JP7217565B1 - Resin compositions, adhesives, sealing materials, cured products, semiconductor devices and electronic components - Google Patents

Abstract

The present invention provides a resin composition and an adhesive which cure under low-temperature conditions, give a cured product having excellent stress relaxation properties, and exhibit a low self-heating temperature during the curing reaction. (A) a polyfunctional epoxy compound, (B) a polyfunctional thiol compound, and (C) having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule. A resin composition comprising a monofunctional compound and (D) a curing catalyst. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to a resinous composition, an adhesive or sealing material containing the same, a cured product thereof, a semiconductor device and an electronic component containing the cured product.

Currently, in the assembly and mounting of parts used in semiconductor devices and electronic parts, for example, semiconductor chips, adhesives and sealing materials containing curable resin compositions, especially epoxy resin compositions, are used for the purpose of maintaining reliability. etc. are often used. In particular, in the case of semiconductor devices and electronic components including components that deteriorate under high temperature conditions, it is necessary to carry out their manufacturing processes under low temperature conditions. Therefore, adhesives and sealing materials used in the manufacture of such devices and parts are required to exhibit sufficient curability even under low-temperature conditions. A curable composition using a thiol-based curing agent as a curing agent is known as such a low-temperature curing epoxy resin composition (for example, Patent Documents 1 and 2).

When the ambient temperature of an assembly in which two parts made of different materials are bonded to each other with an adhesive changes (for example, temperature changes during use or during the cooling process after heat curing), they Each of the parts will experience thermal stress depending on the coefficient of thermal expansion of its material. This thermal stress is non-uniform due to differences in thermal expansion coefficients and cannot be canceled, resulting in deformation of the assembly. The stress associated with this deformation acts particularly on the joints of the parts, that is, the cured adhesive, and in some cases causes peeling of the joints and cracks in the cured product. Such peeling and cracking are likely to occur particularly when the cured product is brittle and lacks flexibility. Therefore, an adhesive for joining parts made of different materials must have flexibility, ie stress relaxation properties, to the extent that it can follow the deformation of the assembly due to the thermal stress of the parts after curing.

Patent Document 3 describes an epoxy resin composition that cures in a short time even under low temperature conditions, has a low glass transition point (Tg), and provides a cured product with excellent moisture resistance reliability after curing. , a thiol-based curing agent comprising a multifunctional thiol compound having three or more thiol groups; (B) at least one multifunctional epoxy resin; (C) a crosslink density modifier comprising at least one monofunctional epoxy resin; and (D) An epoxy resin composition is disclosed which contains a latent curing catalyst and has a specific relationship between the number (quantity) of thiol groups and the number (quantity) of epoxy groups possessed by these components. Patent Document 3 discloses that the cured product of this epoxy resin composition can follow deformation due to thermal expansion of parts in an assembly formed by bonding a plurality of parts made of different materials.

JP-A-6-211969 JP-A-6-211970 JP 2019-156965 A

The resin composition disclosed in Patent Document 3 cures under low-temperature conditions, and the cured product can follow deformation due to thermal expansion of parts, but the self-heating temperature during the curing reaction is high. . Even if the curing conditions are low-temperature conditions, when the self-heating temperature of the resin composition is high, there is a concern that the adherend to which the resin composition is applied and its peripheral members may be overheated. The present invention cures under low temperature conditions, gives a cured product having flexibility to the extent that it can follow the deformation of the assembly due to the thermal stress of the parts, that is, excellent stress relaxation, and self-heating temperature during the curing reaction. An object of the present invention is to provide a resin composition having a low

As a result of examination, it was found that the problem was solved by the following specific means.
A first embodiment of the present invention is the following resin composition.
(1) (A) a polyfunctional epoxy compound,
(B) a polyfunctional thiol compound,
(C) A monofunctional compound having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule, and (D) a resin composition containing a curing catalyst.
(2) The resin composition according to (1) above, wherein component (C) is selected from monofunctional maleimide compounds and monofunctional (meth)acrylate compounds.
(3) The resin composition according to (1) or (2) above, wherein component (C) is a monofunctional (meth)acrylate compound having a molecular weight of 100-450.
(4) Ratio of the group (c) equivalent number of component (C) to the epoxy group equivalent number of component (A) ([group (c) equivalent number of component (C)]/[epoxy group equivalent of component (A) number]) is 0.05 to 2, the resin composition according to any one of the above (1) to (3).
(5) The ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of component (A)]/[number of thiol group equivalents of component (B)]) is , 0.4 to 0.95, the resin composition according to any one of the above (1) to (4).
(6) Ratio of the sum of the number of epoxy group equivalents of component (A) and the number of group (c) equivalents of component (C) to the number of thiol group equivalents of component (B) (([epoxy group equivalents of component (A) number] + [group (c) equivalent number of component (C)]) / [thiol group equivalent number of component (B)]) is 0.7 to 1.5, the above (1) to (5) The resin composition according to any one of.
(7) Ratio of the group (c) equivalent number of component (C) to the thiol group equivalent number of component (B) ([group (c) equivalent number of component (C)] / [thiol group equivalent of component (B) number]) is 0.05 to 0.7, the resin composition according to any one of the above (1) to (6).

A second embodiment of the present invention is (8) an adhesive or a sealing material containing the resin composition according to any one of (1) to (7) above.
A third embodiment of the present invention is a It is a cured product.
A fourth embodiment of the present invention is (10) a semiconductor device or an electronic component comprising the cured product according to (9) above.

According to the first embodiment of the present invention, it is possible to obtain a resin composition that cures under low temperature conditions and gives a cured product having excellent stress relaxation properties. Furthermore, since this resin composition has a low self-heating temperature during the curing reaction, it is possible to suppress overheating of the adherend and its peripheral members. Further, according to the second embodiment of the present invention, an adhesive or An encapsulant can be obtained. Furthermore, according to the third embodiment of the present invention, a cured product having excellent stress relaxation properties can be obtained, and overheating of the adherend of the cured product and its peripheral members can be suppressed. According to the fourth aspect of the present invention, it is possible to obtain a semiconductor device and an electronic component containing a cured product that has excellent stress relaxation properties and suppresses overheating of the adherend and its peripheral members.

It is a dumbbell-shaped test piece used for a tensile test.

In the present specification, following the practice in the field of synthetic resins, a name including the term "resin", which usually refers to a polymer (especially a synthetic polymer), is used for components constituting a curable resin composition before curing. may be used even though the components are not polymeric.
As used herein, the term "cured product having excellent stress relaxation properties" refers to a cured product having flexibility to the extent that it can follow deformation of an assembly due to thermal stress of parts.
As used herein, the "self-heating temperature" of the resin composition refers to the temperature of the resin composition itself during thermosetting. The maximum value of the self-heating temperature of the resin composition is obtained as the maximum value (maximum exothermic temperature) of the sample temperature when thermogravimetric-differential thermal simultaneous measurement (TG-DTA measurement) is performed under the curing reaction condition at a constant temperature. be able to.

