WO2018173991A1 - Resin composition, adhesive for electronic part, semiconductor device, and electronic part - Google Patents

Abstract

The purpose of the present invention is to provide a resin composition that can be cured in a short time and is excellent in drop impact resistance after curing, a semiconductor device including a cured product of the resin composition, and an electronic part. The resin composition is characterized by comprising (A) an epoxy resin, (B) a thiol-based curing agent, and (C) talc, wherein the amount of the (C) component is 5-20 parts by mass in relation to 100 parts by mass of the resin composition. Preferably, the resin composition further comprises (D) calcium carbonate and/or silica.

Description

Resin composition, adhesive for electronic component, semiconductor device, and electronic component

The present invention relates to a resin composition, a semiconductor device, and an electronic component. In particular, the present invention relates to a resin composition suitable for an adhesive for electronic components, a semiconductor device including a cured product of the resin composition, and an electronic component.

Currently, mobile terminals and the like are built with electronic components. This portable terminal has many uses that require a drop impact resistance.

A thermosetting epoxy resin composition containing micro silicone gel beads in a thermosetting epoxy resin composition containing an epoxy resin and its curing agent for the purpose of improving drop impact resistance (Patent Document 1) ) Has been reported.

However, the thermosetting epoxy resin composition characterized by containing these microsilicone gel beads is an improvement due to the viscoelastic properties of the resin, and has a problem that it does not cure in a short time at a low temperature and has a large thermal expansion coefficient. For this reason, it is not suitable for use as an adhesive for electronic components (for example, an adhesive for a voice coil motor (used for VCM, camera focusing, etc.) or an adhesive for a vibration module.

Japanese Patent Laid-Open No. 2015-887

The present invention has been made in view of the above problems, and a resin composition that can be cured in a short time and has excellent drop impact resistance after curing, and a cured product of this resin composition. An object of the present invention is to provide a semiconductor device and an electronic component.

The present inventors have intensively studied to solve the above problems, and a resin composition containing (A) an epoxy resin, (B) a thiol-based curing agent, and a specific amount of (C) talc can be obtained in a short time. It was found that the resin can be cured and has excellent drop impact resistance after curing.

The present invention relates to a resin composition, an electronic component adhesive, a semiconductor device, and an electronic component that have solved the above problems by having the following configuration.
[1] (A) epoxy resin,
(B) including a thiol-based curing agent, and (C) talc,
The resin composition, wherein the component (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition.
[2] The resin composition according to [1], further comprising (D) calcium carbonate and / or silica.
[3] The resin composition as described in [2] above, wherein the total of the component (C) and the component (D) is 5 to 40 parts by mass with respect to 100 parts by mass of the resin composition.
[4] The resin composition as described in any one of [1] to [3] above, wherein the cured product of the resin composition has a glass transition temperature (Tg) of 25 ° C. to 50 ° C.
[5] The resin composition according to any one of [1] to [4], wherein the component (B) contains a thiol compound having no ester bond in the molecule.
[6] An adhesive for electronic parts comprising the resin composition according to any one of [1] to [5].
[7] (A) epoxy resin,
(B) including a thiol-based curing agent, and (C) talc,
The cured product of the resin composition, wherein the component (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition.
[8] A semiconductor device comprising the cured product according to [7].
[9] An electronic component comprising the cured product according to [7] or the semiconductor device according to [8].

According to the present invention [1], it is possible to provide a resin composition that can be cured in a short time and has excellent drop impact resistance after curing.

According to the present invention [7], it is possible to provide a cured product of a resin composition that can be cured in a short time and has excellent drop impact resistance after curing.

According to the present invention [8], a highly reliable semiconductor device including a cured product of a resin composition that can be cured in a short time and has excellent drop impact resistance after curing can be provided. According to the present invention [9], it is possible to provide a highly reliable electronic component including a cured product of a resin composition that can be cured in a short time and has excellent drop impact resistance after curing.

