KR20220039515A - Epoxy resin composition - Google Patents

Abstract

The present invention provides an epoxy resin composition that cures in a short time even under low-temperature conditions to provide a cured product having a low glass transition point (T _g ) and high glue strength, a sealing material comprising the same, a cured product obtained by curing the same, and a cured product thereof It relates to an electronic component comprising a. Since the epoxy resin composition of this invention provides hardened|cured material with a low Tg and high glue strength after hardening, it _is very useful as an adhesive agent for semiconductor devices and electronic components, a sealing material, a dam agent, etc.

Description

Epoxy resin composition {EPOXY RESIN COMPOSITION}

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

At present, for assembling or mounting electronic components used in semiconductor devices, for example, semiconductor chips, for the purpose of maintaining reliability, a curable resin composition, particularly an adhesive, sealing material, etc. containing an epoxy resin composition is often used. In particular, in the case of a semiconductor device including a component that deteriorates under a high temperature condition, all of its manufacturing steps need to be performed under a low temperature condition. Therefore, adhesives and sealing materials used in the manufacture of such devices are required to exhibit sufficient curability even under low-temperature conditions. At the same time, they are also required to be cured in a short time in terms of production cost.

The epoxy resin composition (hereinafter, simply referred to as "curable composition") used for such an adhesive or sealing material for electronic components 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). A hardening|curing agent contains the compound which has two or more functional groups which react with the epoxy group in an epoxy resin. Among these curable compositions, those using a thiol-based curing agent as a curing agent are known to cure appropriately in a short time even under low-temperature conditions of 0°C to -20°C. The thiol-based curing agent includes a compound having two or more thiol groups, that is, a polyfunctional thiol compound. As an example of such a curable composition, what is disclosed by patent document 1 is mentioned.

The epoxy resin composition provides a cured product having various properties depending on the composition thereof. From this point, depending on the purpose of use of the curable composition, etc., it may not be preferable that the glass transition point (T _g ) is high. For example, this is the case of joining two parts each made of a different material using this curable composition.

When the ambient temperature of an assembly formed by bonding two parts each made of different materials to each other with an adhesive changes, the parts each generate thermal stress according to the thermal expansion coefficient of the material. Since this thermal stress is not uniform according to the difference in thermal expansion coefficient, it is not canceled and causes the deformation|transformation of a granulated material. The stress accompanying this deformation acts especially on the joint part of a component, ie, the hardened|cured material of an adhesive agent, and will generate|occur|produce cracks etc. in the hardened|cured material in some cases. Such cracks are particularly likely to occur when the cured product is brittle and lacks flexibility. Accordingly, an adhesive for bonding parts made of different materials needs flexibility (low modulus of elasticity) sufficient to follow the deformation of the assembly due to thermal expansion of the parts after curing. To that end, it is required that the T _g of the cured product be suitably low.

International Publication No. 2012/093510

However, although the epoxy resin composition described in said patent document ₁ showed the outstanding low-temperature hardenability with sufficiently low Tg, the present inventors discovered that there existed a problem that the pull strength was low. There are cases where an electronic component is required to have drop impact resistance. In order to increase the drop impact resistance, it is preferable to improve the adhesive strength of the adhesive.

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

Under these circumstances, the present inventors have intensively researched in order to develop a curable composition that cures in a short time even under low-temperature conditions and provides a cured product having a low T _g and high pull strength. As a result, unexpectedly, as a component of the curable composition, a crosslinking density regulator including an aromatic monofunctional epoxy resin in addition to a thiol-based curing agent and an epoxy resin is used so that the physical property value of the cured product provided by the curable composition is within a predetermined range. It was found that by adjusting, the glue strength of the obtained cured product was increased, that is, it was excellent in the drop impact resistance. Based on the above new knowledge, it came to complete this invention.

That is, although this invention is not limited to the following, the following invention is included.

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

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

(B) at least one polyfunctional epoxy resin;

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

(D) curing catalyst

including,

In the DMA measurement by a frequency of 10 Hz, a temperature increase rate of 3 ° C./min, a tensile method,

The epoxy resin composition which provides the hardened|cured material in which the temperature at which the loss elastic modulus (E") becomes maximum is in the range of 20 degreeC or more and 55 degrees C or less.

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

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

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

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

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

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

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which shows the relationship between calibration pool intensity|strength and the peak temperature (maximum value) of E".

Hereinafter, the present invention will be described in detail.

As described above, the epoxy resin composition (curable composition) of the present invention comprises a thiol-based curing agent (component (A)), a polyfunctional epoxy resin (component (B)), a crosslinking density modifier (component (C)) and a curing catalyst. (component (D)) is included as an essential component. These components (A)-(D) are demonstrated below.