[Resin composition]
The resin composition, which is the first embodiment of the present invention,
(A) a polyfunctional epoxy compound,
(B) a polyfunctional thiol compound,
(C) a monofunctional compound having one group (c) containing an unsaturated double bond and an adjacent electron-withdrawing group in the molecule, and (D) a curing catalyst. According to this embodiment, it is possible to obtain a resin composition that cures under low-temperature conditions, gives a cured product having excellent stress relaxation properties, and has a low self-heating temperature during the curing reaction.

(A) Polyfunctional Epoxy Compound The resin composition of the present embodiment contains (A) a polyfunctional epoxy compound (hereinafter also referred to as "component (A)"). (A) The polyfunctional epoxy compound is not particularly limited as long as it is a compound having at least two epoxy groups, and conventionally commonly used epoxy resins can be used as component (A). Epoxy resin is a general term for thermosetting resins that can be cured by forming a crosslinked network with epoxy groups present in the molecule, and includes prepolymer compounds before curing. In consideration of ensuring heat resistance, the component (A) is more preferably a compound having 2 to 6 epoxy groups, more preferably a compound having 2 epoxy groups.
(A) Polyfunctional epoxy compounds are roughly classified into aromatic polyfunctional epoxy compounds and polyfunctional epoxy compounds having no aromatic ring.

An aromatic polyfunctional epoxy compound is a polyfunctional epoxy compound having a structure containing an aromatic ring such as a benzene ring. Many conventional epoxy resins, such as bisphenol A type epoxy compounds, are of this type. Examples of aromatic polyfunctional epoxy compounds include:
- bisphenol A type epoxy compound;
- branched polyfunctional bisphenol A type epoxy compounds such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether;
- bisphenol F type epoxy compound;
- a novolac type epoxy compound;
- Tetrabromobisphenol A type epoxy compound;
- a fluorene-type epoxy compound;
- biphenyl aralkyl epoxy compounds;
- diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether;
-biphenyl-type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl;
-glycidylamine type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; not to be These may be used alone or in combination of two or more. (B) From the viewpoint of compatibility with the polyfunctional thiol compound, component (A) preferably contains an aromatic polyfunctional epoxy compound. As the aromatic polyfunctional epoxy compound, a bisphenol F type epoxy compound, a bisphenol A type epoxy compound and a glycidylamine type epoxy compound are preferable. Even more preferred is ~400 g/eq. The aromatic polyfunctional epoxy compound may be oxyalkylene modified such as EO (ethylene oxide) modified or PO (propylene oxide) modified. Also, the aromatic polyfunctional epoxy compound is preferably liquid at 25°C. Also, the viscosity at 25° C. is preferably 0.1 to 100 Pa·s, more preferably 0.5 to 100 Pa·s, and particularly preferably 1 to 100 Pa·s.

In this specification, the viscosity is expressed as a value measured according to Japanese Industrial Standard JIS K6833, unless otherwise specified. Specifically, it can be obtained by measuring with an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotors, or measurement range to be used.

Polyfunctional epoxy compounds having no aromatic ring include, for example, aliphatic polyfunctional epoxy compounds and polyfunctional epoxy compounds having heterocyclic rings.

Examples of aliphatic polyfunctional epoxy compounds include
- (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, poly Diepoxy compounds such as tetramethylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, dicyclopentadiene diglycidyl ether;
- triepoxy compounds such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether;
- cycloaliphatic epoxy compounds such as vinyl (3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane;
- hydrogenated bisphenol A diepoxy compounds such as hydrogenated bisphenol A diglycidyl ether;
- glycidylamine-type epoxy compounds such as tetraglycidylbis(aminomethyl)cyclohexane;
-hydantoin-type epoxy compounds such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldi Examples include, but are not limited to, epoxy compounds having a silicone skeleton such as siloxane.
The aliphatic polyfunctional epoxy compound preferably has an epoxy equivalent of 90 to 450 g/eq. Moreover, it is preferable that it is liquid at 25 degreeC. Also, the viscosity at 25° C. is preferably 10 to 10,000 mPa·s, more preferably 10 to 5,000 mPa·s.

Examples of polyfunctional epoxy compounds having a heterocyclic ring include isocyanuric acid-type epoxy compounds (manufactured by Nissan Chemical Industries, Ltd.: TEPIC-S, TEPIC-L, TEPIC-PAS, TEPIC-VL, TEPIC-FL, TEPIC-UC) and glycol. A uril-type epoxy compound (manufactured by Shikoku Kasei Co., Ltd.: TG-G) can be mentioned. The polyfunctional epoxy compound having a heterocyclic ring preferably has an epoxy equivalent of 80 to 450 g/eq. From the viewpoint of workability, it is preferably liquid at 25°C. Also, the viscosity at 25° C. is preferably 100 to 50,000 mPa·s, more preferably 100 to 5,000 mPa·s. On the other hand, from the viewpoint of adhesiveness, the one that is solid at 25°C is preferable.

(B) Polyfunctional Thiol Compound The resin composition of the present embodiment contains (B) a polyfunctional thiol compound (hereinafter also referred to as "component (B)"). In the present embodiment, (B) the polyfunctional thiol compound is a compound containing two or more thiol groups, and the thiol groups are (A) the epoxy groups in the polyfunctional epoxy compound and (C) the epoxy groups in the molecule. It reacts with the group (c) in a monofunctional compound having one group (c) containing a saturated double bond and an electron-withdrawing group adjacent thereto. In the present embodiment, (B) the polyfunctional thiol compound preferably has 3 or more thiol groups. (B) The polyfunctional thiol compound more preferably contains a trifunctional thiol compound and/or a tetrafunctional thiol compound. Trifunctional and tetrafunctional thiol compounds are thiol compounds having 3 and 4 thiol groups, respectively. (B) The thiol equivalent of the polyfunctional thiol compound is preferably 90 to 200 g/eq, more preferably 90 to 150 g/eq, even more preferably 90 to 140 g/eq, and 90 to 130 g. /eq is particularly preferred.

The polyfunctional thiol compound includes a thiol compound having a hydrolyzable partial structure such as an ester bond in the molecule (i.e. hydrolyzable) and a thiol compound having no such partial structure (i.e. non-hydrolyzable). It is divided into
Examples of hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]- Isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis (3-mercaptopropionate) (SC Organic Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko K.K.) : Karenz MT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione ( Karenz MT (registered trademark) NR1) manufactured by Showa Denko K.K. These may be used alone or in combination of two or more.