(Resin composition)
The resin composition of the present invention is
(A) epoxy resin,
(B) including a thiol-based curing agent, and (C) talc,
The component (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition.

(A) The epoxy resin as the component imparts curability, heat resistance, adhesiveness and the like to the resin composition. As component (A), siloxane-modified epoxy resin, liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin, liquid hydrogenated bisphenol type epoxy resin, liquid alicyclic epoxy resin, liquid alcohol ether Type epoxy resin, liquid cycloaliphatic type epoxy resin, liquid fluorene type epoxy resin, liquid siloxane type epoxy resin and the like. As the component (A), an epoxy resin having a flexible skeleton is preferable. Examples of the epoxy resin having a flexible skeleton include a siloxane-modified epoxy resin. When an epoxy resin having a bisphenol skeleton (for example, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin) is used, the component (B) to be combined is preferably a thiol-based curing agent having a flexible skeleton. When at least one of the component (A) and the component (B) has a flexible skeleton, the glass transition temperature (Tg) of the cured product of the resin composition can be set to 25 ° C. to 50 ° C. More specifically, [1] Using an epoxy resin that does not contain a benzene ring as the component (A), and using a thiol-based curing agent having a cyclic structure as the component (B), [2] As the component (A) By using an epoxy resin containing a benzene ring and using a thiol-based curing agent having no cyclic structure as the component (B), the glass transition temperature (Tg) of the cured product of the resin composition is 25 ° C. to 50 ° C. It can be in ° C. When the epoxy resin containing a benzene ring and the epoxy resin not containing a benzene ring are used in combination as the component (A), the component (B) may be appropriately selected according to the degree of the combined use. Similarly, when a thiol curing agent having a cyclic structure and a thiol curing agent not having a cyclic structure are used in combination as the component (B), the component (A) may be appropriately selected according to the degree of the combination. If the Tg of the cured product of the resin composition is less than 25 ° C, the shear strength tends to be low, and if it exceeds 50 ° C, the shear strength increases, but the peel strength tends to decrease. Commercially available products of component (A) include Momentive Performance Materials Japan GK siloxane-modified epoxy resin (product name: TSL9906), Nippon Steel Chemical's bisphenol A type epoxy resin (product name: YD-128), new Examples thereof include bisphenol F type epoxy resin (product name: YDF8170) manufactured by Nippon Steel Chemical Co., Ltd., naphthalene type epoxy resin (product name: HP4032D) manufactured by DIC, and aminophenol type epoxy resin (grade: JER630, JER630LSD) manufactured by Mitsubishi Chemical. (A) A component may be individual or may use 2 or more types together.

(B) The thiol-based curing agent as the component imparts low-temperature and short-time curability to the resin composition. As the component (B), from the viewpoint of moisture resistance, the general formula (1):

(Wherein R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and n is an integer of 0 to 10). Compounds are preferred and are represented by chemical formula (2) or chemical formula (3):

And a functional group (—CH ₂ —CH ₂ —SH) or (—CH ₂ —CH ₂ —CH ₂ —SH) is bonded to each of the four nitrogen atoms of the nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound is more preferable.

Further, the component (B) may be another thiol compound having no ester bond in the molecule. This compound has the general formula (4):

Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or C _n H _2n SH (n is 2 to 6), and R ³ , R ⁴ , R ⁵ and R ^At least one of 6 is represented by CnH2nSH (n is 2 to 6). The thiol compound represented by the general formula (4) is preferably a mercaptopropyl group in which n is 2 to 4 from the viewpoint of curability, and n is 3 from the viewpoint of the balance between the physical properties of the cured product and the curing speed. Is preferred. Further, the thiol compound of the general formula (4) may be a single or different mixture of mercaptoalkyl groups. The thiol compound of the general formula (4) preferably has 2 to 4 mercaptopropyl groups from the viewpoint of curability, and has 3 mercaptopropyl groups from the viewpoint of the balance between the physical properties of the cured product and the curing speed. Is most preferred. Since this thiol compound itself has a sufficiently flexible skeleton, it is effective when it is desired to lower the elastic modulus of the cured product. By adding this thiol compound, the elastic modulus of the cured product can be controlled, so that the adhesive strength (particularly peel strength) after curing can be increased. Examples of the compound represented by the formula (4) include trimethylolpropane dipropanethiol in addition to pentaerythritol tripropanethiol (trade name: PEPT, manufactured by SC Organic Chemical Co., Ltd.). Of these, pentaerythritol tripropanethiol is particularly preferred. As another thiol compound having no ester bond in the molecule, a tri- or more functional polythiol compound having two or more sulfide bonds in the molecule can also be used. Examples of such thiol compounds include 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercapto Propylthio) 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-trithiaundecane, tetrakis (mercaptomethylthiomethyl) Methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthio) Til) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 1,1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6- Dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis (mercaptomethylthio ) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonane, tris (2,2-bis (mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) ) -2-thiabutyl) methane, tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis (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-hexathiononadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) ) -1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-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, 1,5-bis [4- (6-mercaptomethylthio) -1, 3-dithianylthio] -3- [2- (1,3-dithietanyl)] methyl-2,4-dithiapentane, 3- [2- (1,3-dithietanyl)] methyl-7,9-bi (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, 3,7-bis [2- (1,3-dithietanyl)] methyl-1,9-dimercapto Aliphatic polythiol compounds such as -2,4,6,8-tetrathianonane; 4,6-bis {3- [2- (1,3-dithietanyl)] methyl-5-mercapto-2,4-di Thiapentylthio} -1,3-dithiane, 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 (mercapto) Methylthio) -6-mercapto-2,5-dithiahexylthio] -5-mercaptomethylthio-1,3-dithiolane, 4- [3-bis (mercaptomethylthio) methyl-5,6 Bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl] -5-mercaptomethylthio-1,3-dithiolane, 2- {bis [3,4-bis (mercaptomethylthio) -6-mercapto -2,5-dithiahexylthio] methyl} -1,3-dithietane, 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- Lithiaoctyl] mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis {1- [2- (1,3-dithietanyl)]-3-mercapto-2-thiapropylthio} -1,3-dithiolane, 4- {1- [2- (1,3-dithietanyl)]-3-mercapto-2-thiapropylthio} -5- [1,2-bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio]- 1,3-dithiolane, 2- {bis [4- (5-mercaptomethylthio-1,3-dithiolanyl) thio] methyl} -1,3-dithietane, 4- [4- (5-mercaptomethylthio-1,3 -Dithiolanyl) thio] -5- {1- [2- (1,3-dithietanyl)]-3-mercapto-2-thiapropylthio} -1,3-dithiolane and other polythiols having a cyclic structure Compounds.

A thiol-based curing agent having no ester bond is preferable because it is hydrophobic and has good wettability with hydrophobic talc and excellent adhesion. In addition, conventional thiol-based curing agents (for example, pentaerythritol tetrakis (3-mercaptopropionate) manufactured by SC Organic Chemicals (trade name: PEMP), trimethylolpropane tris (3-mercaptopropionate) manufactured by SC Organic Chemicals ( (Trade name: TMMP), pentaerythritol tetrakis (3-mercaptobutyrate) manufactured by Showa Denko (trade name: Karenz MT PE1), etc. all contain an ester bond, and this ester bond is easily hydrolyzed, thus being moisture resistant. May be inferior. On the other hand, (B) component which does not contain an ester bond suppresses the strength reduction after the moisture resistance test. It is preferable that the ratio of the compound which has an ester bond in (B) component is 50 mass parts or less in 100 mass parts of (B) component. Commercially available products of component (B) include thiol glycoluril derivatives (trade name: TS-G (equivalent to chemical formula (2), thiol equivalent: 100 g / eq), C3 TS-G (chemical formula (3), manufactured by Shikoku Kasei Kogyo Co., Ltd.) Thiol equivalent: 114 g / eq)) or thiol compound pentaerythritol tripropanethiol (product name: PEPT (corresponding to three mercaptopropyl groups in the general formula (4), thiol equivalent: 124 g) / Eq)). In addition, when it is an acid anhydride type | system | group and an amine type | system | group, low temperature hardening is difficult and in these systems, since glass transition temperature (Tg) becomes high (about 60 degreeC or more), peel strength will become low. (B) A component may be individual or may use 2 or more types together.