In addition, in this specification, in accordance with the custom in the field of epoxy resins, with respect to the components constituting the epoxy resin composition before curing, a name containing the term "resin" which usually refers to a polymer (especially a synthetic polymer) is used, Even though the component is not a polymer, it is sometimes used.

(1) Thiol-based curing agent (component (A))

The thiol-based curing agent (component (A)) used in the present invention has three or more thiol groups that react with the epoxy groups in the polyfunctional epoxy resin (component (B)) or crosslinking density modifier (component (C)) described later. At least 1 type of polyfunctional thiol compound is included. It is preferable that a component (A) contains a trifunctional and/or tetrafunctional thiol compound. It is preferable that thiol equivalent is 90-150 g/eq, It is more preferable that it is 90-140 g/eq, It is still more preferable that it is 90-130 g/eq. In addition, a trifunctional and tetrafunctional thiol compound is a thiol compound which has 3 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, a component containing a non-hydrolyzable polyfunctional thiol compound that does not have a hydrolyzable partial structure such as an ester bond ( A) is preferably used. The non-hydrolyzable polyfunctional thiol compound hardly undergoes hydrolysis even in a high-temperature and high-humidity environment.

In another aspect of this invention, component (A) contains the thiol compound which has an ester bond in a molecule|numerator, and the thiol compound which does not have an ester bond in a molecule|numerator. Moreover, from a viewpoint of reducing T _g , it is preferable that component (A) contains the thiol resin without a urea bond.

Examples of the hydrolyzable polyfunctional thiol compound include trimethylolpropanetris(3-mercaptopropionate) (manufactured by SC Yuki Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl ]-isocyanurate (SC Yuki Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (SC Yuki Chemical Corporation: PEMP), tetraethylene glycol bis (3-mercaptopropionate) (manufactured by SC Yuki Chemical Corporation: EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Yuki Chemical Corporation: DPMP) ), pentaerythritol tetrakis(3-mercaptobutyrate) (Showa Denko Co., Ltd.: Karenz MT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6(1H,3H,5H)-trion (Showa Denko Co., Ltd.: Karenz MT (trademark) NR1) etc. are mentioned.

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

(during the meal,

R ¹ and R ² are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group,

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of a mercaptomethyl group, a mercaptoethyl group and a mercaptopropyl group)

is a compound represented by Examples of the compound represented by the formula (1) include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (trade name: TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), (1, 3,4,6-tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), 1,3,4,6-tetrakis(mercaptomethyl)glycol uril, 1,3,4,6-tetrakis (mercaptomethyl) -3a-methyl glycoluril, 1,3,4,6-tetrakis (2-mercaptoethyl) -3a-methyl glycoluril, 1, 3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3, 4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1, 3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril; 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluril, etc. These may be used individually, respectively, or 2 or more types may be mixed and used for these. Of these, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril are particularly preferred.

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

(R ⁸ ) _m -A-(R ⁷ -SH) _n (2)

(during the meal,

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

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

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

m is an integer of 0 or more,

n is an integer of 3 or more,

Each of R ⁷ and R ⁸ is bonded to A through the oxygen atom)

is a compound represented by You may use the compound represented by Formula (2) in combination of 2 or more types. Examples of the compound represented by the formula (2) include pentaerythritol tripropanethiol (trade name: PEPT, manufactured by SC Yuki Chemical), pentaerythritol tetrapropanethiol, and the like. Among these, pentaerythritol tripropanethiol is particularly preferable.

As the non-hydrolyzable polyfunctional thiol compound, a trifunctional or higher polythiol compound having two or more sulfide bonds in the molecule can also be used. As such a thiol compound, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3- Mercaptopropylthio) propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tri Thiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 -Trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, 1,1,3,3 -tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane , 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7 -Dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1, 6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl) 3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2 ,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethyl) Thio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto -2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio) )-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto- 2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimer Capto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1 ,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6- dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio- 1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4 -(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2; 4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4 ,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto -2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio ) -1,17-dimercapto-2,4,6,10,12,16-aliphatic polythiol compounds such as hexathiaheptadecane; 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1 ,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethyl Thio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4 -[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis( Mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2 -{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithiethane, 2-[3,4-bis(mer Captomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio) )-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3-bis(mercaptomethylthio)methyl-5, 6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiethane, 4-{1-[2-(1,3) -dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3- and polythiol compounds having a cyclic structure such as dithiolane.