On the other hand, examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril (manufactured by Shikoku Kasei Co., Ltd.: TS-G), (1,3 , 4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Kasei Co., Ltd.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 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(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a- dimethyl glycol uril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethyl glycol uril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenyl glycol uril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluril, tris ( 3-mercaptopropyl)isocyanurate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate , pentaerythritol trippropanethiol (manufactured by SC Organic Chemical Co., Ltd.: PEPT), pentaerythritol tetrapropanethiol, 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-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6 , 9-trithiundecane, tetrakis(mercaptomethylthiomethyl)methane, tet rakis(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)ethane thiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianone, 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(mercaptomethylthio)-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(mercapto methylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-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-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-mercaptomethylthio-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-mercapto methylthio-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(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1, 3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2 -[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl]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-dithiolane etc. can be mentioned. These may be used alone or in combination of two or more.

(C) A monofunctional compound having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule The resin composition of the present embodiment is unsaturated in the molecule (C) A monofunctional compound (hereinafter also referred to as "component (C)") having one group (c) containing a double bond and an adjacent electron-withdrawing group (hereinafter also simply referred to as "group (c)") including. In this embodiment, group (c) in component (C), more specifically the unsaturated double bond in group (c), reacts with the thiol groups in (B) the polyfunctional thiol compound. In the present specification, the term "monofunctional" is used for component (C) to mean having one group (c) that reacts with a thiol group in the molecule. Examples of electron-withdrawing groups include carbonyl groups and cyano groups, with carbonyl groups being preferred.

Containing the component (C) suppresses an increase in the self-heating temperature during the curing reaction of the resin composition. The reason for this is, but not limited to, the following. The unsaturated double bond of the group (c) in the component (C) has high reactivity because the electron-withdrawing group is adjacent to it, and (A) the epoxy group in the polyfunctional epoxy compound (B ) reacts with the thiol groups in the polyfunctional thiol compound. Therefore, the exothermic peak associated with the curing reaction is shifted, the reaction heat is dispersed, and the increase in the self-heating temperature is suppressed. On the other hand, since the reaction system of the resin composition described in Patent Document 3 is mainly based on the reaction of epoxy-thiol, it is considered that the reaction heat was not dispersed and the self-heating temperature increased. In addition, the reaction of epoxy-thiol generates reaction heat due to the ring-opening reaction of the epoxy group, whereas the reaction of component (C) does not involve ring-opening. It is believed that the self-heating temperature is lower than that of the resin composition mainly based on epoxy-thiol reaction described in Patent Document 3. From the viewpoint of suppressing overheating of the adherend to which the resin composition of the present invention is applied and its peripheral members, the temperature difference between the curing temperature and the maximum self-heating temperature (maximum heat generation temperature) is 20° C. or less. It is preferably 15° C. or lower, more preferably 10° C. or lower. The maximum self-heating temperature (maximum heat generation temperature) is preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower.
In addition, since the component (C) is monofunctional, it does not form crosslinks and can suppress an increase in the internal stress of the cured product due to an excessively high crosslink density. Flexibility can be provided.

Component (C) is preferably liquid at 25° C. from the viewpoint of the viscosity of the resin composition.

Examples of component (C) include monofunctional maleimide compounds, monofunctional (meth)acrylate compounds, and monofunctional acrylamide compounds. Group (c) includes a maleimide group and a (meth)acryloyl group. In this embodiment, component (C) is preferably selected from monofunctional maleimide compounds and monofunctional (meth)acrylate compounds, more preferably monofunctional (meth)acrylate compounds.

Monofunctional maleimide compounds are compounds having one maleimide group as group (c), examples of which include maleimide; methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearyl Aliphatic hydrocarbon group-containing maleimides such as maleimide and cyclohexylmaleimide; aromatic ring-containing maleimides such as phenylmaleimide; These may be used alone or in combination of two or more.

A monofunctional (meth)acrylate compound is a compound having one (meth)acryloyl group as group (c). Examples of monofunctional (meth)acrylate compounds include:
- ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate Acrylates, Phenoxyethyl (meth)acrylate, Benzyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Ethoxydiethyleneglycol (meth)acrylate, Phenoxydiethyleneglycol (meth)acrylate, Phenoxypolyethyleneglycol (meth)acrylate, Butoxydiethyleneglycol (meth)acrylate Acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxytriethyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, 2-ethylhexyldiethyleneglycol (meth)acrylate, 4-tert-butyl Esters of monohydric alcohols and (meth)acrylic acid such as cyclohexyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy Butyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, 1-naphthalenemethyl (Meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1 , 3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2-ethyl -2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl -2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropan-2-yl ( meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro- 2-furanyl (meth)acrylate, 2-oxotetrahydrofuran-3-yl (meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl (meth)acrylate, (2-oxo-1,3-dioxolane-4- Mono(meth)acrylates of polyhydric alcohols such as yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), 1-ethoxyethyl(meth)acrylate or Esters of monohydric alcohol and (meth)acrylic acid can be mentioned. These may be used alone or in combination of two or more. From the viewpoint of stress relaxation of the cured product, the monofunctional (meth)acrylate compound preferably has a molecular weight of 450 or less, more preferably 400 or less, even more preferably 380 or less, and 350 or less. is more preferable, and 300 or less is particularly preferable. In order to prevent contamination of peripheral members due to volatilization, the monofunctional (meth)acrylate compound preferably has low volatility and preferably has a molecular weight of 100 or more, more preferably 120 or more. , is more preferably 160 or more, particularly preferably 190 or more, and most preferably 200 or more. In one aspect, the molecular weight of the monofunctional (meth)acrylate compound is preferably 100 to 450, more preferably 120 to 400, even more preferably 140 to 380, and 180 to 350. is particularly preferred, and 200-320 is most preferred.

Component (C) may have a group capable of reacting with a thiol group such as an epoxy group, in addition to group (c). However, from the viewpoint of the flexibility of the resulting cured product, it may be preferable that the component (C) does not contain a group capable of reacting with a thiol group such as an epoxy group.

In the present embodiment, from the viewpoint of achieving both flexibility and adhesive strength, the ratio of the number of equivalents of the group (c) of the component (C) to the number of equivalents of the epoxy group of the component (A) ([group (c) of the component (C) ) equivalent number]/[epoxy group equivalent number of component (A)]) is preferably from 0.05 to 2, more preferably from 0.1 to 1.5, and from 0.15 to 1.5. 25 is more preferred, and 0.2 to 1 is particularly preferred.
In the present embodiment, the ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of component (A)]/[number of thiol group equivalents of component (B)] ) is preferably 0.4 to 0.95, more preferably 0.45 to 0.9, even more preferably 0.5 to 0.9, and 0.55 to 0.95. 9 is particularly preferred.
In the present embodiment, from the viewpoint of curability and bleeding suppression, the ratio of the total number of epoxy group equivalents of component (A) and the group (c) equivalent number of component (C) to the thiol group equivalent number of component (B) (([Epoxy group equivalent number of component (A)] + [Group (c) equivalent number of component (C)]) / [thiol group equivalent number of component (B)]) is 0.7 to 1.5 is preferably 0.75 to 1.4, more preferably 0.8 to 1.3, and most preferably 0.8 to 1.1. In particular, by blending a certain amount of the component (B) with the component (A) and the component (C), it is possible to suppress the remaining unreacted components that cannot react with the thiol group, and to suppress bleeding due to the unreacted components. can be done. It is also expected that volatile components will be suppressed. In the present specification, bleeding means that when an adhesive containing a curable resin composition is used for fixing or bonding parts, unreacted components exude from the adhesive-applied or cured product over time. It is a phenomenon, and the exuded component itself is sometimes called "bleed".
In the present embodiment, the ratio of the number of group (c) equivalents of component (C) to the number of thiol group equivalents of component (B) ([number of group (c) equivalents of component (C)]/[thiol of component (B) Group equivalent number]) is preferably from 0.05 to 0.7, more preferably from 0.1 to 0.6, and even more preferably from 0.15 to 0.55.
In addition, when component (C) contains an epoxy group, after adding the epoxy group equivalent number of component (C) to the epoxy group equivalent number of component (A), the above equivalent number relational expression is satisfied. is preferred.

