KR102555587B1 - Epoxy Resin Composition - Google Patents

Abstract

The present invention provides an epoxy resin composition that can be thermally cured in a short time of about 10 minutes or less at a low temperature of about 100 ° C. or less, and further has excellent adhesive strength and pot life. The epoxy resin composition of the present invention contains (A) an epoxy resin, (B) a thiol-based curing agent, and (C) 1,4-diazabicyclo[2.2.2]octane as an active ingredient (1,4-diazabicyclo[2.2.2] octane (DABCO)) containing an isocyanate adduct type microencapsulation curing accelerator, and the ratio (mass ratio) of the aromatic epoxy resin to the aliphatic epoxy resin in the epoxy resin of component (A) is from 10:0 to 10:0. 2:8, characterized in that the amount of DABCO in the component (C) is 0.01 to 2 parts by mass with respect to the total of 100 parts by mass of the components (A) to (C).

Description

Epoxy Resin Composition

The present invention relates to a resin composition suitable for one-component adhesives for applications requiring low-temperature, short-time curing at 100°C for 20 minutes or less or 80°C for 60 minutes or less.

Since epoxy resins have excellent electrical insulation properties, mechanical strength, heat resistance, moisture resistance, adhesion and other material properties, an epoxy resin composition containing an epoxy resin as a main agent and a curing agent and/or a curing accelerator of the epoxy resin It is widely used as an adhesive for electronic components. Curing agents for epoxy resins used for the above purpose include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and the like. On the other hand, as curing accelerators for epoxy resins used for the above purpose, there are imidazoles and the like.

In the manufacture of an image sensor module used as a camera module of a mobile phone or smart phone, a one-component adhesive that is thermally cured at a relatively low temperature, specifically, about 100° C. or less, is used. Even when manufacturing electronic components such as semiconductor devices, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors, the use of a one-component adhesive that is thermally cured at a temperature of about 100 ° C. is sometimes required.

In Patent Literatures 1 and 2, both excellent low-temperature curing properties and storage stability are achieved by using a microcapsule type latent curing agent as a curing agent for an epoxy resin, but the curing rate can be further improved by using a curing accelerator.

From the viewpoint of productivity improvement, it is desired to further improve the curing rate. Specifically, low-temperature short-time curing at 100°C for 20 minutes or less or 80°C for 60 minutes or less is required.

Patent Literatures 1 and 2 cannot respond to such low-temperature and short-time thermal curing.

Japanese Unexamined Patent Publication No. 2009-161751 Japanese Unexamined Patent Publication No. 2009-203453

In order to solve the problems of the prior art, the present invention provides an epoxy resin composition capable of curing at a low temperature for 20 minutes or less at 100 ° C. or 60 minutes or less at 80 ° C. and having excellent adhesive strength and pot life. The purpose.

In order to achieve the above object, the present invention

(A) an epoxy resin;

(B) a thiol-based curing agent;

(C) an isocyanate adduct type microencapsulated curing accelerator containing 1,4-diazabicyclo[2.2.2]octane (DABCO) as an active ingredient;

The ratio (mass ratio) of the aromatic epoxy resin and the aliphatic epoxy resin in the epoxy resin of the component (A) is 10:0 to 2:8,

An epoxy resin composition characterized in that the amount of DABCO in the component (C) is 0.01 to 2 parts by mass relative to 100 parts by mass in total of the components (A) to (C).

In the epoxy resin composition of the present invention, the thiol-based curing agent of component (B) is preferably a mercaptoalkylglycoluril represented by formula (I).

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a mercaptomethyl group, a 2-mercaptoethyl group, a 3- represents a mercaptoalkyl group selected from a mercaptopropyl group and a 4-mercaptobutyl group, and n is 0 to 3)

The epoxy resin composition of the present invention may further contain (D) a thickening inhibitor.

The thickening inhibitor of the component (D) is preferably at least one selected from the group consisting of boric acid esters, aluminum chelates, and organic acids.

Moreover, this invention provides the resin cured material obtained by heating a resin composition.

In addition, the present invention provides a one-component adhesive comprising the resin composition of the present invention.

