body. A moisture-curing 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, leave it for 12 hours to make the thick plate and the nut sufficient Splice. Then, after fixing the alumina plate to a precision load measuring device (manufactured by Aikoh Engineering, model: 1605HTP) so that the bonding surface was horizontal, the rope was passed through the hole of the nut, and the rope was attached to the jig at 23°C. A tensile load is applied in the vertical direction at a speed of 12 mm/min. The maximum load applied before the alumina plate is separated from the thick plate is divided by the bonding area between the alumina plate and the thick plate, and the obtained value is used as the measured tensile strength (N=6). The unit is N/mm ² . In addition, from the actual measured tensile strength, the corrected tensile strength was obtained using the following formula derived from the comparison of Examples 1 and 2. The unit is N/mm ² . The results are shown in Tables 1 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 if necessary by adding component (E) (filler). However, it can be seen from the comparison of Examples 1 and 2 that when the content of component (E) (filler) increases, the actual measurement of the cured product The 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]

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

In contrast, in Comparative Examples 1 to 2 in which the temperature at which the E" of the cured product is extremely large, and Comparative Example 3 that does not contain component (C), the tensile strength after curing is insufficient. From the comparative example 3 knowing, no For an epoxy resin composition with a predetermined composition, even if the temperature of the hardened product is within a predetermined range when the E" is extremely high, the tensile strength after hardening is not sufficiently improved.

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

(Industrial availability)

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. This hardened product shows low T _g , and has moderate softness and flexibility. In addition, since the cured product exhibits high tensile strength, by using the epoxy resin composition of the present invention, it is possible to easily manufacture electronic parts having excellent drop shock resistance. 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 that are made of different materials and assembled by joining and assembling various parts.

Claims (7)

An epoxy resin composition comprising the following components (A) to (D): (A) A thiol-based hardener, including at least one multifunctional thiol compound having 3 or more thiol groups; (B) At least one multifunctional epoxy resin; (C) A crosslinking density modifier, including at least one aromatic monofunctional epoxy resin; and (D) Hardening catalyst; And it can form a hardened product. The hardened product has a frequency of 10 Hz, a heating rate of 3°C/min, and a DMA measurement by the stretching method. The temperature at which the loss modulus (E") is maximum is 20°C or more, 55 The range below ℃. The epoxy resin composition according to claim 1, wherein the molar ratio (B)/(A) of the component (B) to the component (A) is 1.15 or more and 1.45 or less. The epoxy resin composition according to claim 1 or 2, wherein the molar ratio (C)/(A) of the component (C) to the component (A) is 0.55 or more and 1.65 or less. The epoxy resin composition according to any one of claims 1 to 3, wherein the component (C) comprises an aromatic monofunctional epoxy resin. A sealing material comprising the epoxy resin composition according to any one of claims 1 to 4. A hardened material obtained by hardening the epoxy resin composition according to any one of claims 1 to 4 or the sealing material according to claim 5. An electronic component comprising the hardened object as described in claim 6.

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