In this specification, functional group equivalents such as thiol equivalent, epoxy equivalent, and (meth)acryloyl equivalent represent the molecular weight of a compound per functional group, and the number of thiol group equivalents, the number of epoxy group equivalents, the number of (meth) A functional group equivalent number such as an acryloyl equivalent number represents the number of functional groups (equivalent number) per compound mass (amount charged).

The epoxy equivalent weight of component (A) is theoretically the molecular weight of component (A) divided by the number of epoxy groups in one molecule. The actual epoxy equivalent can be obtained by the method described in JIS K7236. The number of epoxy group equivalents of component (A) is the number of epoxy groups (number of equivalents) per mass (amount charged) of component (A), and the mass (g) of the epoxy compound of component (A) is It is the quotient divided by the epoxy equivalent weight of the compound (if more than one epoxy compound is involved, the sum of such quotients for each epoxy compound). In addition, when a component (C) contains an epoxy group, the epoxy equivalent and epoxy group equivalent number are similarly calculated|required.

The thiol equivalent weight of component (B) is theoretically the molecular weight of component (B) divided by the number of thiol groups in one molecule. The actual thiol equivalent weight can be determined, for example, by potentiometrically determining the thiol number. This method is widely known and disclosed, for example, in paragraph 0079 of JP-A-2012-153794. The thiol group equivalent number of component (B) is the number of thiol groups (equivalent number) per mass (amount charged) of component (B), and the mass (g) of the polythiol compound (B) is the weight of the polythiol compound. It is the quotient divided by the thiol equivalent (if more than one polythiol compound is involved, the sum of such quotients for each polythiol compound).

When the group (c) is a (meth)acryloyl group, the (meth)acryloyl equivalent of the component (C) is theoretically the molecular weight of the (meth)acrylate compound, the acryloyl group (or methacryloyl group) in one molecule. equal to the number divided by the number of The actual (meth)acryloyl equivalent can be measured, for example, by NMR. The number of (meth)acryloyl group equivalents of component (C) is the number (number of equivalents) of (meth)acryloyl groups per mass (amount charged) of component (C), and the mass of (A) (meth)acrylate compound (g) divided by the (meth)acryloyl equivalent of the (meth)acrylate compound (if more than one (meth)acrylate compound is involved, the sum of such quotients for each (meth)acrylate compound) be.

When group (c) is a maleimide group, the maleimide equivalent of component (C) is theoretically equal to the molecular weight of the maleimide compound divided by the number of maleimide groups in one molecule. The actual maleimide equivalent weight can be measured, for example, by NMR. The maleimide group equivalent number of the component (C) is the number of maleimide groups (equivalent number) per mass (amount charged) of the component (C), and the mass (g) of the maleimide compound (C) is defined as the weight of the maleimide compound. It is the quotient divided by the maleimide equivalent (the sum of such quotients for each maleimide compound, if more than one maleimide compound is involved).

(D) Curing Catalyst The resin composition of the present embodiment contains (D) a curing catalyst (hereinafter also referred to as “component (D)”). By using component (D), the resin composition of the present embodiment can be cured in a short time even under low temperature conditions. The curing catalyst used in the present embodiment is not particularly limited as long as it is a curing catalyst for (A) the polyfunctional epoxy compound, and known catalysts can be used.

Component (D) is preferably a latent curing catalyst. A latent curing catalyst is a compound that is inactive at room temperature and is activated by heating to function as a curing catalyst. For example, an imidazole compound that is solid at room temperature; solid-dispersed amine adduct-based latent curing catalysts (amine-epoxy adduct system); reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct system); From the viewpoint of pot life and curability, the component (D) is preferably a solid-dispersed amine adduct latent curing catalyst.

Examples of imidazole compounds that are solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2 -phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2'- methylimidazolyl-(1)′)-ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 -cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-(2-methylimidazolyl-(1) -ethyl)-aziboyldiamide and the like, but are not limited to these.

Examples of the epoxy compound used as one of raw materials for producing the solid-dispersed amine adduct-based latent curing catalyst (amine-epoxy adduct system) include bisphenol A, bisphenol F, catechol, polyhydric phenols such as resorcinol, or glycerin. Polyglycidyl ethers obtained by reacting polyhydric alcohols such as polyhydric alcohols and polyethylene glycol with epichlorohydrin; reaction of epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; 4,4'-diaminodiphenylmethane, m-aminophenol, etc. and epi Glycidylamine compounds obtained by reacting with chlorohydrin; further polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin, butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, etc. and the like, but are not limited to these.

An amine compound used as another raw material for producing a solid-dispersed amine adduct-based latent curing catalyst has in its molecule one or more active hydrogens capable of undergoing an addition reaction with an epoxy group, and has a primary amino group, a secondary Any compound having at least one functional group selected from an amino group and a tertiary amino group in the molecule may be used. Examples of such amine compounds are shown below, but are not limited thereto. Aliphatic amines such as, for example, diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane; 4,4'-diaminodiphenylmethane, 2 -aromatic amine compounds such as methylaniline; nitrogen atom-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine; etc., but not limited to these.

Among these compounds, compounds having a tertiary amino group in the molecule are particularly raw materials that provide latent curing catalysts having excellent curing accelerating ability. Examples of such compounds include, for example, dimethylaminopropylamine , diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine and other amine compounds, 2-methylimidazole, 2-ethylimidazole, 2-ethyl- Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as 4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2- hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2- ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl) Phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercapto Benzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic hydrazide alcohols, phenols, thiols, carboxylic acids and hydrazides having a tertiary amino group in the molecule such as , nicotinic acid hydrazide, and isonicotinic acid hydrazide, but are not limited to these. do not have.