(2) epoxy resin (component (B))

There is no restriction|limiting in particular as long as the epoxy resin (component (B)) used in this invention contains at least 1 type of polyfunctional epoxy resin. Therefore, conventionally used epoxy resins can be used as component (B). As described above, the polyfunctional epoxy resin refers to an epoxy resin having two or more epoxy groups. In one aspect of the present invention, the component (B) contains a bifunctional epoxy resin.

Polyfunctional epoxy resins are largely divided into aliphatic polyfunctional epoxy resins and aromatic polyfunctional epoxy resins.

As an example of an aliphatic polyfunctional epoxy resin,

- (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether , Trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, dicyclopentadiene diepoxy resins such as diglycidyl ether;

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

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

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

hydantoin-type epoxy resins such as -1,3-diglycidyl-5-methyl-5-ethylhydantoin; and

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

etc. are mentioned, but it is not limited to these.

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

In one aspect of the present invention, component (B) contains an aliphatic polyfunctional epoxy resin. When using an aliphatic polyfunctional epoxy resin as a component (B), it is preferable that the component (A) to combine contains a trifunctional thiol compound or a tetrafunctional thiol compound which has a glycoluril skeleton or an isocyanuric skeleton. It is preferable that the ratio ([epoxy functional group equivalent]/[thiol functional group equivalent]) of the epoxy functional group equivalent in the aliphatic polyfunctional epoxy resin to the glycoluril skeleton or the thiol compound having an isocyanuric skeleton is 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 a glycoluril skeleton or an isocyanuric skeleton. When a trifunctional thiol compound or a tetrafunctional thiol compound having a glycoluril skeleton or an isocyanuric skeleton is used as the component (A), as the component (B), a cyclohexane-type diglycidyl ether or a silicone skeleton is used. It is preferable to use an epoxy resin. In particular, it is preferable to use 1,4-cyclohexanedimethanol diglycidyl ether or 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane.

Further, in one aspect of the present invention, the component (A) is a trifunctional thiol compound or a tetrafunctional thiol compound (specifically, a polyether skeleton, a polysulfide skeleton, or a trifunctional thiol compound or a tetrafunctional thiol compound having a polyester skeleton). In order to set the temperature at which E" becomes the maximum in a desired range, in the epoxy resin composition, the aliphatic polyfunctional epoxy resin and the trifunctional thiol compound or the tetrafunctional thiol compound which does not have a glycoluril skeleton or an isocyanuric skeleton It is preferable that they are 10 mass % or more and 55 mass % or less, It is more preferable that total amounts are 20 mass % or more and 50 mass % or less, It is more preferable that they are 25 mass % or more and 50 mass % or less.

An aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin which has a structure containing aromatic rings, such as a benzene ring. There are many such types of epoxy resins which are conventionally used frequently, such as a bisphenol A epoxy resin. As an example of an aromatic polyfunctional epoxy resin,

-Bisphenol A type epoxy resin;

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

-Bisphenol F-type epoxy resin;

-Novolac-type epoxy resin;

-Tetrabromobisphenol A type epoxy resin;

-fluorene-type epoxy resin;

-biphenylaralkylepoxy resins;

a diepoxy resin such as -1,4-phenyldimethanol diglycidyl ether;

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

- glycidylamine type epoxy resins such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; and

-Naphthalene ring-containing epoxy resin

etc. are mentioned, but it is not limited to these. From the viewpoint of compatibility with the thiol compound, the component (B) further preferably contains an aromatic polyfunctional epoxy resin rather than an aliphatic polyfunctional epoxy resin. As the aromatic polyfunctional epoxy resin, bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, and glycidylamine-type epoxy resin are preferable, and among them, the epoxy equivalent of 90 to 200 g/eq is particularly preferable, and the epoxy equivalent is Most preferably, it is 110 to 190 g/eq.

When an aromatic polyfunctional epoxy resin is used as the component (B), the component (A) to be combined is a trifunctional thiol compound or a tetrafunctional thiol compound having a polyether skeleton, a polysulfide skeleton, or a polyester skeleton. desirable. The ratio ([epoxy functional group equivalent]/[thiol functional group equivalent]) of the epoxy functional group equivalent in the aromatic polyfunctional epoxy resin to the thiol compound having a polyether skeleton, polysulfide skeleton, or polyester skeleton is 0.30 to 1.10 it is preferable 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 the component (A), as the component (B), a bisphenol A-type epoxy resin; It is preferable to use at least one of a bisphenol F-type epoxy resin and a naphthalene ring containing epoxy resin.