Talc as component (C) imparts heat resistance, low thermal expansion and impact resistance to the resin composition. Talc is a mineral that belongs to a silicate mineral and has a plate-like shape, a high aspect ratio, and a layered structure. Minerals have the property of breaking in a specific direction (cleavage), and in the case of talc, cleavage occurs between layers. For this reason, destruction of hardened | cured material occurs as follows. it is conceivable that.

Observe the fracture surface of the cured product after the test that drops and forcibly destroys the cured product. When the talc is less than 5 parts by mass, the fracture surface is relatively flat, and the brittle fracture of the resin. You can see that there are many. What is brittle fracture? It is considered that the impact energy cannot be absorbed because it is a mode that is seen when destruction proceeds at a stretch. On the other hand, the cured product of the resin composition according to the present invention has good drop impact resistance, and when the fracture surface of the cured product is observed, the fracture surface is very rough. This is because when talc absorbs the impact, it cleaves between the layers, and this part branches the direction of the fracture, lengthens the fracture path, and absorbs the impact energy, so the drop impact resistance is improved. Can be guessed. In addition, since talc is used in this invention, it is preferable to use what does not contain an ester bond in (B) component. This is because in the cured product of the resin composition containing an ester bond as the component (B), when the ester bond is hydrolyzed, a hydrophilic portion is generated, and the adhesion to hydrophobic talc is likely to be lowered. In the present invention, the drop impact resistance is preferably 450 mm or more, and more preferably 600 mm or more, in the <Measurement of Drop Impact Resistance> described in the examples below.

The shape of the talc powder as the component (C) is preferably a plate shape or a flat shape. The aspect ratio of the talc powder is preferably 5 or more and 20 or less. When the aspect ratio is less than 5, the above-described fracture path is shortened, and the impact energy cannot be sufficiently absorbed, so that the drop impact resistance may be inferior. If the aspect ratio exceeds 20, it may be difficult to uniformly disperse the component (C) in the resin composition. The aspect ratio was determined by heating the cured product of the resin composition at 500 to 600 ° C., and observing 50 talc powders with a scanning electron microscope (SEM) of the remainder (ash content) of the cured product obtained by thermally decomposing the organic material. It can obtain | require from ratio of the average value of the major axis, and the average value of thickness. The average particle size (length in the surface direction) of the talc powder is not particularly limited, but is 1 to 15 μm, and the dispersibility of the component (C) in the resin composition and the reduction in the viscosity of the resin composition In view of the above, it is preferably 1 to 10 μm. If it is less than 1 μm, the viscosity of the resin composition increases, and the workability of the resin composition may be deteriorated. If it exceeds 15 μm, it may be difficult to uniformly disperse the component (C) in the resin composition. Here, the average particle diameter of the component (C) refers to a volume-based median diameter measured by a laser diffraction method. The average particle diameter of other components is measured in the same manner. Commercially available products include Matsumura Sangyo Talc (product name: 5000PJ) and the like. (C) A component may be individual or may use 2 or more types together. [1] Montmorillonite, which is the same silicate mineral as talc, is not suitable as an electronic material because it has a high impurity concentration, and easily swells. [2] Kaolinite has a high impurity concentration, and the surface condition is high. The hydrophilic part and the opposite side consist of a hydrophobic part (silicate), and the hydrophilic part has poor wettability with the resin. [3] Mica has a structure similar to talc (3 layers: hydrophobic, hydrophilic, hydrophobic However, talc is cleaved from the interface between the hydrophobic parts, whereas cleaving occurs easily from the interface between the hydrophilic layer and the hydrophobic layer in mica. For this reason, the hydrophilic portion appears at the interface, and the wettability with the resin becomes worse.