Examples of isocyanate compounds used as solid-dispersed amine adduct-based latent curing catalysts and as another manufacturing raw material include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; methylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc. polyfunctional isocyanate compounds; Furthermore, terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds can also be used. Examples of such terminal isocyanate group-containing compounds include an addition compound having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, and a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and pentaerythritol. but not limited thereto.

Urea compounds include, for example, urea and thiourea, but are not limited to these.

The solid-dispersed latent curing catalyst that can be used in the present embodiment includes, for example, the above (a) two components of an amine compound and an epoxy compound, (b) three components of these two components and an active hydrogen compound, or (c ) Binary or ternary combinations of amine compounds and isocyanate compounds and/or urea compounds. These components are mixed and reacted at a temperature from room temperature to 200° C., then solidified by cooling and pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and after removing the solvent, , can be easily produced by pulverizing the solid content.

Typical examples of commercially available latent curing catalysts include amine-epoxy adduct (amine adduct) such as "Amicure PN-23" (product name of Ajinomoto Fine-Techno Co., Ltd.) and "Amicure PN-40". (Ajinomoto Fine-Techno Co., Ltd. product name), “Amicure PN-50” (Ajinomoto Fine-Techno Co., Ltd. product name), “Hardner X-3661S” (ACR Co., Ltd. product name), “Hardner X-3670S” (ACR Co., Ltd. product name), “Novacure HX-3742” (Asahi Kasei Co., Ltd. product name), “Novacure HX-3721” (Asahi Kasei Co., Ltd. product name), “Novacure HXA9322HP” (Asahi Kasei Co., Ltd. product name) ), “Novacure HXA3922HP” (Asahi Kasei Corp. product name), “Novacure HXA3932HP” (Asahi Kasei Corp. name), “Novacure HXA5945HP” (Asahi Kasei Corp. name), “Novacure HXA5911HP” (Asahi Kasei Corp. name), "Novacure HXA9382HP" (Asahi Kasei Corp. product name), etc., and urea-type adducts include "Fujicure FXE-1000" (T&K TOKA Corp. trade name), Fujicure FXR1020" (T&K TOKA Corp. trade name) ), “Fujicure FXR-1030” (T&K TOKA Co., Ltd. product name), “Fujicure FXR1121” (T&K TOKA Co., Ltd. product name), “Fujicure FXR1081” (T&K TOKA Co., Ltd. product name), “Fujicure FXR1061” (T&K TOKA (product name of T&K TOKA Corporation), "Fujicure FXR1171" (product name of T&K TOKA Corporation), etc., but not limited thereto. Any one of component (D) may be used, or two or more thereof may be used in combination.

Component (D) is preferably contained in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, relative to the total mass of the resin composition.

Incidentally, component (D) may be provided in the form of a dispersion dispersed in an epoxy compound. When using such a form of component (D), it should be noted that the amount of epoxy compound in which it is dispersed is also included in the amount of component (A) in the resin composition of this embodiment. .

If desired, the resin composition of the present embodiment may contain optional components other than the components (A) to (D), such as those described below.

(E) Polyfunctional (meth)acrylate compound The resin composition of the present embodiment includes (E) a polyfunctional (meth)acrylate compound (hereinafter, also referred to as "component (E)") as long as the effects of the present invention are not impaired. ) may be contained.

Examples of polyfunctional (meth)acrylate compounds include tris(2-hydroxyethyl)isocyanurate diacrylate and/or dimethacrylate; tris(2-hydroxyethyl)isocyanurate triacrylate and/or trimethacrylate; trimethylolpropane Triacrylate and/or trimethacrylate, or oligomers thereof; pentaerythritol triacrylate and/or trimethacrylate, or oligomers thereof; polyacrylate and/or polymethacrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris (acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; alkyl-modified dipentaerythritol polyacrylate and/or polymethacrylate; caprolactone-modified dipentaerythritol polyacrylate and/or polymethacrylate; A diacrylate and/or ethoxylated bisphenol A dimethacrylate; dihydrocyclopentadiethyl acrylate and/or dihydrocyclopentadiethyl methacrylate, and poly( Examples include meth)acrylates, polyurethanes having two or more (meth)acryloyl groups in one molecule, and polyesters having two or more (meth)acryloyl groups in one molecule.
As the polyfunctional (meth)acrylate compound, any one of the polyfunctional (meth)acrylate compounds described above may be used, or two or more thereof may be used in combination.

Examples of commercially available polyfunctional (meth)acrylate compounds include polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Ornex Co., Ltd., ditrimethylolpropane tetraacrylate (product name: EBECRYL140) manufactured by Daicel-Ornex Co., Ltd., and Toagosei Co., Ltd. Polyester acrylate (product name: M7100) manufactured by Kyoeisha Chemical Co., Ltd. Dimethylol-tricyclodecane diacrylate (product name: light acrylate DCP-A) manufactured by Nippon Kayaku Co., Ltd. Neopentyl glycol-modified trimethylolpropane diacrylate (product name: Kayarad R -604) and the like.

(F) Filler The resin composition of the present embodiment may contain (F) a filler (hereinafter also referred to as “component (F)”) within a range that does not impair the effects of the present invention. By including (F) a filler in the resin composition, the coefficient of linear expansion of the cured product obtained by curing the resin composition can be lowered, and the thermal cycle resistance is improved. In addition, if the filler has a low elastic modulus, the stress generated in the cured product can be relaxed, improving long-term reliability. (F) Fillers are roughly classified into inorganic fillers and organic fillers.

The inorganic filler is not particularly limited as long as it is composed of particles made of an inorganic material and has the effect of lowering the coefficient of linear expansion when added. Inorganic materials include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, oxide Titanium, zinc oxide, silicon carbide, silicon nitride, boron nitride and the like can be used. Any one of the inorganic fillers may be used, or two or more thereof may be used in combination. As the inorganic filler, it is preferable to use a silica filler because the filling amount can be increased. Silica is preferably amorphous silica. The surface of the inorganic filler may be treated with a coupling agent such as a silane coupling agent.

Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, fillers having a urethane skeleton, fillers having a butadiene skeleton, and styrene fillers. The organic filler may be surface-treated.

The shape of the filler is not particularly limited, and may be spherical, scaly, acicular, amorphous, or the like.

The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. As used herein, the average particle diameter refers to a volume-based median diameter (d ₅₀ ) measured by a laser diffraction method according to ISO-13320 (2009), unless otherwise specified. By setting the average particle diameter of the filler to the upper limit or less, it is possible to suppress the sedimentation of the filler, suppress the formation of coarse particles, and reduce the wear of the nozzle of the jet dispenser and the resin discharged from the nozzle of the jet dispenser. Scattering of the composition outside the desired region can be suppressed. Although the lower limit of the average particle size of the filler is not particularly limited, it is preferably 0.005 µm or more, more preferably 0.1 µm or more, from the viewpoint of the viscosity of the resin composition. In one aspect of the present embodiment, the average particle size of the (F) filler is preferably 0.01 μm to 5.0 μm, more preferably 0.1 μm to 3.0 μm. Fillers having different average particle sizes may be used in combination. For example, a filler with an average particle size of 0.005 μm or more and less than 0.1 μm and a filler with an average particle size of 0.1 μm to 6.0 μm may be used in combination.