In addition, the present invention provides an encapsulant comprising the epoxy resin composition of the present invention.

In addition, the present invention provides an image sensor module manufactured using the one-component adhesive of the present invention.

In addition, the present invention provides an electronic component manufactured using the one-component adhesive of the present invention.

In addition, the present invention provides a semiconductor device having a flip chip type semiconductor element sealed using the encapsulant of the present invention.

The epoxy resin composition of the present invention can be cured at 100°C for 20 minutes or less or at 80°C for 60 minutes or less for a short time. The epoxy resin composition of the present invention is also excellent in adhesive strength and pot life. For this reason, it is suitable as a one-component adhesive used in the manufacture of image sensor modules and electronic components.

Hereinafter, the epoxy resin composition of the present invention will be described in detail.

The resin composition of the present invention contains components (A) to (C) shown below as essential components.

(A) component: epoxy resin

(A) The epoxy resin of component should just have one or more epoxy groups per molecule. As an example of the epoxy resin of the component (A), monovalent or polyhydric phenols such as phenol, bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol, alkyl alcohol, glycerin, polyethylene glycol, etc. Monoglycidyl ether or polyglycidyl ether obtained by reacting alcohol with epichlorohydrin, hydroxycarboxylic acids such as benzoic acid, p-hydroxybenzoic acid, and β-hydroxynaphthoic acid, and epichlorohydrin reaction glycidyl ether esters obtained by reacting carboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin, monoglycidyl esters or polyglycidyl esters obtained by reacting epichlorohydrin, 1,6-bis(2,3-epoxypropoxy) Epoxy resins having a naphthalene skeleton such as naphthalene, epoxidized phenol novolak resins, epoxidized cresol novolac resins, epoxidized polyolefins, cyclic aliphatic epoxy resins, urethane-modified epoxy resins, silicone-modified epoxy resins, etc. not limited to these

Among the epoxy resins exemplified above, an aromatic epoxy resin having a benzene ring contributes to an improvement in the curing rate. In addition, the aromatic epoxy resin having a benzene ring is difficult to dissolve the microcapsules of (C) described later. Therefore, in the epoxy resin composition of the present invention, the epoxy resin of component (A) contains an aromatic epoxy resin, and the proportion of the aromatic epoxy resin in the epoxy resin of component (A) is high. Specifically, in the epoxy resin of component (A), the ratio (mass ratio) of the aromatic epoxy resin to the aliphatic epoxy resin is 10:0 to 2:8. Here, an aromatic epoxy resin in this specification refers to an epoxy resin having a benzene ring. As the aromatic epoxy resin, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin is preferable. On the other hand, an aliphatic epoxy resin refers to an epoxy resin having no benzene ring, for example, cyclohexane dimethanol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, urethane A modified epoxy resin, a silicone modified epoxy resin, etc. correspond. The aliphatic epoxy resin acts as a reactive diluent and can lower the viscosity of the epoxy resin composition.

(A) Component epoxy resin WHEREIN: It is preferable that the ratio (mass ratio) of an aromatic type epoxy resin and an aliphatic type epoxy resin is 10:0 - 3:7.

(B) thiol-based curing agent

The thiol-based curing agent of component (B) is a curing agent for the epoxy resin of component (A).

As the thiol-based curing agent of component (B), aliphatic polythiols, aromatic polythiols, thiol-modified reactive silicone oils, and the like can be used. However, the use of mercaptoalkyl glycoluril represented by the following formula (I) is preferred from the viewpoint of moisture resistance.

In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a mercaptomethyl group, a 2-mercaptoethyl group, a 3-mer represents a mercaptoalkyl group selected from a captopropyl group and a 4-mercaptobutyl group, and n is 0 to 3.

In the epoxy resin composition of the present invention, the compound of component (B) acts as a curing agent for the epoxy resin of component (A).

In the mercaptoalkyl glycoluril represented by the above formula (I), when R ¹ or R ² is a lower alkyl group, the lower alkyl group usually has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and most Preferably it is 1, that is, a methyl group.

The compound of the mercaptoalkylglycoluril (B) component represented by the formula (I) is preferably a compound in which R ¹ and R ² independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a partial formula in Formula (I) above.