The component (A) is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of the viscosity of the resin composition.

The thiol equivalent of the component (B) is preferably 0.5 to 2.5 equivalents and more preferably 0.6 to 1.8 equivalents with respect to 1 equivalent of the epoxy of the component (A). The thiol equivalent of the component (B) is a number obtained by dividing the molecular weight of the component (B) by the number of thiol groups in one molecule. By setting the thiol equivalent of the component (B) and the epoxy equivalent of the component (A) within the above-mentioned range, it becomes possible to prevent the resin composition after curing from being insufficient in hardness and insufficient in toughness.

The component (C) is 5 to 20 parts by mass, preferably 5 to 15 parts by mass with respect to 100 parts by mass of the resin composition. When the component (C) is less than 5 parts by mass, the drop impact resistance is lowered. From the viewpoint of drop impact resistance, the component (C) is effective if it is 15 parts by mass, and even if it exceeds 15 parts by mass, the effect does not change, but the resin increases as the amount of component (C) increases. Problems such that the viscosity of the composition increases and the thixotropy (fluctuation index) easily changes with time change occur, workability deteriorates, and practicality becomes poor. This is because the shape of (C) is a plate shape or a flat shape. For this reason, (C) component is 20 mass parts or less, Preferably it is 15 mass or less.

It is preferable that the resin composition further contains (D) calcium carbonate and / or silica from the viewpoint of improving the drop impact resistance. When fillers having different particle shapes and characteristics are kneaded, dispersibility may be improved rather than dispersing the filler alone. By using calcium carbonate and / or silica together, it is considered that the dispersion state of the filler in the resin composition becomes more uniform than that of talc alone, and the drop impact resistance is easily improved. From the viewpoint of moisture resistance, the component (D) is preferably calcium carbonate. In addition, when the calcium carbonate is included as the component (D), the shear strength after the moisture resistance test (temperature: 85 ° C., humidity: 85%, 100 hours) is remarkably increased as compared with the case where silica is included. This is because, since calcium carbonate is hydrophilic, there is no hydrophilic part in the cured product of the resin composition when the component (B) does not contain an ester bond, so it aggregates in the cured product during the shear strength test. This is considered to be because the starting point of destruction is easy to make. On the other hand, silica is more hydrophobic than calcium carbonate, so it has good wettability with the resin, and during the shear strength test, interfacial peeling is likely to occur between the adherend and the cured product, and the moisture resistance test It is thought that later share strength will become low. Examples of commercially available calcium carbonate powder include calcium carbonate powder (product name: CS4ND) manufactured by Ube Materials.

Examples of the silica powder include colloidal silica, hydrophobic silica, fine silica, and nano silica. Note that the addition of silica may reduce the shear strength after the moisture absorption test of the cured resin composition, so care should be taken.

The average particle diameter of the component (D) is not particularly limited, but is 0.1 to 15 μm from the viewpoint of dispersibility of the component (D) in the resin composition and lowering the viscosity of the resin composition. ,preferable. If it is less than 0.1 μm, the viscosity of the resin composition increases, and the workability of the resin composition may be deteriorated. If it exceeds 15 μm, it may be difficult to uniformly disperse the component (D) in the resin composition. Examples of commercially available calcium carbonate powder include calcium carbonate powder (product name: CS4ND, average particle size: 12 μm) manufactured by (Ube Materials). Commercially available silica powders (silica fillers) include Admatex silica (product name: SO-E2, average particle size: 0.5 μm), Tatsumori silica (product name: MP-8FS, average particle size: 0.8). 7 μm), silica from DENKA (product name: FB-5D, average particle size: 5 μm), and the like. (D) A component may be individual or may use 2 or more types together.