The content of the filler in the resin composition of the present embodiment is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, relative to the total mass of the resin composition, and 20 to 40% by mass. % is more preferred. By setting the content of the filler within the above range, thermal cycle resistance is improved, and the viscosity of the resin composition is set within an appropriate range, thereby improving applicability to dispensing.

(G) Photoradical initiator The resin composition of the present embodiment may contain (G) a photoradical initiator (hereinafter also referred to as "component (G)") within a range that does not impair the effects of the present invention. good. By including (G) a photoradical initiator, the reaction of the component (B) with the component (C) and the optional component (E) by light irradiation is promoted.
(G) Photoradical initiators include, for example, alkylphenone-based compounds and acylphosphine oxide-based compounds.

Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available, Omnirad 651 manufactured by IGM Resins B.V.); α-aminoalkylphenones such as 2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available from IGM Resins B.V., Omnirad 907); 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available α-hydroxyalkylphenone such as Omnirad 184) manufactured by IGM Resins BV; 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)- Butan-1-one (commercially available as Omnirad 379EG manufactured by IGM Resins B.V.), 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone (commercially available as Omnirad manufactured by IGM Resins B.V.) 369) and the like.

Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins B.V.), bis(2,4,6- trimethylbenzoyl)-phenylphosphine oxide (as a commercial product, Omnirad 819 manufactured by IGM Resins B.V.) and the like.

(G) As the photoradical initiator, in addition to the photoradical initiators described above, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl )-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2- Hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether , benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl- 4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, camphorquinone and the like.

(G) The content of the photoradical initiator, from the viewpoint of photoirradiation reactivity, with respect to a total of 100 parts by mass of the monofunctional (meth) acrylate compound and the polyfunctional (meth) acrylate compound, preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass.

(H) Stabilizer If desired, the resin composition of the present embodiment contains (H) a stabilizer (hereinafter also referred to as “component (H)”) within a range that does not impair the effects of the present invention. It's okay. The stabilizer can improve the storage stability and prolong the pot life of the resin composition of the present embodiment. Various stabilizers known as stabilizers can be used, but at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates and organic acids is highly effective in improving storage stability. One is preferred.

Examples of liquid borate compounds include 2,2′-oxybis(5,5′-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, trioctadecylborate, tris( 2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentoxatetradecyl)(1,4,7-trioxaundecyl) ) borane, tribenzylborate, triphenylborate, tri-o-tolylborate, tri-m-tolylborate, triethanolamineborate and the like. Since the liquid borate ester compound is liquid at room temperature (25° C.), it is preferable because the viscosity of the formulation can be kept low. As the aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used. As an organic acid, for example, barbituric acid can be used.
Any one of the stabilizers may be used, or two or more of them may be used in combination.

When a stabilizer is added, the amount added is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, relative to the total mass of the resin composition. More preferably, it is 0.1 to 20% by mass.

(I) Coupling agent If desired, the resin composition of the present embodiment contains (I) a coupling agent (hereinafter also referred to as “component (I)”) within a range that does not impair the effects of the present invention. It's okay. The coupling agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds with the inorganic material, and the other of which chemically bonds with the organic material. It is a functional group. By including a coupling agent in the resin composition, the adhesion strength of the resin composition to a substrate or the like is improved.

(I) Examples of coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, titanium coupling agents, and the like, depending on the type of functional group that chemically bonds with the inorganic material.

Examples of coupling agents include various types of coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto, depending on the type of functional group that chemically bonds with the organic material. It is not limited to these. Among these, an epoxy-based coupling agent containing an epoxy group is preferable from the viewpoint of moisture resistance reliability.

Specific examples of epoxy-based silane coupling agents include 3-glycidoxypropyltrimethoxysilane (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (product name: KBE-403, Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldiethoxysilane (product name: KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldimethoxysilane (product name: KBM402, manufactured by Shin-Etsu Chemical Co., Ltd.) , 8-glycidoxyoctyltrimethoxysilane (product name: KBM-4803, Shin-Etsu Chemical Co., Ltd.), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name: KBM-303, Shin-Etsu Chemical Co., Ltd.) ) and the like.

Specific examples of methacrylic silane coupling agents include 3-methacryloxypropyltrimethoxysilane (product name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxysilane (product name: KBM502, manufactured by Shin-Etsu Chemical Co., Ltd.). ), 3-methacryloxypropylmethyldiethoxysilane (product name: KBE502, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltriethoxysilane (product name: KBE503, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

Specific examples of acrylic silane coupling agents include 3-acryloxypropyltrimethoxysilane (product name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.).

In the present embodiment, the methacrylic silane coupling agent and the acrylic silane coupling agent are not included in the component (C), unlike the component (C) in that they have functional groups that chemically bond with the inorganic material. .

Specific examples of mercapto-based silane coupling agents include 3-mercaptopropyltrimethoxysilane (product name: KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-mercaptopropylmethyldimethoxysilane (product name: KBM802, manufactured by Shin-Etsu Chemical Co., Ltd.). ).

Any one of the coupling agents may be used, or two or more thereof may be used in combination.

When a coupling agent is added, the amount of the coupling agent added is preferably 0.01% by mass to 30% by mass with respect to the total mass of the resin composition, from the viewpoint of improving adhesive strength, and 0.1% by mass. It is more preferably from 10% by mass to 10% by mass.

(J) Other Additives The resin composition of the present embodiment may, if desired, include other additives such as carbon black, titanium black, ion trapping agents, leveling agents within the scope of the present embodiment. , an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a coloring agent, a solvent, and the like. The type and amount of each additive are as per conventional methods.

A method for producing the resin composition of the present embodiment is not particularly limited. For example, components (A) to components (D), and if necessary components (E), components (F), components (G), components (H), components (I), (J) other additives, etc. The resin composition of the present embodiment can be obtained by simultaneously or separately introducing into an appropriate mixer, stirring and mixing while melting by heating if necessary, and making a uniform composition. can. Although the mixer is not particularly limited, a Laikai machine, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like equipped with a stirring device and a heating device can be used. Also, these devices may be used in combination as appropriate.

The resin composition thus obtained is thermosetting, and at a temperature of 80° C., it preferably cures within 5 hours, more preferably within 3 hours, and within 1 hour. It is more preferable to cure to When the curable composition of the present embodiment is used for manufacturing a semiconductor module including parts that deteriorate under high temperature conditions, it is preferable to heat cure the composition at a temperature of 50 to 90° C. for 30 to 120 minutes. . Moreover, the resin composition of this embodiment has low volatility. Volatility can be determined from heat loss. The weight loss on heating is preferably 1% or less, more preferably 0.7% or less, even more preferably 0.5% or less.

