TWI815031B - 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, wherein the epoxy resin composition cures in a short time even under low temperature conditions, has a low glass transition point (T_g), and gives a cured product in which T_g hardly changes even after a long period of time after curing.

The epoxy resin composition of the present invention has a low T_g, and the T_g hardly changes even after a long time has passed after curing, and gives a cured product having excellent shear strength. Further, the epoxy resin composition of the present invention exhibits a low viscosity and is suitable for application by a jet dispenser or the like, and is therefore very useful as an adhesive, a sealing material, a dam agent or the like for semiconductor devices and electronic parts.

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.

Currently, curable resin compositions, especially adhesives and sealants containing epoxy resin compositions, are often used in the assembly and installation of electronic components used in semiconductor devices, such as semiconductor wafers, for the purpose of maintaining reliability. 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 based hard The chemical agent contains a compound having two or more thiol groups, that is, a polyfunctional thiol compound. Examples of such curable compositions include those disclosed in Patent Document 1 or 2.

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.

Patent Document 3 describes an epoxy resin composition that can be cured in a short time to form a cured product with low Tg even under low-temperature conditions.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 6-211969

[Patent Document 2] Japanese Patent Application Laid-Open No. 6-211970

[Patent Document 3] International Publication No. 2012/093510

However, the epoxy resin compositions described in Patent Documents 1 and 2 have a problem that their viscosity is not low enough for use in electronic components. On the other hand, the epoxy resin composition described in Patent Document 3 has a problem in that it forms a cured product with a low Tg and the shear strength of the cured product is low.

An example of means for improving the mechanical strength of a cured product obtained by curing a curable resin composition is to appropriately add a filler (eg, silica filler) to the curable resin composition. The addition of a filler is also useful from the viewpoint of improving the heat cycle resistance of the cured product. However, the viscosity of the curable resin composition increases with the addition of the filler, which sometimes limits its application.

With the miniaturization of electronic components and modules in recent years, curable resin compositions are increasingly applied to tiny areas, and jet dispensers are often used for this purpose. In order to be used in a jet dispenser, the curable resin composition must have a low viscosity to a certain extent, and in order to cope with the narrow gap, the viscosity needs to be reduced to ensure fluidity. However, a curable resin composition whose viscosity increases due to the addition of a filler becomes difficult to apply to a jet dispenser, and there is a problem that desired fluidity cannot be obtained in a narrow gap.

The present invention was completed in view of the above 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 viscosity and low temperature conditions and has a low glass transition point (T _g ) after curing. , can form a hardened product with excellent shear strength, and provide a sealing material containing the epoxy resin composition. 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 concentrated on detailed research in order to develop a hardened material that can be hardened in a short time even under low-temperature conditions and can have a low Tg after hardening and excellent shear strength. As a result, it was unexpectedly discovered that, in addition to thiol-based hardeners and epoxy resins, crosslinking density adjusters containing monofunctional epoxy resins are used as components of the curable composition. By making the thiols contained in these The number (amount) of groups and epoxy groups satisfies a predetermined relationship, and the initial Tg of the obtained cured product becomes moderately low. The inventors further unexpectedly discovered that by adding a specific filler, the curable composition will not be reduced. Excessive increase in viscosity can increase the shear strength of the resulting hardened material. 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, which contains the following components (A) to (E):

(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 one monofunctional epoxy resin;

(D) Hardening catalyst; and

(E) Silica filler with an average particle size of less than 5.0 μm;

The ratio of the total epoxy functional group equivalents of the above components (B) and (C) to the thiol functional group equivalents of the above component (A) ([epoxy functional group equivalents]/[thiol functional group equivalents]) Above 0.70 and below 1.10,

The amount (mol) of the above-mentioned component (C) is 25 to 75% of the total amount (mol) of the above-mentioned component (B) and the amount (mol) of the above-mentioned component (C),

The viscosity at 30℃ is 2000mPa. s or less.

2. The epoxy resin composition as described in the preceding item 1, wherein the content of component (E) is 15 to 50 mass % relative to the total amount of the epoxy resin composition.

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

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

5. A hardened product obtained by hardening the epoxy resin composition as described in any one of the preceding paragraphs 1 to 3 or the sealing material as described in the preceding paragraph 4.