Represents a mercaptoalkyl group such as, n in the above partial formula is 0 to 3.

That is, in the mercaptoalkyl glycoluril represented by the formula (I), when one, two or three of R ³ , R ⁴ and R ⁵ are mercaptoalkyl groups, the mer represented by the formula (I) All of the mercaptoalkyl groups of the captoalkylglycolurils are preferably the same.

Therefore, as preferred specific examples of the mercaptoalkyl glycolurils according to the present invention, for example,

1-mercaptomethylglycoluril,

1-(2-mercaptoethyl)glycoluril;

1-(3-mercaptopropyl) glycoluril,

1-(4-mercaptobutyl)glycoluril;

1,3-bis(mercaptomethyl)glycoluril;

1,3-bis(2-mercaptoethyl)glycoluril;

1,3-bis(3-mercaptopropyl)glycoluril;

1,3-bis(4-mercaptobutyl)glycoluril;

1,4-bis(mercaptomethyl)glycoluril;

1,4-bis(2-mercaptoethyl)glycoluril;

1,4-bis(3-mercaptopropyl)glycoluril;

1,4-bis(4-mercaptobutyl)glycoluril;

1,6-bis(mercaptomethyl)glycoluril;

1,6-bis(2-mercaptoethyl)glycoluril;

1,6-bis(3-mercaptopropyl) glycoluril;

1,6-bis(4-mercaptobutyl) glycoluril;

1,3,4-tris(mercaptomethyl)glycoluril;

1,3,4-tris(2-mercaptoethyl) glycoluril;

1,3,4-tris(3-mercaptopropyl) glycoluril,

1,3,4-tris(4-mercaptobutyl)glycoluril;

1,3,4,6-tetrakis(mercaptomethyl)glycoluril;

1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril,

1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril,

1,3,4,6-tetrakis(4-mercaptobutyl)glycoluril;

1-mercaptomethyl-3a-methylglycoluril;

1-mercaptomethyl-6a-methylglycoluril,

1-(2-mercaptoethyl)-3a-methylglycoluril;

1-(2-mercaptoethyl)-6a-methylglycoluril;

1-(3-mercaptopropyl)-3a-methylglycoluril;

1-(3-mercaptopropyl)-6a-methylglycoluril,

1-(4-mercaptobutyl)-3a-methylglycoluril;

1-(4-mercaptobutyl)-6a-methylglycoluril;

1,3-bis(mercaptomethyl)-3a-methylglycoluril;

1,3-bis(2-mercaptoethyl)-3a-methylglycoluril;

1,3-bis(3-mercaptopropyl)-3a-methylglycoluril,

1,3-bis(4-mercaptobutyl)-3a-methylglycoluril;

1,4-bis(mercaptomethyl)-3a-methylglycoluril;

1,4-bis(2-mercaptoethyl)-3a-methylglycoluril;

1,4-bis(3-mercaptopropyl)-3a-methylglycoluril,

1,4-bis(4-mercaptobutyl)-3a-methylglycoluril;

1,6-bis(mercaptomethyl)-3a-methylglycoluril;

1,6-bis(mercaptomethyl)-6a-methylglycoluril;

1,6-bis(2-mercaptoethyl)-3a-methylglycoluril;

1,6-bis(2-mercaptoethyl)-6a-methylglycoluril;

1,6-bis(3-mercaptopropyl)-3a-methylglycoluril;

1,6-bis(3-mercaptopropyl)-6a-methylglycoluril;

1,6-bis(4-mercaptobutyl)-3a-methylglycoluril;

1,6-bis(4-mercaptobutyl)-6a-methylglycoluril;