The resin composition of the present embodiment can be used, for example, as an adhesive or a sealing material for fixing, bonding or protecting parts constituting a semiconductor device or an electronic component, or as a raw material thereof.

[Adhesive or sealing material]
The adhesive or encapsulant of the second embodiment of the present invention contains the resin composition of the first embodiment described above. This adhesive or encapsulant provides good fixation, bonding or protection to engineering plastics (e.g. LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g. copper, nickel, etc.). It can be used for fixing, joining or protecting parts constituting a semiconductor device or an electronic component. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits.
The adhesive or sealing material of the present embodiment can be cured under low temperature conditions and can give a cured product having excellent stress relaxation properties, so that productivity is high, and for example, multiple adhesives made of different materials It is suitable for use in the manufacture of semiconductor devices and electronic parts that are assembled by joining parts of In addition, the adhesive or sealing material of the present embodiment has a low self-heating temperature during the curing reaction, so that it is suitable for use, for example, in manufacturing a semiconductor module equipped with miniaturized electronic components.

[Resin composition or adhesive or cured product of sealing material]
The cured product of the third embodiment of the present invention is a cured product obtained by curing the resin composition of the first embodiment or the adhesive or sealing material of the second embodiment. This cured product has excellent stress relaxation properties.

[Semiconductor devices, electronic components]
Since the semiconductor device or electronic component of the fourth embodiment of the present invention contains the cured product of the above-described third embodiment, the semiconductor device or electronic component assembled by joining a plurality of parts made of different materials in particular It has high reliability in Here, the term "semiconductor device" refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic equipment, and the like. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples, parts and % are parts by weight and % by weight unless otherwise specified.

[Examples 1 to 24, Comparative Examples 1 to 2]
Resin compositions were prepared according to the formulations shown in Table 1 by mixing predetermined amounts of each component using a three-roll mill. In Table 1, the amount of each component is expressed in parts by mass (unit: g). Components used in Examples and Comparative Examples are as follows.

- (A) polyfunctional epoxy compound (component (A))
(A-1): Bisphenol F type epoxy resin/bisphenol A type epoxy resin mixture (product name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165 g/eq)
(A-2): Liquid epoxy compound (product name: JER YX7400, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 450 g/eq)
(A-3): PO-modified bisphenol type liquid epoxy resin (product name: AER9000, manufactured by Asahi Kasei Corporation, epoxy equivalent: 380 g/eq)
(A-4): Bisphenol F type epoxy resin (product name: jER4005P, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 1004 g/eq)
(A-5): Epoxy resin in component (D-1) (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 180 g/eq)

· (B) polyfunctional thiol compound (component (B))
(B-1): Pentaerythritol tetrakis(3-mercaptopropionate) (product name: PEMP, manufactured by SC Organic Chemical, thiol equivalent: 122 g/eq)
(B-2): 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (product name: TS-G, manufactured by Shikoku Kasei Co., Ltd., thiol equivalent: 100 g/eq)
(B-3): 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (product name: C3 TS-G, manufactured by Shikoku Kasei Co., Ltd., thiol equivalent: 114 g/eq)
(B-4): Trimethylolpropane tris(3-mercaptopropionate) (product name: TMMP, manufactured by SC Organic Chemical, thiol equivalent: 133 g/eq)
(B-5): Pentaerythritol trippropanethiol (product name: PEPT, manufactured by SC Organic Chemical, thiol equivalent: 124 g/eq)

- (C) a monofunctional compound having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule (component (C))
(C-1): Dicyclopentanyl acrylate (product name: FA513AS, manufactured by Showa Denko Materials Co., Ltd., (meth)acryloyl equivalent: 206 g / eq)
(C-2): isobornyl acrylate (product name: IBXA, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 208 g/eq)
(C-3): 2-(o-phenylphenoxy)ethyl acrylate (Product name: HRD-01, Nisshoku Techno Fine Chemical Co., Ltd., (meth)acryloyl equivalent: 268 g/eq)
(C-4): (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (product name: MEDOL-10, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 200 g/ eq)
(C-5): Cyclic trimethylolpropane formal acrylate (product name: Viscoat #200, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 200 g/eq)
(C-6): m-phenoxybenzyl acrylate (Product name: Light Acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 254 g/eq)
(C-7): Isostearyl acrylate (product name: ISTA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 325 g/eq)
(C-8): n-octyl acrylate (product name: NOAA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 184 g/eq)
(C-9): Methoxyethylene oxide-modified acrylate (product name: Light Acrylate 130A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 428 g/eq)
(C-10): butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 128 g / eq)

・(D) Curing catalyst (component (D))
(D-1): Amine-epoxy adduct-based latent curing catalyst (product name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation)
(D-2): Urea-type adduct latent curing catalyst (product name: Fujicure FXR1121, manufactured by T&K TOKA Co., Ltd.)

The latent curing catalyst (D-1) is a particulate latent curing catalyst dispersed in an epoxy resin (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (epoxy equivalent: 180 g/eq)). It is provided in the form of a dispersion (latent curing catalyst/mixture of bisphenol A epoxy resin and bisphenol F epoxy resin = 33/67 (mass ratio)). The epoxy resin that makes up this dispersion is treated as forming part of component (A). Therefore, in Table 1, the amount of only the latent curing catalyst in (D-1) is shown in the column for component (D), and the amount of the epoxy resin in (D-1) is shown in the column for component (A). A-5).

(E) Polyfunctional (meth)acrylate compound (component (E))
(E-1): Dimethyloltricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 152 g/eq)

・(F) Filler (component (F))
(F-1): Silica filler 1 (product name: SE2300, manufactured by Admatechs Co., Ltd., average particle size: 0.6 μm)
(F-2): Silica filler 2 (product name: Admanano YA050C-SM1, Admatechs Co., Ltd., average particle size: 50 nm)
(F-3): Crosslinked styrene monodisperse particles (product name: SX350H, manufactured by Soken Chemical Co., Ltd., average particle size: 3.5 μm)

- (G) photoradical initiator (component (G))
(G-1): α-aminoalkylphenone; 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.)