6. An electronic component containing the hardened material as described in the preceding item 5.

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)), curing catalyst (Component (D)) and silica filler (Component (E)) are essential components. These components (A) to (E) 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 below. (Component (B)) or the epoxy group reaction in the cross-linking density adjuster (Component (C)). Component (A) preferably contains a trifunctional and/or tetrafunctional thiol compound. The thiol equivalent is preferably 90 to 150 g/eq, more preferably 90 to 140 g/eq, and particularly preferably 90 to 130 g/eq. In addition, trifunctional and tetrafunctional thiol compounds are thiol compounds having three and four 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), dipenterythritol 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.

Preferred non-hydrolyzable polyfunctional thiol compounds that can be used in the present invention are compounds 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-trisulfoundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercapto) Propylthiomethyl)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)ethylthio Alcohol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithioheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5, 8-trisulfononane, 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(mercaptomethyl) methylthio)-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-hexathioheptadecane, 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-hexasulfohexadecane, 8-[bis(mercaptomethyl thio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexasulfopentadecane, 4 ,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithioheptylthio]-1,3-dithiocyclohexane, 4-[3,5 -Bis(mercaptomethylthio)-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) methyl)-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-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiopentadecane and other aliphatic polythiol compounds; 4,6- Bis[4-(6-mercaptomethylthio)-1,3-dithiocyclohexylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithiocyclohexylthio base]-1,3-dithiocyclohexane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto -2,5,7,10-tetrathioundecyl]-5-mercaptomethylthio-1,3-dithiocyclopentane, 4,5-bis[3,4-bis(mercaptomethylthio) base)-6-mercapto-2,5-dithiohexylthio]-1,3-dithiocyclopentane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2, 5-dithiohexylthio]-5-mercaptomethylthio-1,3-dithiocyclopentane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercapto) Methylthio)-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-dithiohexylthio]mercaptomethylthiomethyl-1,3-dithiocyclobutane, 2-[3,4,8,9-tetrakis(mercaptomethyl) Thio)-11-mercapto-2,5,7,10-tetrathioundecylthio]mercaptomethylthiomethyl-1,3-dithiocyclobutane, 2-[3-bis(mercapto) Methylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithioctyl]mercaptomethylthiomethyl-1,3-disulfide cyclobutane, 4-{1-[2-(1,3-dithiocyclobutyl)]-3-mercapto-2-thiopropylthio}-5-[1,2-bis(mercaptomethyl) Polythiol compounds with cyclic structures such as thio)-4-mercapto-3-thiobutylthio]-1,3-dithiocyclopentane.

(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 -Hexanediol diglycidyl ether, trimethylolpropyl ether Alkane Diglycidyl Ether, Polytetramethylene Diol Diglycidyl Ether, Glycerin Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, Cyclohexane Diglycidyl Propyl Ether Ether, dicyclopentadiene-type diepoxy resin of diglycidyl ether;

-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 one with "-2 epoxypropyl groups bonded to a divalent saturated hydrocarbon group with a dicyclopentadiene skeleton as the parent structure through ether bonds." structure of the compound. 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 combined component (A) is preferably a trifunctional or tetrafunctional thiol compound having an acetylene urea skeleton or an isocyanuric acid skeleton. Relative to thiol compounds having an acetylene urea skeleton or an isocycyanuric acid skeleton, regarding aliphatic The ratio of epoxy functional group equivalents ([epoxy functional group equivalents]/[thiol functional group equivalents]) of the multifunctional epoxy resin is preferably 0.40 to 0.85.

In one aspect of the present invention, component (A) contains a trifunctional thiol compound or a tetrafunctional thiol compound having an acetylene urea skeleton or an isocyanuric acid skeleton. When using a trifunctional thiol compound or a tetrafunctional thiol compound having an acetylene urea skeleton or an isocycyanuric acid skeleton as the component (A), use a compound having a cyclohexane type diepoxypropyl ether or polysiloxy skeleton. Epoxy resin is preferred as component (B). In particular, 1,4-cyclohexanedimethanol diglycidyl ether or 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisilica Oxane is preferred.