The total of the component (C) and the component (D) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the resin composition. If the total of the component (C) and the component (D) is less than 5 parts by mass, the scope of the present invention is exceeded, and the drop impact resistance of the cured product is inferior. If it exceeds 40 parts by mass, the viscosity of the resin composition tends to increase, and the peel strength and drop impact resistance of the cured product tend to decrease.

In the resin composition, in addition to a curing accelerator, a stabilizer, a filler other than the component (C) and the component (D) (for example, alumina), a stabilizer, and the like, as long as the purpose of the present invention is not impaired. Agents (eg, organic acids, borate esters, metal chelates), carbon black, titanium black, silane coupling agents, ion trapping agents, leveling agents, antioxidants, antifoaming agents, alteration agents, and other additives Etc. can be blended. Moreover, you may make a resin composition mix | blend a viscosity modifier, a flame retardant, or a solvent.

As the curing accelerator, a latent curing agent is preferable. The latent curing accelerator is a compound that is inactive at room temperature and activated by heating to function as a curing accelerator. For example, an imidazole compound that is solid at room temperature; an amine compound and an epoxy compound Examples thereof include solid dispersion type amine adduct type latent curing accelerators such as reaction products (amine-epoxy adduct system); reaction products of amine compound and isocyanate compound or urea compound (urea type adduct system) and the like. The curing accelerator can cure the resin composition at a low temperature speed in combination with the component (B).

The resin composition can be obtained, for example, by stirring, melting, mixing, and dispersing the components (A) to (C) and other additives simultaneously or separately, with heat treatment as necessary. The mixing, stirring, and dispersing devices are not particularly limited, but a raikai machine, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. equipped with a stirring and heating device are used. be able to. Moreover, you may use combining these apparatuses suitably.

The resin composition thus obtained is thermosetting. The thermosetting of the resin composition is preferably 60 to 90 ° C. and 30 to 120 minutes.

As described above, from the viewpoint of peel strength, the glass transition temperature (Tg) of the cured product of the resin composition is preferably 25 ° C. to 50 ° C. However, since there are uses where high peel strength is not required, the scope of the present invention is not limited to this Tg.

[Hardened resin composition]
The cured product of the resin composition of the present invention is (A) an epoxy resin,
(B) including a thiol-based curing agent, and (C) talc,
The component (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition.

The (A) component, the (B) component, and the (C) component are as described above, and the component (D) and other components may be added as described above.

[Semiconductor devices, electronic components]
Since the semiconductor device of the present invention includes a cured product of the resin composition described above, it has excellent drop impact resistance and high reliability.

Since the electronic component of the present invention includes the above-described cured product or the above-described semiconductor device, the electronic component is excellent in drop impact resistance and highly reliable.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and mass% unless otherwise specified.

For the (A) component siloxane skeleton epoxy resin, Momentive Performance Materials Japan GK siloxane skeleton epoxy resin (product name: TSL9906, epoxy equivalent: 181 g / eq),
For the bisphenol F type epoxy resin of component (A), Nippon Steel & Sumikin Chemical's bisphenol F type epoxy resin (product name: YDF8170, epoxy equivalent: 158 g / eq),
For component (B) thiol 1 (C3 TS-G), a glycoluril derivative (product name: C3 TS-G, thiol equivalent: 114 g / eq) manufactured by Shikoku Kasei Kogyo,
For the thiol 2 (PEMP) of the component (B), pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMP, thiol equivalent: 128 g / eq) manufactured by SC Organic Chemicals,
For the thiol 3 (PEPT) of the component (B), pentaerythritol tripropanethiol (trade name: PEPT, thiol equivalent: 124 g / eq) manufactured by SC Organic Chemicals,
For the acid anhydride of component (B ′), Hitachi Chemical acid anhydride (product name: HN5500, acid anhydride equivalent: 168 g / eq),
For the amine of (B ′) component, Nippon Kayaku amine (product name: Kayahard AA, amine equivalent: 64 g / eq),
For the talc of the component (C), talc manufactured by Matsumura Sangyo (product name: 5000 PJ, average particle size: 4 μm),
For the mica of component (C ′), mica manufactured by Yamaguchi Mica (product name: SJ-005, average particle size: 5 μm),
For the barium sulfate of component (C ′), barium sulfate manufactured by Sakai Chemical (product name: H, average particle size: 8 μm),
Component (D) is calcium carbonate made by Ube Materials (product name: CS4ND, average particle size: 12 μm) for the calcium carbonate, and silica made by Admatex (product name: SO-E2, average particle size: 0.00). 5 μm)
The other component curing accelerator (Novacure) is a latent curing agent (product name: HXA9322HP, 2/3 (mass ratio) manufactured by Asahi Kasei E-Materials, and bisphenol A type / F type mixed epoxy resin (epoxy equivalent: 180 g / eq) latent curing agent, epoxy equivalent: 180 × 3/2 g / eq),
used.

