EPOXY RESIN COMPOSITION

Abstract

An epoxy resin composition includes at least one thiol-based curing agent, a main epoxy resin, and a curing catalyst. The at least one thiol-based curing agent includes a non-hydrolyzable polyfunctional thiol compound having at least one hydroxyl group and/or urea bond. The main epoxy resin is at least one main aliphatic polyfunctional epoxy resin selected from a polyethylene glycol diglycidyl ether, a cyclohexane-based diglycidyl ether, and a dicyclopentadiene-based diglycidyl ether. The epoxy resin composition has a viscosity at 25° C. of 0.05 Pa.Math.s or higher and 3 Pa.Math.s or lower

Claims

1. An epoxy resin composition comprising components (A) to (C) below: (A) at least one thiol-based curing agent comprising a non-hydrolyzable polyfunctional thiol compound having at least one hydroxyl group and/or urea bond; (B) a main epoxy resin consisting of at least one main aliphatic polyfunctional epoxy resin selected from the group consisting of components (B-1) to (B-3) below: (B-1) a polyethylene glycol diglycidyl ether, (B-2) a cyclohexane-based diglycidyl ether, and (B-3) a dicyclopentadiene-based diglycidyl ether; and (C) a curing catalyst; wherein the epoxy resin composition has a viscosity at 25° C. of at least 0.05 Pa.Math.s and not more than 3 Pa.Math.s.

2. The epoxy resin composition according to claim 1, wherein the non-hydrolyzable polyfunctional thiol compound is a compound having no ester bond.

3. The epoxy resin composition according to claim 1, wherein the non-hydrolyzable polyfunctional thiol compound is a compound represented by formula (1) below: ##STR00005## wherein: R.sup.1 and R.sup.2 are, each independently, selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a phenyl group; and R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are, each independently, selected from the group consisting of a mercaptomethyl group, a mercaptoethyl group and a mercaptopropyl group.

4. The epoxy resin composition according to claim 3, wherein the compound represented by formula (I) is 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and/or 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril.

5. The epoxy resin composition according to claim 1, wherein the non-hydrolyzable polyfunctional thiol compound is a compound represented by formula (2) below:
(R.sup.8).sub.m-A-(R.sup.7—SH).sub.n   (2) wherein: A is a residue of a polyhydric alcohol having n+m hydroxyl groups, and comprises n+m oxygen atoms derived from the hydroxyl groups, R.sup.7 is each, independently, an alkylene group having 1 to 10 carbon atoms, R.sup.8 is each, independently, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m is an integer equal to or greater than 0, n is an integer equal to or greater than 2, wherein R.sup.7 and R.sup.8 are each bonded to A via one of the oxygen atoms.

6. The epoxy resin composition according to claim 1, further comprising an auxiliary epoxy resin (B′) comprising at least one selected from the group consisting of: (B′-1) at least one auxiliary aliphatic polyfunctional epoxy resin which is an aliphatic polyfunctional epoxy resin other than the main aliphatic polyfunctional epoxy resin, and (B′-2) at least one aromatic polyfunctional epoxy resin.

7. The epoxy resin composition according to claim 1, further comprising a monofunctional epoxy resin.

8. The epoxy resin composition according to claim 1, wherein the component (B) has a viscosity at 25° C. of 0.3 Pa.Math.s or lower.

9. The epoxy resin composition according to claim 1, wherein the component (C) is a latent curing catalyst.

10. A sealing material or an adhesive comprising the epoxy resin composition according to claim 1.

11. A cured product obtained by curing the epoxy resin composition according to claim 1.

12. An electronic component comprising the cured product according to claim 11.

13. A cured product obtained by curing the sealing material or the adhesive according to claim 10.

14. An electronic component comprising the cured product according to claim 13.

Description

EXAMPLES

[0149] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In the following examples, parts and percentages, unless otherwise specified, represent parts by mass and percentages by mass.

Examples 1 to 13 and Comparative Examples 1 to 4

[0150] Epoxy resin compositions were prepared by mixing each of the components in the amounts according to the formulations shown in Tables 1 and 2 using a three-roll mill. In Tables 1 and 2, the amount of each component is expressed in parts by mass. The values in the parentheses represent the thiol functional group equivalent quantities (or the epoxy functional group equivalent quantities) for the corresponding thiol compounds (or epoxy resins). The ratios of the amount of the main epoxy resin to the total amount of the main epoxy resin and the auxiliary epoxy resin (component (B)/(component (B)+component (B′)) are expressed as ratios by mass.