Furthermore, in one aspect of the present invention, component (A) contains a trifunctional thiol compound or a tetrafunctional thiol compound that does not have an acetyleneurea skeleton or an isocycyanuric acid skeleton (specifically, a compound having a polyether skeleton, Polysulfide skeleton, or trifunctional thiol compound or tetrafunctional thiol compound of polyester skeleton). In order to set Tg in the desired range, in the epoxy resin composition, an aliphatic multifunctional epoxy resin and a trifunctional thiol compound or tetrafunctional thiol compound that does not have an acetylene urea skeleton or an isocyanuric acid skeleton are used. The total amount of the compound is preferably not less than 20% by mass and not more than 55% by mass, more preferably not less than 20% by mass and not more than 50% by mass.

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 combined component (A) is a trifunctional or tetrafunctional thiol compound having a polyether skeleton, a polysulfide skeleton, or a polyester skeleton. Better. The ratio of the epoxy functional group equivalent of the aromatic polyfunctional epoxy resin relative to the thiol compound having a polyether skeleton, a polysulfide 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 polysulfide skeleton, or a polyester skeleton as component (A), use bisphenol A type epoxy resin or bisphenol F type epoxy resin. It is preferable that at least one of resin and naphthalene ring-containing epoxy resin is used as the component (B).

In addition, in order to set Tg in a desired range, in the epoxy resin composition, aromatic epoxy resins (monofunctional and polyfunctional aromatic epoxy resins), and compounds having an acetylene urea skeleton or an isocycyanuric acid skeleton The total amount of the trifunctional thiol compound or the tetrafunctional thiol compound is preferably 45 mass% or more and 80 mass% or less, more preferably 50 mass% or more and 80 mass% or less.

(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 preferably substantially aromatic monofunctional epoxy resin.

Examples of aromatic monofunctional epoxy resins that may be included in component (C) include: phenyl glycidyl ether, tolyl glycidyl ether, and p-second butyl phenyl glycidyl ether. 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-methyl Cyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, glycidyl neodecanoate, etc., but not limited to And so on.

(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 the epoxy resin (component (B) mentioned above), and a conventional one can be used. Component (D) is preferably a latent curing catalyst. A 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 epoxy compounds Solid-dispersed amine adducts such as reaction products of compounds (amine-epoxy adduct systems) are potential curing catalysts; reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems) )wait. 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" (Ajinomoto Fine-Techno Co., Ltd. Trade 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. Company 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.), and urea-type adduct systems can be listed For example: "Fujicure FXE-1000" (trade name of T&K TOKA Co., Ltd.), "Fujicure FXR-1030" (trade name of T&K TOKA Co., Ltd.), 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.

In the epoxy resin composition of the present invention, the number (amount) of the thiol groups of the above component (A) and the number (amount) of the epoxy groups of the above components (B) and (C) must satisfy a predetermined relationship, and, The amount (mol) of the above-mentioned component (B) and the amount (mol) of the above-mentioned component (C) must satisfy a predetermined relationship. Specifically,

(i) The ratio of the total epoxy functional group equivalents of the above-mentioned components (B) and (C) with respect to the thiol functional group equivalents of the above-mentioned component (A) ([epoxy functional group equivalent]/[thiol functional group Equivalent]) is above 0.70 and below 1.10.

(ii) The amount (mol) of the above-mentioned component (C) is 25 to 70% of the total amount (mol) of the above-mentioned component (B) and the amount (mol) of the above-mentioned component (C).