In addition, in order to set the temperature at which E" becomes the maximum in a desired range, in the epoxy resin composition, it has an aromatic epoxy resin (monofunctional and polyfunctional aromatic epoxy resin) and a glycoluril skeleton or isocyanuric skeleton, The total amount of the trifunctional thiol compound or the tetrafunctional thiol compound is preferably 45 mass % or more and 90 mass % or less, more preferably 50 mass % or more and 80 mass % or less, and still more preferably 50 mass % or more and 75 mass % or less. .

(3) crosslinking density modifier (component (C))

There is no restriction|limiting in particular as long as the crosslinking density regulator (component (C)) used in this invention contains at least 1 sort(s) of aromatic monofunctional epoxy resin. A monofunctional epoxy resin is an epoxy resin which has one epoxy group, and is conventionally used for viscosity adjustment of an epoxy resin composition as a reactive diluent. Monofunctional epoxy resins are largely divided into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the component (C) preferably has an epoxy equivalent of 180 to 400 g/eq. In this invention, it is preferable that a component (C) contains an aromatic monofunctional epoxy resin from a viewpoint of a viscosity and low volatility. Moreover, it is more preferable that component (C) is an aromatic monofunctional epoxy resin substantially.

Examples of the aromatic monofunctional epoxy resin contained in the component (C) include phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, and p-tert-butylphenyl glycidyl. Although ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, etc. are mentioned, It is not limited to these. Of these, p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferable, and p-tert-butylphenyl glycidyl ether is particularly preferable. Examples of the aliphatic monofunctional epoxy resin include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pineneoxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1 ,2-Epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, neodecane Although acid glycidyl ester etc. are mentioned, It is not limited to these.

(4) curing catalyst (component (D))

The curing catalyst (component (D)) used in the present invention is not particularly limited as long as it is a curing catalyst for an epoxy resin (component (B)), and a known curing catalyst can be used. It is preferable that component (D) is a latent curing catalyst. A latent curing catalyst is a compound which is inactive at room temperature, is activated by heating, and functions as a curing catalyst, For example, the imidazole compound which is solid at normal temperature; solid dispersion type amine adduct system latent curing catalysts, such as reaction products of an amine compound and an epoxy compound (amine-epoxy adduct system); A reaction product of an amine compound and an isocyanate compound or a urea compound (urea type adduct system), etc. are mentioned. By using the said component (D), the epoxy resin composition of this invention can be hardened in a short time also under low-temperature conditions.

Representative examples of commercially available latent curing catalysts include "Amicure PN-23" (Ajinomoto Fine Techno Co., Ltd. brand name), "Amicure PN-40" (Ajinomoto) as an amine-epoxy adduct system (amine adduct system). Fine Techno Co., Ltd. brand name), “Amicure PN-50” (Ajinomoto Fine Techno Co., Ltd. brand name), “Hardner X-3661S” (ACR Co., Ltd. brand name), “Hardner X-3670S” (ACR Co., Ltd.) brand name), "Novacure HX-3742" (Asahi Kasei Co., Ltd. brand name), "Novacure HX-3721" (Asahi Kasei Co., Ltd. brand name), "Novacure HXA9322HP" (Asahi Kasei Co., Ltd. brand name), " “Novacure HXA3922HP” (Asahi Kasei Co., Ltd. brand name), “Novacure HXA3932HP” (Asahi Kasei Co., Ltd. brand name), “Novacure HXA5945HP” (Asahi Kasei Co., Ltd. brand name), “Novacure HXA9382HP” (Asahi Gassei) Note) brand name), "Fuji Cure FXR1121" (T&K TOKA Co., Ltd. brand name), etc. are mentioned, In addition, as an element type adduct system, "Fuji Cure FXE-1000" (T&K TOKA Co., Ltd. brand name), "Fuji Cure FXR-1030" (T&K TOKA Co., Ltd. brand name) etc. are mentioned, However, It is not limited to these. Component (D) may be individual or may use 2 or more types together. As a component (D), a solid dispersion type amine adduct system latent curing catalyst is preferable from a pot life and a sclerosing|hardenable viewpoint.

In addition, some are provided in the form of the dispersion liquid disperse|distributed to a polyfunctional epoxy resin as a component (D). When using the component (D) of such a form, it should be careful that the quantity of the polyfunctional epoxy resin in which it is disperse|distributed is also included in the quantity of the said component (B) in the epoxy resin composition of this invention.