[0151] Non-hydrolyzable Polyfunctional Thiol Compound (Component (A))

[0152] The following lists the compounds used as component (A) in the Examples and Comparative Examples.

[0153] (A-1): 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (trade name: TS-G, manufactured by Shikoku Chemicals Corporation, thiol equivalent weight: 100)

[0154] (A-2): 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Chemicals Corporation, thiol equivalent weight: 114)

[0155] Main Epoxy Resin (Component (B))

[0156] The following lists the compounds used as component (B) in the Examples and Comparative Examples.

[0157] (B-1): polyethylene glycol glycidyl ether (average degree of polymerization: 9) (trade name: SR-8EGS, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent weight: 262)

[0158] (B-2): 1,4-cyclohexanedimethanol diglyeidyl ether (trade name: CDMDG, manufactured by Showa Denko K.K., epoxy equivalent weight: 133)

[0159] (B-3): dicyclopentadiene dimethanol diglycidyl ether (trade name: 4088L, manufactured by ADEKA Corporation, epoxy equivalent weight: 165)

[0160] Auxiliary Epoxy Resin (Component (B′))

[0161] The following lists the compounds used as component (B′) in the Examples and Comparative Examples.

[0162] (B′-1)1: 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane (trade name: TSL9906, manufactured by Momentive Performance Materials Japan LLC, average molecular weight: 362, epoxy equivalent weight: 181)

[0163] (B′-1)-2: polypropylene glycol diglycidyl ether (average molecular weight: 640) (trade name: PG-207GS, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent weight: 320)

[0164] (B′-2): bisphenol F-based epoxy resin (average molecular weight: 318) (trade name: YDF-8170, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent weight: 159)

[0165] Curing Catalyst (Component (C))

[0166] The following lists the compounds used as component (C) in the Examples and Comparative Examples.

[0167] (C-1): amine-epoxy adduct-based latent curing catalyst 1 (trade name: Novacure HXA9322HP, manufactured by Asahi Kasci Corp.)

[0168] (C-2): amine-epoxy adduct-based latent curing catalyst 2 (trade name: Fujicure FXR1121, manufactured by T & K TOKA Co., Ltd.)

[0169] The curing catalyst (C-1) above is provided in the form of a dispersion liquid (latent curing catalyst/bisphenol A-based epoxy resin/bisphenol F-based epoxy resin=33/53/14 (mass ratio)) in which the latent curing catalyst in particulate form is dispersed in an epoxy resin (a mixture of a bisphenol A-based epoxy resin (epoxy equivalent weight: 180) and a bisphenol F-based epoxy resin (epoxy equivalent weight: 159)). The epoxy resins constituting this dispersion are treated as forming part of component (B′). In Tables 1 and 2, therefore, the row for component (C) shows the amount of the latent curing catalyst in (C-1) only, and the amount of epoxy resin in (C-1) is shown in a row for component (B′).

[0170] Monofunctional Epoxy Resin

[0171] In the Examples and Comparative Examples, p-tert-butylphenylglycidyl ether (trade name: ED-509S, manufactured, epoxy equivalent weight: 206) was used as the monofunctional epoxy resin.

[0172] Stabilizer and Filler

[0173] In the Examples and Comparative Examples, triisopropyl borate was used as a stabilizer and a silica filler was used as a filler.

[0174] In the Examples and Comparative Examples, the characteristics of the epoxy resin compositions were measured in the following manners.

[0175] <Compatibility>

[0176] The epoxy resin compositions prepared were visually examined and evaluated as a ◯ (good) if no clear separation of components was observed, Δ (acceptable) if observed to be in suspension, or × (poor) if a clear separation of components was observed.

[0177] <Viscosity>

[0178] The viscosities (unit: Pa.Math.s) of the epoxy resin compositions were measured within 1 hour of their preparation using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. (model number: TVE-22H, name of rotor: 1° 34′×R24) (set to a suitable measuring range (H, R or U)) at a rotor revolution speed of 10 rpm. Lower viscosity is preferable for ease of injection. The results are shown in Tables 1 and 2. Viscosity was not measured for the compositions the compatibilities of which were evaluated as ×. Those having a viscosity of 1 Pa.Math.s or lower were evaluated as ⊚ (very good), those having a viscosity of over 1 Pa.Math.s and 3 Pa.Math.s or lower were evaluated as ◯ (good), and those having a viscosity of over 3 Pa.Math.s were evaluated as × (poor).

TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 Component (A) (A-1) 28 42 37 27 28 28 28 (0.28) (0.42) (0.37) (0.27) (0.28) (0.28) (0.28) (A-2) 30 (0.26) Component (B) (B-1) 67 65 71 67 67 67 (0.26) (0.24) (0.27) (0.26) (0.26) (0.26) (B-2) 53 (0.40) (B-3) 58 (0.35) Component (B)′ (B′-1)-1 (B′-1)-2 (B′-2) Epoxy resin 3.35 3.35 3.35 3.35 3.35 3.35 3.35 in (C-1) (0.02) (0.02) (0.02) (0.02) (0.02) (0.02) (0.02) Component (C) (C-1) 1.65 1.65 1.65 1.65 1.65 1.65 1.65 (Catalyst only) (C-2) 2 Monofunctional epoxide Stabilizer 0.1 Filter 30 30 30 30 30 30 50 Total 130.0 130.0 130.0 130.0 130.0 130.1 100.0 150.0 Component (B)/(Component (B) + 0.95 0.94 0.95 0.95 100 0.95 0.95 0.95 Component (B′)) Epoxy functional group equivalent 0.91 0.95 0.95 0.94 1.00 0.91 0.91 0.91 quantity for component (B)/thiol functional group equivalent quantity for component (A) Ratio of functional group equivalent 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 quantities (for the entire curable composition) Results of Compatibility ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ evaluation Viscosity ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯

TABLE-US-00002 TABLE 2 Compar- Compar- Compar- Compar- ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 9 ple 10 ple 11 ple 12 ple 13 ple 1 ple 2 ple 3 ple 4 Component (A) (A-1) 36 36 36 32 23 35 24 32 38 (0.36) (0.36) (0.36) (0.32) (0.23) (0.35) (0.24) (0.32) (0.38) (A-2) Component (B) (B-1) 63 72 (0.24) (0.27) (B-2) 6 (0.04) (B-3) 17 39 33 17 (0.10) (0.24) (0.20) (0.10) Component (B)′ (B′-1)-1 20 26 60 (0.11) (0.14) (0.33) (B′-1)-2 71 (0.22) (B′-2) 9 40 (0.06) (0.25) Epoxy resin 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 3.35 in (C-1) (0.02) (0.02) (0.02) (0.02) (0.02) (0.02) (0.02) (0.02) (0.02) Component (C) (C-1) 1.65 1.65 1.65 1.65 1.65 1.65 1.65 1.65 1.65 (Catalyst only) (C-2) Monofunctional epoxide 28 63 (0.14) (0.30) Stabilizer Filler 30 30 30 30 30 30 30 30 30 Total 131.0 130.0 130.0 130.0 130.0 130.0 130.0 130.0 130.0 Component (B)/(Component (B) + 0.65 0.95 0.95 0.95 0.96 0.95 0.95 0 0.28 Component (B′)) Epoxy functional group equivalent 0.41 0.65 0.55 0.75 1.19 0 0 0 0.27 quantity for component (B)/thiol functional group equivalent quantity for component (A) Ratio of functional group equivalent 1.0 1.0 1.0 1.2 0.8 1.0 1.0 1.0 1.0 quantities (for the entire curable composition) Results of Compatibility ◯ ◯ Δ ◯ ◯ X X X ◯ evaluation Viscosity ⊚ ⊚ ⊚ ⊚ ⊚ — — — X

[0179] As can be seen from Tables 1 and 2, in all of Examples 1 to 13, the viscosity was as low as 3 Pa.Math.s or lower, and no clear separation of components was observed. By contrast, in all of Comparative Examples 1 to 3, which did not comprise component (B), a clear separation of components was observed and it was not possible to obtain a homogeneous composition. Further, in Comparative Example 4, which only had a small amount of component (B), although a homogenous composition was obtained, the composition had a high viscosity of over 3 Pa.Math.s.

INDUSTRIAL APPLICABILITY

[0180] The epoxy resin composition of the present invention is very useful as an adhesive, sealing material, dam agent or the like for semiconductor devices and electronic components, because the epoxy resin composition cures in a short time even under low temperature conditions to give a cured product having excellent moisture resistance and has a low viscosity of 3 Pa.Math.s or lower, thereby allowing it to be easily applied to or injected into an application site.