1,3,4-tris(mercaptomethyl)-3a-methylglycoluril,

1,3,4-tris(mercaptomethyl)-6a-methylglycoluril,

1,3,4-tris(2-mercaptoethyl)-3a-methylglycoluril,

1,3,4-tris(2-mercaptoethyl)-6a-methylglycoluril,

1,3,4-tris(3-mercaptopropyl)-3a-methylglycoluril,

1,3,4-tris(3-mercaptopropyl)-6a-methylglycoluril,

1,3,4-tris(4-mercaptobutyl)-3a-methylglycoluril,

1,3,4-tris(4-mercaptobutyl)-6a-methylglycoluril,

1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril,

1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril,

1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril,

1,3,4,6-tetrakis(4-mercaptobutyl)-3a-methylglycoluril,

1-mercaptomethyl-3a,6a-dimethylglycoluril,

1-(2-mercaptoethyl)-3a,6a-dimethylglycoluril,

1-(3-mercaptopropyl)-3a,6a-dimethylglycoluril,

1-(4-mercaptobutyl)-3a,6a-dimethylglycoluril;

1,3-bis(mercaptomethyl)-3a,6a-dimethylglycoluril,

1,3-bis(2-mercaptoethyl)-3a,6a-dimethylglycoluril,

1,3-bis(3-mercaptopropyl)-3a,6a-dimethylglycoluril,

1,3-bis(4-mercaptobutyl)-3a,6a-dimethylglycoluril,

1,4-bis(mercaptomethyl)-3a,6a-dimethylglycoluril,

1,4-bis(2-mercaptoethyl)-3a,6a-dimethylglycoluril,

1,4-bis(3-mercaptopropyl)-3a,6a-dimethylglycoluril,

1,4-bis(4-mercaptobutyl)-3a,6a-dimethylglycoluril,

1,6-bis(mercaptomethyl)-3a,6a-dimethylglycoluril,

1,6-bis(2-mercaptoethyl)-3a,6a-dimethylglycoluril,

1,6-bis(3-mercaptopropyl)-3a,6a-dimethylglycoluril,

1,6-bis(4-mercaptobutyl)-3a,6a-dimethylglycoluril;

1,3,4-tris(mercaptomethyl)-3a,6a-dimethylglycoluril,

1,3,4-tris(2-mercaptoethyl)-3a,6a-dimethylglycoluril,

1,3,4-tris(3-mercaptopropyl)-3a,6a-dimethylglycoluril,

1,3,4-tris(4-mercaptobutyl)-3a,6a-dimethylglycoluril,

1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril,

1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril,

1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril,

1,3,4,6-tetrakis(4-mercaptobutyl)-3a,6a-dimethylglycoluril,

1-mercaptomethyl-3a,6a-diphenyl glycoluril,

1-(2-mercaptoethyl)-3a,6a-diphenyl glycoluril;

1-(3-mercaptopropyl)-3a,6a-diphenyl glycoluril,

1-(4-mercaptobutyl)-3a,6a-diphenylglycoluril;

1,3-bis(mercaptomethyl)-3a,6a-diphenyl glycoluril,

1,3-bis(2-mercaptoethyl)-3a,6a-diphenyl glycoluril,

1,3-bis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril,

1,3-bis(4-mercaptobutyl)-3a,6a-diphenyl glycoluril;

1,4-bis(mercaptomethyl)-3a,6a-diphenylglycoluril;

1,4-bis(2-mercaptoethyl)-3a,6a-diphenyl glycoluril,

1,4-bis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril,

1,4-bis(4-mercaptobutyl)-3a,6a-diphenyl glycoluril;

1,6-bis(mercaptomethyl)-3a,6a-diphenyl glycoluril;

1,6-bis(2-mercaptoethyl)-3a,6a-diphenyl glycoluril;

1,6-bis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril,

1,6-bis(4-mercaptobutyl)-3a,6a-diphenyl glycoluril;

1,3,4-tris(mercaptomethyl)-3a,6a-diphenylglycoluril,

1,3,4-tris(2-mercaptoethyl)-3a,6a-diphenylglycoluril,

1,3,4-tris(3-mercaptopropyl)-3a,6a-diphenyl glycoluril,

1,3,4-tris(4-mercaptobutyl)-3a,6a-diphenylglycoluril,

1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril,

1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenyl glycoluril,

1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril,

1,3,4,6-tetrakis(4-mercaptobutyl)-3a,6a-diphenylglycoluril etc. are mentioned.