The thiol functional group equivalent means the total number of thiol groups of the thiol compound contained in the component or composition of interest, and the quotient obtained by dividing the mass (g) of the thiol compound contained in the component or composition of interest by the thiol equivalent of the thiol compound (When two or more thiol compounds are contained, it is the sum total with respect to each thiol compound). A thiol equivalent can be determined by the iodine titration method. This method is widely known and is disclosed, for example, in paragraph 0079 of Japanese Patent Application Laid-Open No. 2012-153794. When a thiol equivalent cannot be calculated|required by this method, you may calculate as the quotient obtained by dividing the molecular weight of the thiol compound by the number of thiol groups in one molecule of the thiol compound.

On the other hand, the epoxy functional group equivalent means the total number of epoxy groups of the epoxy resin (components (B) and (C)) contained in the component or composition, and the mass of the epoxy resin contained in the component or composition of interest (g) , is a quotient divided by the epoxy equivalent of the epoxy resin (when a plurality of epoxy resins are included, the sum of those quotients for each epoxy resin). An epoxy equivalent can be calculated|required by the method described in JISK7236. When an epoxy equivalent cannot be calculated|required by this method, you may compute as the quotient which divided 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 excessive with respect to the epoxy resin provides a cured product having a low initial T _g (T _g immediately after curing). However, when a thiol-type hardening|curing agent is excessive with respect to an epoxy resin in this way, it does not react with an epoxy group, but the thiol group which remains in hardened|cured material with unreacted state increases. In Patent Document 1, the present inventors disclosed a composition having a small change in T _g after the heat resistance test. After that, in such a composition, in a moisture resistance reliability test (especially at 85° C. for 100 hours under an environment of 85%), after the test , discovered that there is a possibility that new crosslinking by excessive thiol groups may occur. Although progress of this crosslinking is moderate compared with the case _where an epoxy resin is excessive with respect to a thiol-type hardening|curing agent, it causes a raise of Tg. In one aspect of the present invention, for this reason, the ratio ([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 such a curable composition, since the epoxy group contained in the said component (C) which reduces the unreacted thiol group exists, as a result of the reaction between them, most of unreacted thiol group lose|disappears. The polyfunctional epoxy resin contained in the component (B) has a function of linking two molecules of the polyfunctional thiol compound contained in the component (A) to extend a polymer chain or form crosslinking between polymer chains . However, since the monofunctional epoxy resin contained in the component (C) does not have such a function, the reaction between the components (A) and (C) causes a new crosslinking that raises the T _g of the cured product. can be suppressed Therefore, since the cured product provided by such a curable composition has a small content of a functional group capable of forming a new cross-link, even after a long period of time after curing, a rise in T _g accompanying the formation of a new cross-link is hardly observed.

In one aspect of the present invention, the ratio of the sum of the epoxy functional group equivalents for the components (B) and (C) to the thiol functional group equivalent to the component (A) ([epoxy functional group equivalent] / [thiol functional group equivalent ]) of 0.70 or more and 1.10 or less, the proportion of the epoxy group and the thiol group involved in the reaction between the epoxy group and the thiol group is at least a certain ratio with respect to both the epoxy group and the thiol group in the composition, so that the properties of the resulting cured product are appropriate. When the above ratio is less than 0.70, since there is an excess of thiol groups with respect to the epoxy groups, the number of thiol groups remaining in the cured product as unreacted increases, and it becomes difficult to suppress the T _g increase of the cured product accompanying the reaction of the thiol groups. On the other hand, when the above ratio is more than 1.10, since the epoxy group is excessive with respect to the thiol group, in addition to the reaction between the epoxy group and the thiol group, the reaction (single polymerization) of the excess epoxy group proceeds. As a result, since intermolecular bridge|crosslinking by these both reaction is formed in the hardened|cured material _obtained , a crosslinking density becomes high too much, and Tg rises. Or low-temperature hardening of 1 hour at 80 degreeC becomes difficult.

If desired, the curable composition of this invention may contain arbitrary components other than the said (A)-(D) component, for example, what is demonstrated below as needed.

ㆍStabilizer

A stabilizer can be added to the epoxy resin composition of this invention if desired. A stabilizer can be added to the epoxy resin composition of this invention in order to improve the storage stability and to lengthen a pot life. Various known stabilizers can be used as stabilizers for one-part adhesives based on epoxy resins, but from the high effect of improving storage stability, at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates and organic acids is preferred Do.

Examples of the liquid boric acid ester compound include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, and triisopropyl Borate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, triocta Decylborate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4, 7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate. Since a liquid boric acid ester compound is liquid at room temperature (25 degreeC), since it can suppress the compounding viscosity low, it is preferable. As the aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used.