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 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 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 curing agent is in excess relative to the epoxy resin, as in the curable composition of Patent Document 3, will form a cured product with a low initial T _g (T _g immediately after curing). 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. Therefore, in the cured product formed of the epoxy resin composition described in Patent Document 3, the initial Tg becomes too low and the shear strength becomes low. In the present invention, the ratio of the sum of the epoxy functional group equivalents of components (B) and (C) to the thiol functional group equivalents of the component (A) is ([epoxy functional group equivalent]/[thiol functional group equivalent] Basis equivalent]) is 0.70 or more and 1.10 or less, the crosslinking density becomes appropriate, and the initial Tg of the cured product can be made between 30°C and 65°C. As a result, the shear strength can be improved. Furthermore, the present inventors disclosed in Patent Document 3 a curable composition that forms a cured product with a small change in T _g after a heat resistance test. However, they later found that such a curable composition has poor performance in the moisture resistance reliability test. (Especially 100 hours in an environment of 85°C and 85%), after the test, new cross-linking may occur 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 . Therefore, in 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]/[thiol Functional group equivalent]) is 0.70 or more and 1.10 or less, preferably 0.75 or more and 1.10 or less, more preferably 0.80 or more and 1.05 or less. In the curable composition of the present invention, since there are epoxy groups contained in the above component (C) that reduce the unreacted thiol groups, as a result of the reaction between these components, most of the unreacted thiol groups disappear. 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, a new interaction may occur that causes the T _g of the cured product to increase due to the reaction between the components (A) and (C). The association is inhibited. Therefore, the cured product formed from the curable composition of the present invention has a small content of functional groups that can form new crosslinks. Therefore, even if a long time passes after curing, T caused by the formation of new crosslinks is hardly recognized. _g rises.

The cured product formed by the epoxy resin composition of the present invention is particularly suitable for LCP (liquid crystal polymer), PC (polycarbonate), PBT (polybutylene terephthalate), SUS, alumina, nickel (including The surface is nickel-plated) and the substrate is selected from glass to exhibit excellent shear strength. These can also be surface treated with plasma or the like. In this specification, "shear strength" generally refers to the shear strength of the material being worn.

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 When 0.70 or more and 1.10 or less (satisfying the relationship (i) above), for both the epoxy group and the thiol group in the same composition, the one related to the reaction between the epoxy group and the thiol group becomes The ratio is above a certain level, so the characteristics of the obtained hardened product are appropriate. 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, if 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.

The relationship (ii) above means that among all the epoxy resin molecules contained in the epoxy resin composition of the present invention, 25 to 70% are molecules belonging to the monofunctional epoxy resin (component (C)). The reaction with the monofunctional epoxy resin reduces the cross-linking points of the component (A) containing a thiol compound with three or more thiol groups. For example, a thiol compound with four thiol groups refers to a thiol compound with two functions. It is used in the form of a thiol compound or a trifunctional thiol compound. When the above-mentioned amount ratio exceeds 70%, there is too little polyfunctional epoxy resin that is a cross-linking component, so there is a concern that the resulting cured product melts at high temperature and exhibits properties like a thermoplastic resin. On the other hand, when the above ratio is less than 25%, there is too much polyfunctional epoxy resin that is a cross-linking component, so the reaction of components (A) and (B) in the resulting cured product may cause excessive formation of intermolecular cross-links. There is a concern that the cross-link density will become too high and the _Tg of the hardened product will rise excessively.

The amount (mol) of component (C) is preferably 30 to 70%, more preferably 33 to 70%, relative to the sum of the amount (mol) of component (B) and the amount (mol) of component (C).

By satisfying the relationship (i) and (ii) above, the thiol group of component (A) that has not reacted with component (B) reacts with component (C), and the unreacted thiol group remaining in the cured product becomes Since it is less, the characteristics of the obtained hardened material become appropriate.

In addition, since the present invention requires a certain amount of component (C), the viscosity of the epoxy resin composition can be reduced. As described above, since the epoxy resin composition of the present invention is intended to be used in a jet dispenser, in order to discharge the epoxy resin composition at high speed through micropores with an inner diameter of several hundred μm, the viscosity at the temperature at the tip of the nozzle is low. Which is better. Moreover, it is preferable that the epoxy resin composition after being discharged has fluidity. Therefore, the viscosity of the epoxy resin composition at 30°C is 2000mPa. s or less, preferably 1000mPa. s or less, preferably 800mPa. s or less. Also, from a workability point of view, the viscosity is 100mPa. s or above is preferred. In the present invention, the viscosity can be determined based on Japanese Industrial Standards JIS K6833. Specifically, the viscosity at 30°C can be obtained by using an E-type viscometer at 1 rpm to read the value 1 minute after the measurement starts. The equipment, rotor and measuring range used are not particularly limited.