In the epoxy resin composition of the present invention, the content of the compound of component (B) is 0.3 to 2.5 equivalents in terms of the thiol equivalent ratio of the compound of component (B) to the epoxy equivalent of component (A) (epoxy resin). Since the adhesive strength of a resin composition becomes high, it is preferable.

The content of the compound of component (B) is more preferably 0.6 to 2.3 equivalents in terms of the thiol equivalent ratio of the compound of component (B) to the epoxy equivalent of component (A) (epoxy resin).

(C) Component: Microencapsulation Curing Accelerator

The microencapsulation curing accelerator of component (C) contains 1,4-diazabicyclo[2.2.2]octane (DABCO) as an active ingredient. 1,4-diazabicyclo[2.2.2]octane (DABCO) is also called 1,4-ethylenepiperazine or triethylenediamine.

The microencapsulation curing accelerator of component (C) contains DABCO as an active ingredient, and in combination with the compound of component (B), low-temperature short-time curing at 100 ° C. for 20 minutes or less or 80 ° C. for 60 minutes or less is possible. .

In the epoxy resin composition of the present invention, an isocyanate adduct type microencapsulation curing accelerator is used as the microencapsulation curing accelerator of component (B). The isocyanate adduct type microencapsulated curing accelerator is a latent curing accelerator obtained by coating (microencapsulating) a powder containing an amine-based curing accelerator by adding an isocyanate resin to the powder.

By using an isocyanate adduct type microencapsulated curing accelerator, the pot life of the epoxy resin composition is improved while enabling low-temperature, short-time curing of the epoxy resin composition at 100°C for 20 minutes or less or 80°C for 60 minutes or less. When DABCO, which is not in the form of a microencapsulation curing accelerator, is directly contained as component (B), the pot life of the epoxy resin composition is remarkably reduced.

In the epoxy resin composition of the present invention, the amount of DABCO in component (C) is 0.01 to 2 parts by mass with respect to 100 parts by mass in total of components (A) to (C).

If the amount of DABCO in component (C) is less than 0.01 part by mass relative to 100 parts by mass of the total of components (A) to (C), low-temperature short-time curing at 100°C for 20 minutes or less or 80°C for 60 minutes or less is not possible. It happens.

On the other hand, if the amount of DABCO in component (C) exceeds 2 parts by mass with respect to 100 parts by mass of the total of components (A) to (C), the viscosity of the resin composition increases and workability deteriorates. In addition, the pot life also tends to deteriorate.

The amount of DABCO in component (C) is preferably from 0.05 to 1 part by mass, more preferably from 0.1 to 0.5 part by mass, based on 100 parts by mass in total of components (A) to (C).

The epoxy resin composition of the present invention may contain, as necessary, components described below in addition to the components (A) to (C).

Ingredient (D): thickening inhibitor

The resin composition of the present invention may contain a thickening inhibitor as component (D) in order to improve the storage stability at room temperature (25°C) and lengthen the pot life.

As the thickening inhibitor of component (D), at least one selected from the group consisting of boric acid esters, aluminum chelates, and organic acids is highly effective in improving storage stability at room temperature (25°C).

As boric acid ester, for example, 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triiso Propylborate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, trihexadecylborate Octadecylborate, 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 can be used.

Here, since the boric acid ester to be contained as component (D) is liquid at room temperature (25°C), it is preferable to keep the viscosity of the blend low.

(D) When a boric acid ester is contained as component, it is preferably 0.1 to 8.9 parts by mass, more preferably 0.1 to 4.4 parts by mass, and 0.1 to 0.1 to 4.4 parts by mass relative to 100 parts by mass of the total amount of component (A) to component (D). It is more preferable that it is 3.5 mass parts.

As an aluminum chelate, aluminum trisacetylacetonate (For example, ALA: aluminum chelate A by Kawaken Fine Chemicals Co., Ltd.) can be used, for example.

When an aluminum chelate is contained as component (D), it is preferably 0.1 to 14.0 parts by mass, more preferably 0.1 to 13.0 parts by mass, and 0.1 to 13.0 parts by mass relative to 100 parts by mass of the total amount of component (A) to component (D). It is more preferable that it is 12.0 mass parts.

As an organic acid, for example, barbituric acid can be used.