[Examples 1 to 12, Comparative Examples 1 to 8]
The ingredients shown in Tables 1 to 3 were mixed and then dispersed at room temperature using a three-roll mill to prepare resin compositions of Examples 1 to 12 and Comparative Examples 1 to 8.

<Measurement of shear strength>
《Members used for measuring shear strength》
-Member 1: SUS substrate-Component 2: Alumina chip Size 3 mm x 1.5 mm x 0.5 mm

<Measurement method of shear strength>
(I) The prepared resin composition (sample) was applied as an adhesive on the SUS substrate. The application size was 3 mm × 1.5 mm × 0.06 mm.
(Ii) An alumina chip was placed on the coated sample to obtain a test piece.
(Iii) The test piece was put into an oven heated to 80 ° C., and the sample was heated and cured for 30 minutes.
However, Comparative Example 7 was cured by heating at 150 ° C. for 60 minutes. In Comparative Example 8, heat curing was performed at 150 ° C. for 120 minutes.
(Iv) After heat-curing the sample, the test piece was taken out from the oven, and the shear strength was measured at room temperature using a universal bond tester (manufactured by Dage).
The shear strength after the moisture absorption test was measured at room temperature after the test piece was left at a temperature of 85 ° C. and a humidity (RH) of 85% for 100 hours. Tables 1 to 3 show the results.

<Measurement of peel strength>
《Members used for measuring peel strength》
-Member 1: SUS board-Component 2: SUS ribbon, Size: 5 mm x 15 mm x 0.02 mm

<Measurement method of peel strength>
(I) A resin composition (sample) prepared on a SUS substrate was applied as an adhesive. The application size was set to width: 5 mm × length: 15 mm × thickness: 0.1 mm.
(Ii) A SUS ribbon was placed on the coated sample to obtain a test piece.
(Iii) The test piece was put into an oven heated to 80 ° C., and the sample was heated and cured for 30 minutes.
However, Comparative Example 7 was cured by heating at 150 ° C. for 60 minutes. In Comparative Example 8, heat curing was performed at 150 ° C. for 120 minutes.
(Iv) After the sample was heat-cured, the test piece was taken out from the oven, and the peel strength was measured at room temperature using a tensile / compression tester (manufactured by Minebea). The peel strength is preferably 1 N / mm or more, and more preferably 5 N / mm or more. Tables 1 to 3 show the results.

<Measurement of drop impact resistance>
《Members used for measurement of drop impact test》
-Member 1: SUS substrate-Component 2: Ni coat block, Size: Width: 9 mm x Length: 9 mm x Thickness: 4 mm