The viscosity of the epoxy resin composition of the present invention at 60°C is 300mPa. Those below s are better. If the rotation speed is small, the viscosity measured by the E-type viscometer will have a detection limit. Therefore, it is better to measure the viscosity at 60°C at 50 rpm or an appropriate rotation speed.

(5) Silica filler (ingredient (E))

The epoxy resin composition of the present invention contains silica filler (component (E)). Thereby, the epoxy resin composition is cured, thereby improving the heat cycle resistance of the resulting cured product. The addition of fillers such as silica filler improves the heat cycle resistance because the linear expansion coefficient of the hardened material is reduced, that is, the expansion/shrinkage of the hardened material is suppressed due to thermal cycles.

In the present invention, a silica filler having an average particle diameter of 5.0 μm or less is used. In this specification, unless otherwise specified, the average particle diameter refers to the volume-based median diameter (d50) measured by the laser diffraction method in accordance with ISO-13320 (2009). The average particle diameter of the silica filler is preferably 4.0 μm or less, more preferably 3.0 μm or less. When the average particle diameter exceeds 5.0 μm, the silica filler becomes prone to sedimentation. Furthermore, coarse particles tend to be contained, and the nozzle of the jet dispenser is worn, so that the discharged resin composition tends to scatter outside a desired area. The minimum value of the average particle diameter is not particularly limited. However, when the average particle diameter is less than 0.1 μm, the viscosity of the epoxy resin composition tends to increase. Therefore, it is preferably 0.1 μm or more, and more preferably 0.2 μm or more. In one aspect, the average particle diameter of the silica filler used in the present invention is 0.1 μm or more and 5.0 μm or less, preferably 0.2 μm or more and 3.0 μm or less.

The content of the silica filler in the epoxy resin composition of the present invention is preferably 15 to 50 mass%, more preferably 20 to 45 mass%, and more preferably 20 to 40 mass% relative to the total amount of the epoxy resin composition. Mass %. If the content of the silica filler is too low, the heat cycle resistance becomes insufficient. When the content is too high, the viscosity of the epoxy resin composition becomes too high, making it difficult to apply it to a jet dispenser.

Silica filler can also be used in combination with other fillers. Other fillers are not particularly limited, and various fillers can be used. Specific examples of other fillers include alumina fillers, talc fillers, calcium carbonate fillers, polytetrafluoroethylene (PTFE) fillers, polysiloxy fillers, acrylic fillers, styrene fillers, and the like.

In the present invention, the silica filler and other fillers can also be surface treated.

If necessary, the curable composition of the present invention may contain any components other than the above-mentioned components (A) to (E), 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 stabilizers for single-liquid adhesives using epoxy resin as the main ingredient, various conventional stabilizers can be used. agent, but in view of the high effect of improving storage stability, it is preferable to select at least one from the group consisting of liquid borate ester compounds, aluminum chelates and organic acids.

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 (E). parts 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-triethyl Oxysilyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 8-epoxypropoxyoctyltrimethoxysilane, 3-ureidopropyltrimethoxysilane Ethoxysilane, 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 added amount of the coupling agent is preferably from 0.01 to 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 method for producing the epoxy resin composition of the present invention is not particularly limited. For example, ingredients (A) to (E) and other additives as required 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. Also, you can Hardening takes place at a temperature of 150°C, a high temperature of 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 Tg of the cured product of the epoxy resin composition of the present invention is preferably 65°C or lower, more preferably 60°C or lower, and 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 μm, by the stretching method. And find out. 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”)/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 electronic components, a sealing material, a dam agent, or its raw materials.

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.

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 13, Comparative Examples 1 to 5

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): Neopenterythritol tetrakis(3-mercaptopropionate) (trade name: PEMP, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 122)

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

‧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 type epoxy resin mixture (trade name: EXA-835LV, manufactured by DIC Co., Ltd., epoxy equivalent: 165)

(B-3): 1,4-cyclohexanedimethanol diglycidyl ether (trade name: CDMDG, manufactured by Showa Denko Co., Ltd., epoxy equivalent: 133)

(B-4): 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane (trade name: TSL9906, Momentive Performance Materials Japan LLC 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 1 (trade name: Fujicure FXR1121, manufactured by T&K TOKA Co., Ltd.)