When an organic acid is contained as component (D), it is preferably 0.1 to 8.9 parts by mass, more preferably 0.1 to 7.1 parts by mass, and 0.1 to 4.0 parts by mass relative to 100 parts by mass of the total amount of component (A) to component (D). It is more preferable that it is a mass part.

(Other compounding agents)

The epoxy resin composition of the present invention may further contain components other than the above components (A) to (D) as needed. Specific examples of such components include fillers, ion trapping agents, leveling agents, antioxidants, antifoaming agents, flame retardants, colorants and the like. The type and amount of each compounding agent are the same as in the usual method.

The resin composition of the present invention is subjected to heat treatment of the above components (A) to (C), and, when contained, further component (D), and other compounding agents to be further blended as necessary, simultaneously or separately, as necessary. It can be obtained by stirring, melting, mixing, and dispersing while adding. Although it is not specifically limited as an apparatus for these mixing, stirring, dispersing, etc., a Leica machine equipped with a stirring and heating apparatus, a 3 roll mill, a ball mill, a planetary mixer, a bead mill, etc. can be used. Moreover, you may use these apparatuses combining suitably.

The epoxy resin composition of the present invention can be cured at 100°C for 20 minutes or less or at 80°C for 60 minutes or less for a short time. For this reason, it is suitable as a one-component adhesive used in the manufacture of image sensor modules and electronic components.

In addition, as a use of the epoxy resin composition of the present invention, there is also a possibility of a liquid encapsulant used at the time of manufacturing a semiconductor device.

The epoxy resin composition of the present invention has sufficient adhesive strength. Specifically, the adhesive strength (shear strength, heat curing at 70°C for 10 min) measured in the procedure described below is preferably 20 N/chip or more, more preferably 50 N/chip, and still more preferably 80 N/chip. Further, (shear strength, heat curing at 80°C for 10 min) is preferably 20 N/chip or more, more preferably 50 N/chip, and still more preferably 80 N/chip.

The epoxy resin composition of the present invention has good storage stability at room temperature and has a long pot life. In this specification, the time at which the thickening rate measured by the procedure described in the examples described later becomes 1.2 times is used as an index of pot life. In the epoxy resin composition of the present invention, the time for the thickening ratio to increase by 1.2 times, as measured by the procedure described in the examples described later, is preferably 6 hours or more, more preferably 12 hours or more, and still more preferably 24 hours or more.

Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

(Preparation of Epoxy Resin Composition)

An epoxy resin composition was prepared by mixing each component according to the formulation shown in the table below. On the other hand, in the table below, all numbers indicating the blending ratio of component (A) to component (D) indicate parts by mass.

Each component in a table|surface is as follows.

(A) component

YDF8170: Bisphenol F type epoxy resin (aromatic epoxy resin) (Nittetsu Chemical Co., Ltd., epoxy equivalent 160)

ZX1658GS: cyclohexane dimethanol diglycidyl ether (aliphatic epoxy resin) (Nittetsu Chemical Co., Ltd., epoxy equivalent 135)

EP4088L: dicyclopentadiene dimethanol diglycidyl ether (aliphatic epoxy resin) (manufactured by ADEKA Corporation, epoxy equivalent 165)

EXA835LV: bisphenol F type epoxy resin and bisphenol A type epoxy resin mixture (aromatic epoxy resin) (manufactured by DIC Corporation, epoxy equivalent 165)

(B) component

TS-G: 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd., thiol group equivalent 94)

1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Kasei Industrial Co., Ltd., thiol equivalent 108, described as C3 TS-G in the table)

PEMP: pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemistry, thiol group equivalent 122)

(B') component

MEH8005: allylated phenolic resin, manufactured by Maywa Chemical Co., Ltd.

(C) component

HXA5945HP: Novacure HXA5945HP (isocyanate adduct type microencapsulation curing accelerator containing DABCO as an active ingredient) (manufactured by Asahi Kasei E-Materials Co., Ltd., DABCO 3% by mass)

HXA5934HP: Novacure HXA5934HP (isocyanate adduct type microencapsulation curing accelerator containing DABCO as an active ingredient) (manufactured by Asahi Kasei E-Materials Co., Ltd., DABCO 3% by mass)

(C') component

HXA3922HP: Novacure HXA3922HP (isocyanate adduct type microencapsulated curing accelerator) (manufactured by Asahi Kasei E-Materials Co., Ltd.)