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

ㆍFillers

A filler can be added to the epoxy resin composition of this invention if desired. When the epoxy resin composition of the present invention is used as a one-component adhesive, adding a filler thereto improves moisture resistance and thermal cycle resistance, particularly thermal cycle resistance, of the bonded site. The reason that the thermal cycle resistance is improved by the addition of the filler is that the coefficient of linear expansion of the cured product is reduced, that is, expansion and contraction of the cured product due to the thermal cycle is suppressed.

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

When adding a filler, it is preferable that content of the filler in the epoxy resin composition of this invention is 5-80 mass % in the whole epoxy resin composition, It is more preferable that it is 5-65 mass %, 5- It is more preferable that it is 50 mass %.

ㆍCoupling agent

A coupling agent can be added to the epoxy resin composition of this invention if desired. The addition of a coupling agent, especially a silane coupling agent, is preferable from a viewpoint of an adhesive strength improvement. As a coupling agent, various silane coupling agents, such as an epoxy type, an amino type, a vinyl type, a methacryl type, an acryl type, a mercapto type, can be used. Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-bu). Thylidene) propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltri Methoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-iso Cyanatopropyltriethoxysilane etc. are mentioned. These silane coupling agents may be used independently or may use 2 or more types together.

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

ㆍOther additives

To the epoxy resin composition of the present invention, if desired, other additives such as carbon black, titanium black, ion trapping agent, leveling agent, antioxidant, antifoaming agent, thixotropic agent, viscosity Adjusters, flame retardants, colorants, solvents and the like may be added. The type and amount of each additive are as usual.

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

A person skilled in the art can adjust the amounts of components (A) to (D) and the like constituting the epoxy resin composition of the present invention so that the cured product provided by the composition has a predetermined loss modulus. In addition, the measuring method of a loss elastic modulus is well-known, and a person skilled in the art can measure a loss elastic modulus easily using the conventional dynamic viscoelasticity measuring apparatus.

As described above, in the cured product provided by the epoxy resin composition of the present invention, the temperature at which the loss elastic modulus (E″) is maximized is in the range of 20°C or more and 55°C or less. Epoxy whose temperature is not in the above range In a resin composition, the pull strength of hardened|cured material, ie, drop impact resistance, does not fully improve.

The epoxy resin composition of this invention provides the hardened|cured material in which the temperature at which a loss elastic modulus becomes maximum, Preferably it is 20 degreeC or more and 50 degrees C or less, More preferably, it exists in the range of 20 degreeC or more and 45 degrees C or less.

From the viewpoint of making 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) and the component (A) is preferably 1.15 or more and 1.45 or less am.

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

The relationship between the molar ratio (B)/(A) of the component (B) and the component (A) reduces the crosslinking point of the component (A) containing a thiol compound having three or more thiol groups, for example, thiol If it is a thiol compound having four groups, it means that it is used as a bifunctional thiol compound or a trifunctional thiol compound. When the above ratio is less than 1.15, since there is too little polyfunctional epoxy resin as a crosslinking component, there exists a possibility that the hardened|cured material obtained may exhibit the property similar to a thermoplastic resin that melt|dissolves under high temperature. On the other hand, if the above ratio is more than 1.45, since there are too many polyfunctional epoxy resins as a crosslinking component, intermolecular crosslinking by the reaction of components (A) and (B) in the obtained cured product is excessively formed, and the crosslinking density becomes too high. , there is a possibility that the pull strength may become small.

The relationship between the molar ratio (C)/(A) of the component (C) and the component (A) is that the thiol group of the component (A) is appropriate with respect to the number (amount) of epoxy groups contained in the component (C). It means excess. Since this relationship is satisfied, a cured product having an appropriate density of crosslinking formed by the reaction of components (A) and (B) can be obtained, which is preferable.

By satisfying the relationship between the molar ratio (B)/(A) of the component (B) and the component (A), and the molar ratio (C)/(A) of the component (C) to the component (A), the component (B) ) and the unreacted thiol group of the component (A) reacts with the component (C), and the unreacted thiol group remaining in the cured product decreases, so that the properties of the resulting cured product are appropriate.

In particular, the cured product provided by the epoxy resin composition of the present invention is LCP (liquid crystal polymer), PC (polycarbonate), PBT (polybutylene terephthalate), SUS, alumina, nickel (the surface is nickel-plated It exhibits excellent adhesive strength to an adherend selected from among the following). These may be surface-treated with plasma etc. In this specification, "pull strength" typically means the glue strength in the case where these to-be-adhered bodies are these materials.