(D-2) Amine-epoxy adduct latent curing catalyst 2 (trade name: Novacure HXA9322HP, manufactured by Asahi Kasei Co., Ltd.)

The latent curing catalyst (D-2) 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 resin)). Equivalent: 170)) is provided in the form of a dispersion (mixture of latent curing catalyst/bisphenol A-type epoxy resin and bisphenol F-type epoxy resin = 33/67 (mass ratio)). (D-2) 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, "the number of functional groups in (B)", "(B)/(A) (functional group equivalent ratio)", "{(B)+(C)}/(A) (functional group equivalent ratio)" in Tables 1 to 2 Ratio)" and (B) of "(C)/{(B)+(C)} (molar ratio)" include the amount of epoxy resin in (D-2).

‧Silica filler (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.)

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

(E’-1): Silica filler 1’ (trade name: FB-7SDX, average particle size 5.5 μm, manufactured by Denka Co., Ltd.)

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

<Viscosity of curable composition>

Using an E-type viscometer (model: TVE-22H, rotor name: 1°34'×R24) manufactured by Toki Sangyo Co., Ltd. (set to an appropriate measurement range (H, R or U)), the viscosity of the epoxy resin composition (Unit: mPa·s), within 1 hour after preparation, read the value 1 minute after the start of the measurement at 30°C and the rotor rotation speed 1 rpm. The results are shown in Tables 1 to 2. In addition, when measured at a rotor rotation speed of 1 rpm, the viscosity is less than 640 mPa. The situation of s is outside the measurable range, so Tables 1 to 2 show that it is at least less than 640mPa. s and recorded as "<640". The viscosity must be 2000mPa. s or less.

(Preparation of hardened materials)

The resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were heated at 80° C. for 120 minutes, respectively, to obtain cured products.

(Glass transition temperature (Tg) of hardened material)

Measurements are made in accordance with Japanese Industrial Standards JIS C6481. Specifically, first, a Teflon (registered trademark) sheet was attached to the surface of a glass plate with a thickness of 3 mm, and the film thickness at the time of curing was placed on it to form Spacers (made by overlapping heat-resistant tape) are arranged in two places with a diameter of 400±150μm. 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 to perform tensile testing in the range of -20°C to 110°C at a frequency of 10 Hz, a temperature rise rate of 3°C/min, and a strain amplitude of 5 μm. method to measure the initial Tg. Tg is determined from the peak temperature of tan δ obtained from E”/E’.

(Shear strength of hardened material)

2mm的大小、125μm的厚度藉由孔版印刷進行塗布，在經塗布的樹脂組成物上積層3.2mm×1.6mm×0.45mm厚的氧化鋁小片，以輕微負重的狀態下使樹脂組成物硬化，製作試驗片。此時的硬化條件係在送風乾燥機中以80℃、120分鐘進行。將此SUS板上的氧化鋁小片在23℃中，以黏結強度試驗機(Dage公司製，4000系列)測定由側面突起，氧化鋁小片剝離時的應力(N)。此測定針對7個試驗片進行，算出所得應力的平均值。將此平均值作為硬化物的剪切強度(單位：N/Chip)示於表1、表2。剪切強度較佳為50N/Chip以上，更佳為80N/Chip以上。 On the SUS board, place the resin composition with

The size of 2 mm and the thickness of 125 μm are applied by stencil printing, and 3.2 mm × 1.6 mm × 0.45 mm thick alumina flakes are laminated on the coated resin composition, and the resin composition is hardened under a slight load to produce Test piece. The hardening conditions at this time were performed in a blower dryer at 80° C. and 120 minutes. The alumina flakes on this SUS board were measured at 23° C. using a bonding strength testing machine (4000 series manufactured by Dage Corporation) to measure the stress (N) when the alumina flakes were peeled off from the side protrusions. This measurement was performed on seven test pieces, and the average value of the obtained stresses was calculated. This average value is shown in Table 1 and Table 2 as the shear strength (unit: N/Chip) of the hardened material. The shear strength is preferably 50N/Chip or more, more preferably 80N/Chip or more.