(D) component

Triisopropyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.)

Tripropylborate (manufactured by Tokyo Chemical Industry Co., Ltd.)

Aluminum chelate: Aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.)

Barbituric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Evaluation of gel time]

The gel time of the prepared epoxy resin composition is when the resin composition: 5 ± 1 mg is supplied on a hot plate heated at 80 ° C. or 100 ° C., and the stirring rod is lifted and removed while stirring in a circular motion with the stirring rod. , obtained by measuring the time until the cove webbing disappears. The measurement results are shown in the table below.

[Evaluation of Port Life]

About the prepared epoxy resin composition, the viscosity (Pa·s) in 25 degreeC was measured at 50 rpm using rotational viscometer HBDV-1 by Brookfield (using spindle SC4-14). Next, the epoxy resin composition was placed in an airtight container and stored at 25°C, and the time until the viscosity became 1.2 times the initial value was the pot life.

The adhesive strength (shear strength) of the prepared epoxy resin composition was measured in the following procedure. Results are shown in the table below.

About Example 8, adhesive strength was evaluated in the following procedure.

[Evaluation of Adhesion Strength]

(1) A sample is stencil-printed on a glass epoxy substrate in a size of 2 mmφ.

(2) An alumina chip of 1.5 mm x 3 mm is placed on the printed sample. This is thermally cured at 70°C for 10 minutes or at 80°C for 10 minutes using a blow dryer.

(3) The shear strength was measured with a tabletop universal tester (1605HTP manufactured by Aiko Engineering Co., Ltd.).

Example 1 is an example in which only an aromatic epoxy resin is used as the epoxy resin of component (A), and in Examples 2 and 3, an aromatic epoxy resin and an aliphatic epoxy resin are used together as the epoxy resin of component (A), and It is an example in which a thickening inhibitor is added as component (D), Example 4 is an example in which the aromatic epoxy resin used as the epoxy resin of component (A) is changed, and Example 5 is different from Example 4, (C ) is an example in which the isocyanate adduct type microencapsulated curing accelerator containing DABCO as an active ingredient used as the component is changed, and Examples 6 and 7 are examples in which the thiol-based curing agent of component (B) is changed in relation to Example 4. Example, Example 8 is an example in which a thickener is added as component (D) to Example 4, and Examples 9 to 11 are examples in which the thickener of component (D) is changed from Example 8. am.

In all of these examples, low-temperature short-time curing at 100°C for 20 minutes or less or 80°C for 60 minutes or less was possible. In addition, the pot life is 12 hours or more, and the pot life of Examples 2, 3, and 8 to 11 in which a thickening inhibitor was added as component (D) was 72 hours.

The adhesive strength evaluated for Example 8 was 80 N/chip or more for both 70°C 10 min heat curing and 80°C 10 min heat curing. Example 7 using PEMP with a relatively low Tg as the component (B) had an adhesive strength of 100 N/chip at 80 ° C. for 10 min, but Examples 4 and 6 using TS-G and C3 TS-G with high Tg were 80 ° C. The adhesive strength at 10 min showed a high value of 250 N/chip.

In Comparative Examples 1 and 2 using only an aliphatic epoxy resin as the epoxy resin of component (A), the ratio (mass ratio) of the aromatic epoxy resin in the epoxy resin of component (A) to the aliphatic epoxy resin is 2: Comparative Examples 3 and 4 with fewer than 8 gelled during preparation of the epoxy resin composition. For this reason, evaluation of the gel time and evaluation of the pot life were not performed.