The method of manufacturing the epoxy resin composition of this invention is not specifically limited. For example, components (A) to (D) and, if desired, other additives are introduced simultaneously or separately into a suitable mixer, and if necessary, by heating and melting with stirring and mixing to obtain a uniform composition, the present invention of epoxy resin composition can be obtained. Although this mixer is not specifically limited, A brain grinder equipped with a stirring device and a heating device, a Henschel mixer, a three roll mill, a ball mill, a planetary mixer, a bead mill, etc. can be used. Moreover, you may use combining these apparatuses suitably.

Thus, the obtained epoxy resin composition is thermosetting, and on the conditions of the temperature of 80 degreeC, it is preferable to harden|cure within 5 hours, and it is more preferable to harden|cure within 1 hour. In addition, curing at a high temperature of several seconds at a temperature of 150° C. and in a very short time is also possible. When the curable composition of the present invention is used for manufacturing an image sensor module including a component that deteriorates under high temperature conditions, the composition is thermally cured at a temperature of 60 to 90° C. for 30 to 120 minutes, or 120 to 200° C. It is preferable to thermoset it at a temperature of 1 to 300 seconds.

The epoxy resin composition of this invention hardens|cures in a short time also under low-temperature conditions, and provides the hardened|cured material with low _Tg . It is preferable that T _g is 65 degrees C or less, as for the hardened|cured material of the epoxy resin composition of this invention, It is more preferable that it is 60 degrees C or less, It is still more preferable that it is 50 degrees C or less. Moreover, it is preferable that it is 30 degreeC or more, and, as for T _g of hardened|cured material from an adhesive viewpoint, it is more preferable that it is 32 degreeC or more. In the present invention, T _g is, using a dynamic thermomechanical measurement device (DMA), in the range of -20°C to 110°C, a frequency of 1 to 10 Hz, a temperature increase rate of 1 to 10°C/min, a strain amplitude of 5.0 μm, and tensile can be obtained by law. A preferred frequency is 10 Hz, and a preferred temperature increase rate is 3° C./min. T _g is calculated|required from the peak temperature of loss tangent (tanδ) calculated|required from loss elastic modulus (E")/storage elastic modulus (E').

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

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

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

In this invention, the electronic component containing the hardened|cured material of this invention is also provided.

<Example>

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. In addition, in the following examples, parts and % represent mass parts and mass % unless otherwise indicated.

Examples 1 to 9, Comparative Examples 1 to 3

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

ㆍThiol-based curing agent (component (A))

In an Example and a comparative example, the compound used as a component (A) is as follows.

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

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

(A-3): pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMP, SC Yuki Chemical Co., Ltd., thiol equivalent: 122)

ㆍEpoxy resin (component (B))

In an Example and a comparative example, the compound used as a component (B) is as follows.

(B-1): Bisphenol F-type epoxy resin (trade name: YDF-8170, manufactured by Shinnitetsu Sumikin Co., Ltd., epoxy equivalent: 159)

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

(B-3): dicyclopentadiene type epoxy resin (trade name: EP4088L, manufactured by ADEKA Corporation, epoxy equivalent 165)

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

(B-5): 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane (trade name: TSL9906, Momentive Performance Materials, manufactured by Kodo Japan Corporation; Epoxy equivalent: 181)

ㆍCrosslinking density control agent (component (C))

In an Example and a comparative example, the compound used as a component (C) is as follows.

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

ㆍCure catalyst (component (D))

In an Example and a comparative example, the compound used as a component (D) is as follows.

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

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

・Other ingredients (component (E))

In an Example and a comparative example, the compound used as a component (E) is as follows.

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

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

In the Example and the comparative example, the characteristic of the hardened|cured material obtained by hardening|curing an epoxy resin composition was measured as follows.

(Production of cured products)

Hardened|cured material was obtained by heating the resin composition of Examples 1-9 and Comparative Examples 1-3 at 80 degreeC for 120 minutes, respectively.

<Loss modulus of cured product (E") >

It carried out using the measuring method of Tg of Japanese Industrial Standards JIS _C6481 . Specifically, first, a Teflon (registered trademark) sheet is affixed on the surface of a glass plate having a thickness of 3 mm, and two spacers (heat-resistant tape superimposed on it) are placed thereon so that the film thickness when cured is 400 ± 150 µm. placed in Next, a resin composition was applied between the spacers, and sandwiched between separate glass plates with a Teflon (registered trademark) sheet attached to the surface so as not to entrap air bubbles, and cured at 80° C. for 120 minutes to obtain a cured product. Finally, after peeling this hardened|cured material from the glass plate to which the Teflon (trademark) sheet was stuck, it cut out to predetermined dimensions (10 mm x 40 mm) with a cutter, and obtained the test piece. In addition, the cutouts were smoothed with sandpaper. This cured product was subjected to a dynamic thermomechanical measurement device (DMA) (manufactured by Seiko Instruments) in a range of -20°C to 110°C, a frequency of 10 Hz, a temperature increase rate of 3°C/min, a strain amplitude of 5.0 µm, and a tensile method; The loss elastic modulus (E") of the cured product was measured, and the temperature (°C) at which E" became the maximum was determined. The results are shown in Tables 1 and 2.