(H) stabilizer (component (H))
(H-1): triisopropyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(H-2): N-nitroso-N-phenylhydroxylamine aluminum salt (product name: Q1301, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)

- (Z) monofunctional epoxy compound (component (Z))
(Z-1): p-tert-butylphenyl glycidyl ether (product name: ED509S, manufactured by ADEKA Corporation, epoxy equivalent: 205 g/eq)

In Table 1, the symbols in the column of "equivalent number calculation" represent the following meanings.
"((A) + (C) + (E) + (Z)) / (B)" is the number of epoxy group equivalents of component (A) with respect to the number of thiol group equivalents of component (B) and the number of component (C) Ratio of the sum of the group (c) equivalent number, the (meth)acryloyl group equivalent number of component (E), and the epoxy group equivalent number of component (Z) (([epoxy group equivalent number of component (A)] + [component Group (c) equivalent number of (C)] + [(meth)acryloyl group equivalent number of component (E)] + [epoxy group equivalent number of component (Z)]) / [thiol group equivalent number of component (B) ]).
"(A)/(B)" is the ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (B) ([the number of epoxy group equivalents of component (A)]/[the number of component (B) thiol group equivalent number]).
"(C) / (B)" is the ratio of the number of group (c) equivalents of component (C) to the number of thiol group equivalents of component (B) ([number of group (c) equivalents of component (C)] / [ Thiol group equivalent number of component (B)]).
"(E)/(B)" is the ratio of the (meth)acryloyl group equivalent number of component (E) to the thiol group equivalent number of component (B) ([(meth)acryloyl group equivalent number of component (E)] /[thiol group equivalent number of component (B)]).
"(Z)/(B)" is the ratio of the number of epoxy group equivalents of component (Z) to the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of component (Z)]/[component (B) thiol group equivalent number]).

In Examples and Comparative Examples, properties of resin compositions and cured products obtained by curing the resin compositions were measured as follows.

[Evaluation of flexibility]
Each resin composition was applied to a Teflon (registered trademark) sheet with a thickness of 0.3 mm, and subjected to heat curing treatment by heating at 80° C. for 60 minutes in a blower dryer to prepare a cured product sheet. . A dumbbell for tensile test (shown in FIG. 1) was prepared from the obtained cured product sheet, and a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation) was used to test the tensile strength at room temperature (22 ° C.). The elongation at break (unit: %) was measured at a speed of 5 mm/min. Evaluation of flexibility was performed at n=4. Table 1 shows the measurement results.
It can be seen that the elongation at break obtained by the above test is higher in Examples 1 to 24 containing component (C) than in Comparative Example 1 not containing component (C). The elongation at break is preferably 40% or more, more preferably 70% or more, and even more preferably 100% or more.

[Evaluation of self-heating temperature]
Maximum sample temperature during TG-DTA measurement: (°C)
20 mg of each resin composition was placed in an aluminum container for TG-DTA, and measured from 25 ° C. to 80 ° C. with a thermogravimetric-differential thermal simultaneous measurement device (TG-DTA, manufactured by Rigaku Co., Ltd.: Thermo plus EVO (registered trademark)). The temperature of the resin composition was measured while the temperature was raised at a rate of 3° C./min and maintained at 80° C. for 10 min. Table 1 shows the maximum exothermic temperature in the obtained temperature curve. Table 1 shows the temperature difference between the curing temperature (80° C.) and the maximum exothermic temperature of the resin composition.
The maximum exothermic temperature of the resin composition is preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower.

[Evaluation of volatilization amount during heat curing treatment]
1 g of each resin composition was placed in a SUS container having a diameter of 5 cm and a depth of 6 mm, and the entire bottom surface of the container was filled so that the surface area was uniform. After measuring the weight of the entire container containing the resin composition, the resin composition was cured by heat curing treatment at 80° C. for 60 minutes in a blower dryer. After the heat curing treatment, the container was allowed to stand until the heat cooled down, and the weight of the entire container containing the cured product of the resin composition was measured. After that, the volatilization amount was calculated from the weight change before and after the heat treatment using the following formula (1). Evaluation of volatilization amount during heat curing was performed with n=3.
[Amount of volatilization (%)] = 100 × {[Weight of the entire container containing the resin composition before heat curing (g)] - [Weight of the entire container after heat curing (g)]} / [Initial Weight of resin composition (g)] Formula (1)
The volatilization amount during heat curing obtained by the above test is preferably 1.0% or less, more preferably 0.7% or less, and even more preferably 0.5% or less.

It can be seen that the cured products of the resin compositions of Examples 1 to 24 all have high elongation at break and excellent flexibility (stress relaxation properties). In addition, the resin compositions of Examples 1 to 24 had low self-heating temperatures during the curing reaction. In addition, the resin compositions of Examples 1 to 24 had a small amount of volatilization during the heat curing treatment.
On the other hand, the cured product of the resin composition of Comparative Example 1, which did not contain the component (C), had a low elongation at break and did not satisfy the required stress relaxation criteria. In addition, the resin composition of Comparative Example 1 had a high self-heating temperature during the curing reaction.
The resin composition of Comparative Example 2 containing (Z) the monofunctional epoxy compound instead of the component (C) had a high self-heating temperature during the curing reaction.

The present invention is a resin composition that cures under low temperature conditions to give a cured product with excellent stress relaxation properties and has a low self-heating temperature during the curing reaction, and joins multiple parts made of different materials. It is very useful as an adhesive or sealing material suitable for use in manufacturing semiconductor devices and electronic parts that are assembled together.

Claims (10)

(A) a polyfunctional epoxy compound,
(B) a polyfunctional thiol compound,
(C) a monofunctional compound having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule, and (D) a curing catalyst .
Component (C) is selected from monofunctional maleimide compounds and monofunctional (meth)acrylate compounds,
The ratio of the epoxy group equivalent number of component (A) to the thiol group equivalent number of component (B) ([epoxy group equivalent number of component (A)]/[thiol group equivalent number of component (B)]) is 0. 4 to 0.95,
Ratio of group (c) equivalent number of component (C) to thiol group equivalent number of component (B) ([group (c) equivalent number of component (C)]/[thiol group equivalent number of component (B)]) is 0.05 to 0.7,
Does not contain a compound containing a thiirane ring in an amount such that the number of thiirane rings contained is 60 or more with respect to the number of oxirane rings contained in the resin composition of 40;
Resin composition . 2. The resin composition according to claim 1, wherein component (C) is a monofunctional (meth)acrylate compound having a molecular weight of 100-450. Ratio of the group (c) equivalent number of component (C) to the epoxy group equivalent number of component (A) ([group (c) equivalent number of component (C)]/[epoxy group equivalent number of component (A)]) is 0.05 to 2, the resin composition according to claim 1. Ratio of the sum of the number of epoxy group equivalents of component (A) and the number of group (c) equivalents of component (C) to the number of thiol group equivalents of component (B) (([epoxy group equivalent number of component (A)] + The resin composition according to claim 1, wherein [group (c) equivalent number of component (C)])/[thiol group equivalent number of component (B)]) is from 0.7 to 1.5. 2. The resin composition according to claim 1, wherein (A) the polyfunctional epoxy compound is liquid at 25[deg.]C. An adhesive or sealing material comprising the resin composition according to any one of claims 1 to 5 . A cured product obtained by curing the resin composition according to any one of claims 1 to 5 . A cured product obtained by curing the adhesive or sealing material according to claim 6 . A semiconductor device or electronic component comprising the cured product according to claim 7 . A semiconductor device or electronic component comprising the cured product according to claim 8 .

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