Comparative Examples 5 to 7 using an isocyanate adduct type microencapsulation curing accelerator not containing DABCO as component (C') could not achieve low-temperature short-time curing at 100°C for 20 minutes or less or 80°C for 60 minutes or less. In Comparative Examples 5, 6, and 7, instead of the isocyanate adduct type microencapsulation curing accelerator containing DABCO as an active ingredient of component (C), isocyanate adduct type microencapsulation curing that does not contain DABCO as component (C′) Except for using the accelerator, it is the same as Examples 4, 6, and 7. For these examples, comparing the ratio of the 80°C gel time to the 100°C gel time (80°C gel time (without DABCO/with DABCO), 100°C gel time (without DABCO/with DABCO)), the 80°C gel Time ratio (without DABCO (Comparative Example 5)/with DABCO (Example 4)) = 7.4, 100°C gel time ratio (without DABCO (Comparative Example 5)/with DABCO (Example 4)) = 4.7, 80 ℃ gel time ratio (not containing DABCO (Comparative Example 6) / containing DABCO (Example 6)) = 7.3, 100 ℃ gel time ratio (not containing DABCO (Comparative Example 6) / containing DABCO (Example 6)) = 4.7 , 80 ° C. gel time ratio (DABCO-free (Comparative Example 7) / DABCO-containing (Example 7)) = 5.4, 100 ° C. gel time ratio (DABCO-free (Comparative Example 6) / DABCO-containing (Example 6)) = 4.7.

Comparative Examples 8 to 11 using a phenol-based curing agent as the component (B') instead of the thiol-based curing agent as the component (B) could not achieve low-temperature short-time curing of 20 minutes or less at 100 ° C. or 60 minutes or less at 80 ° C. . In particular, in Comparative Example 10, 5 times as much component (C) was added as compared to Comparative Example 8, but the gel time was not as short as in Example 4.

Further, 80 ° C. gel time ratio (DABCO non-containing (Comparative Example 11) / DABCO containing (Comparative Example 10)) = 2.3, 100 ° C. gel time ratio (DABCO non-containing (Comparative Example 11)) of Comparative Example 10 and Comparative Example 11 /DABCO containing (Comparative Example 10) = 1.6, and since Comparative Example 10 has a shorter gel time than Comparative Example 11 which does not contain (C) component, by containing (C) component, (B') phenolic curing agent It can be seen that the gel time can be shortened even in the system containing

However, in a system containing (B') a phenol-based curing agent, even if the component (C) is included in the formulation, it can be seen that a remarkable curing accelerating effect is not obtained as much as a formulation containing a thiol-based curing agent (B).

From the above, the effect of the present invention that low-temperature and short-time curing is possible is unique to formulations containing (B) a thiol-based curing agent.

Claims (10)

(A) an epoxy resin;
(B) a thiol-based curing agent;
(C) an isocyanate adduct type microencapsulated curing accelerator containing 1,4-diazabicyclo[2.2.2]octane (DABCO) as an active ingredient;
The ratio (mass ratio) of the aromatic epoxy resin and the aliphatic epoxy resin in the epoxy resin of the component (A) is 10:0 to 2:8,
The amount of DABCO in the component (C) is 0.01 to 2 parts by mass with respect to the total of 100 parts by mass of the components (A) to (C),
The content of the component (B) is 0.3 to 2.5 in terms of a thiol equivalent ratio of the component (B) to the epoxy equivalent of the component (A). According to claim 1,
An epoxy resin composition in which the thiol-based curing agent of the component (B) is a mercaptoalkyl glycoluril represented by formula (I):
[Equation 1]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a mercaptomethyl group, or a 2-mer represents a mercaptoalkyl group selected from the group consisting of a captoethyl group, a 3-mercaptopropyl group and a 4-mercaptobutyl group, and n is 0 to 3). According to claim 1 or 2,
Further, (D) an epoxy resin composition containing a thickening inhibitor. According to claim 3,
The thickening inhibitor of the component (D) is at least one selected from the group consisting of boric acid esters, aluminum chelates, and organic acids. A cured resin obtained by heating the epoxy resin composition according to claim 1 or 2. A one-component adhesive comprising the epoxy resin composition of claim 1 or 2. An encapsulant comprising the epoxy resin composition of claim 1 or 2. An image sensor module manufactured using the one-component adhesive of claim 6. An electronic component manufactured using the one-component adhesive of claim 6. A semiconductor device having a flip chip type semiconductor element sealed using the encapsulant of claim 7 .