<Actual measured glue strength and calibrated glue strength of cured product>

Spacers (heat-resistant tape with a thickness of 150 µm) were arranged in two places on an alumina plate having a length of 20 mm x a width of 20 mm x a thickness of 1.6 mm. Then, 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 placed on the spacer so as to be in contact with the applied resin composition. Then, the test body was obtained by heat-hardening at 80 degreeC for 120 minute(s). A nut was attached to the upper part of the thick plate of this test specimen using a moisture-curing adhesive, and in order to prevent peeling between the thick plate and the nut when measuring the pull strength, it was left for 12 hours to sufficiently bond the thick plate and the nut. After that, after fixing the alumina plate to a precision load measuring machine (manufactured by Aiko Engineering, model number: 1605HTP) so that the bonding surface is level, pass the string through the wheel of the nut, install this string on the jig, and , a tensile load was applied at a rate of 12 mm/min in the vertical direction. The value obtained by dividing the maximum load applied until the alumina plate and the thick plate were separated by the bonding area between the alumina plate and the thick plate was taken as the measured glue strength (N=6). The unit is N/mm 2 . In addition, from this measured pool strength, the corrected pool strength was calculated|required using the following formula derived from the comparison of Examples 1 and 2. The unit is N/mm 2 . The results are shown in Tables 1 and 2.

Calibration pool strength = measured pool strength/((100-component (E) content (wt%) × 1.2)/100)

Although the epoxy resin composition of this invention can be used, adding component (E) (filler) as needed, content of component (E) (filler) increases so that the comparison of Examples 1 and 2 may show The measured glue strength of the cured product on the lower surface tends to decrease. The corrected pool strength is the pool strength that canceled the influence of the component (E).

As is apparent from Tables 1 to 2, in any of Examples 1 to 9, the glue strength after curing (particularly the correction pool strength) was a satisfactory value.

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

The relationship between the calibration pool strength of Tables 1 and 2 and the peak temperature (maximal value) of E" is shown in Fig. 1. In Fig. 1, from the relationship of the straight line between I and II, the thiol functional group equivalent of component (A) As the epoxy functional group equivalent of component (C) increases, it turns out that the pull strength becomes high.

The epoxy resin composition of the present invention is cured in a short time even under low-temperature conditions to provide a cured product. This hardened|cured material shows low _Tg , and has moderate softness|flexibility and flexibility. Moreover, since this hardened|cured material shows high pull strength, by using the epoxy resin composition of this invention, the electronic component excellent in drop impact resistance can be manufactured easily. Accordingly, the epoxy resin composition of the present invention is particularly useful as an adhesive, a sealing material, a damming agent, etc. for a semiconductor device or electronic component assembled by bonding a plurality of components made of different materials.

Claims (7)

An epoxy resin composition comprising the following components (A) to (D):
(A) at least one thiol-based curing agent comprising a polyfunctional thiol compound having three or more thiol groups;
(B) at least one polyfunctional epoxy resin;
(C) a crosslinking density modifier comprising at least one aromatic monofunctional epoxy resin; and
(D) curing catalyst
including,
In the DMA measurement by a frequency of 10 Hz, a temperature increase rate of 3 ° C./min, a tensile method,
The epoxy resin composition which provides the hardened|cured material in which the temperature at which the loss elastic modulus (E") becomes maximum is in the range of 20 degreeC or more and 55 degrees C or less. The epoxy resin composition according to claim 1, wherein the molar ratio (B)/(A) of the component (B) and the component (A) is 1.15 or more and 1.45 or less. The epoxy resin composition according to claim 1 or 2, wherein the molar ratio (C)/(A) of the component (C) and the component (A) is 0.55 or more and 1.65 or less. The epoxy resin composition according to any one of claims 1 to 3, wherein component (C) comprises an aromatic monofunctional epoxy resin. The sealing material containing the epoxy resin composition in any one of Claims 1-4. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4 or the sealing material according to claim 5. The electronic component containing the hardened|cured material of Claim 6.

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