(Presence or absence of coarse particles in the curable composition)

Use a grinding fineness meter (Type: No. 527 Particle Size Tester [Small], groove depth 0 to 50 μm, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) to detect and measure the hardenable composition. The particle size of relatively large particles (coarse particles). The results are shown in Table 1 and Table 2. Curable compositions with coarse particles having a detected particle size of 15 μm or more were evaluated as ×.

[Table 1]

[Table 2]

In Tables 1 and 2, the functional group equivalent ratios ((B)+(C))/(A), (B)/(A) and (C)/(A) are derived from components (A) and (B) And the calculated value of the mass of (C) and the corresponding thiol equivalent (or epoxy equivalent). These functional group equivalent ratios are the functional group equivalents calculated from the rounded thiol functional group equivalents (or epoxy functional group equivalents) of ingredients (A), (B) and (C) in the table. is more correct than.

It is obvious from Tables 1 to 2 that the curable compositions of Examples 1 to 13 have a viscosity of 2000 mPa. s or less is low, so it is not only suitable for adhesives applied to minute areas using a jet dispenser, but also can form a hardened product showing high shear strength.

In contrast, the curable composition of Comparative Example 1 using a silica filler with an average particle diameter of 5.0 μm or more resulted in a cured product with low viscosity and sufficient shear strength. However, it had coarse particles and was not suitable for use. In applications using jet dispensers.

The ratio of the total epoxy functional group equivalents of components (B) and (C) to the thiol functional group equivalents of component (A) is less than 0.70. The curable composition of Comparative Example 2 has a high viscosity, and its viscosity is high. The formed hardened product exhibits numerically excellent shear strength, but exhibits thermoplasticity, so it is considered difficult to use above 70°C.

The curable composition of Comparative Example 3, in which the ratio of the total epoxy functional group equivalents of components (B) and (C) to the thiol functional group equivalents of component (A) exceeds 1.10, forms a cured The material becomes brittle and it is impossible to prepare a test piece for Tg measurement. Therefore, the shear strength was not measured.

The amount (mol) of component (C) is less than 25% of the total amount (mol) of component (B) and the amount (mol) of component (C). The curable composition of Comparative Example 4 has high viscosity and is not suitable for use. Purpose of using a jet dispenser.

In Comparative Example 5, in which the amount (mol) of component (C) exceeds 70% of the total amount (mol) of component (B) and component (C), the hardened material formed becomes brittle and Tg cannot be produced. Test piece for measurement. Therefore, the shear strength was not measured.

As described above, any of Comparative Examples 1 to 5 is difficult to apply as an adhesive or the like applied to a minute area using a jet dispenser.

[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. Therefore, in an assembly in which multiple parts made of different materials are joined together, the hardened product can be accompanied by deformation caused by thermal expansion of the parts. Furthermore, the hardened material is excellent in shear strength. Furthermore, the epoxy resin composition of the present invention is not only added with silica filler to improve shear strength, but also has low viscosity, making it suitable for use in micro-region applications such as using a jet dispenser. 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 multiple components made of different materials are joined and assembled.

Claims (6)

An epoxy resin composition, which contains the following components (A) to (E): (A) 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 type of monofunctional epoxy resin (but not silane coupling agent); (D) hardening catalyst; and (E) average particle size Silica filler with a diameter of 0.1 μm or more and 5.0 μm or less; the ratio of the total epoxy functional group equivalents of the above components (B) and (C) to the thiol functional group equivalents of the above component (A) ([epoxy Functional group equivalent]/[thiol functional group equivalent]) is 0.70 or more and 1.10 or less, and the amount (mol) of the above-mentioned component (C) is the amount (mol) of the above-mentioned component (B) and the amount (mol) of the above-mentioned component (C) ( mol), the viscosity at 30°C is 100mPa. s above 2000mPa. s or less. The epoxy resin composition according to claim 1, wherein the content of component (E) is 15 to 50 mass% relative to the total amount of the epoxy resin composition. The epoxy resin composition according to claim 1 or 2, wherein component (C) contains aromatic monofunctional epoxy resin. A sealing material comprising the epoxy resin composition as described in any one of claims 1 to 3. A hardened product obtained by hardening the epoxy resin composition according to any one of claims 1 to 3 or the sealing material according to claim 4. An electronic component including the hardened material according to claim 5.