<Measuring method for drop impact resistance test>
(I) The prepared resin composition (sample) was applied as an adhesive on the SUS substrate. The application size was set to width: 9 mm × length: 9 mm × thickness: 0.3 mm.
(Ii) A Ni coat block was placed on the coated sample to obtain a test piece.
(Iii) The test piece was put into an oven heated to 80 ° C., and the sample was heated and cured for 30 minutes.
However, Comparative Example 7 was cured by heating at 150 ° C. for 60 minutes. In Comparative Example 8, heat curing was performed at 150 ° C. for 120 minutes.
(Iv) After heat-curing the sample, take out the test piece from the oven, and drop the height at which the Ni coat block peels from the SUS plate using a drop impact tester (manufactured by Hitachi Technology & Service) at room temperature. It was height. The drop height was tested starting from 200 mm, increasing the height every 100 mm up to 500 mm, and increasing the height by 50 mm above 500 mm. In addition, the frequency | count of dropping was performed 5 times at each height, and if it did not peel, the test was performed at the next height. The test was performed with 2 samples (N = 2). The drop impact resistance is preferably 450 mm or more. Tables 1 to 3 show the results. In the table, the numerical value obtained by rounding off the third digit of the average value of the two samples is shown.

<Measurement of glass transition temperature (Tg)>
The glass transition temperature (Tg) of the produced resin composition was measured using dynamic viscoelasticity measurement (DMA). A resin composition was applied to a glass plate having a release agent on the surface so that the film thickness after heat curing was 250 ± 100 μm to form a coating film, and was heat-cured at 80 ° C. for 30 minutes. After peeling off this coating film from the glass plate at room temperature, it was cut into a predetermined dimension (5 mm × 40 mm) with a cutter. The cut end was smooth with sandpaper. This coating film was measured using DMS6100 manufactured by SII Nano Technology (temperature rising rate: 3 ° C./min, measuring range: −40 to 220 ° C.). The peak temperature of tan δ was read and used as Tg. Tables 1 to 3 show the results.

As can be seen from Tables 1 to 3, in all of Examples 1 to 12 using the resin composition containing the components (A) to (C), the shear strength and the drop impact resistance were good. Further, in Examples 1 to 9, 11, and 12, the peel strength was high. Although not shown in Table 1, the shear strength after the moisture resistance test of Example 5 (temperature: 85 ° C., humidity: 85%, 100 hours) is 100 N, and the shear strength of Example 7 is 30N, and the value in Example 5 was higher. The shear strength after the moisture resistance test of Example 12 using only the thiol compound having an ester bond as the component (B) was 10 N, whereas the shear strength after the moisture resistance test of Example 1 was 60 N. Yes, the shear strength after the moisture resistance test of Example 11 was 50 N, and the shear strength was high even after the moisture resistance test. On the other hand, Comparative Example 1 in which the amount of the component (C) is too small was poor in drop impact resistance. (C) In Comparative Example 2 in which there are too many components, it was judged that the rate of change over time of the fluctuation index was too large to be practical, and evaluation was not performed (not shown in the table, but after 24 hours) The rate of change of the tremor index was 50%). In Comparative Example 3 using mica instead of the component (C), the peel strength was low and the drop impact resistance was also poor. In Comparative Example 4 using barium sulfate instead of the (C) component, and Comparative Example 5 using (D) calcium carbonate without using the (C) component, the drop impact resistance was poor. (C) Without using the component, (D) Comparative Example 6 using silica, (B) In place of the component, Comparative Example 7 using an acid anhydride, (B) In place of the component, using an amine In Comparative Example 8, the peel strength was low, the curing temperature was high, the internal stress was large, or the drop impact resistance was poor.

The resin composition of the present invention can be cured in a short time, has excellent drop impact resistance after curing, and is very useful. Moreover, the semiconductor device and electronic component containing the cured product of this resin composition are excellent in drop impact resistance and highly reliable.

Claims (9)

(A) epoxy resin,
(B) including a thiol-based curing agent, and (C) talc,
The resin composition, wherein the component (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition. The resin composition according to claim 1, further comprising (D) calcium carbonate and / or silica. The resin composition according to claim 2, wherein the total of the component (C) and the component (D) is 5 to 40 parts by mass with respect to 100 parts by mass of the resin composition. The resin composition according to any one of claims 1 to 3, wherein the cured product of the resin composition has a glass transition temperature (Tg) of 25 ° C to 50 ° C. The resin composition according to any one of claims 1 to 4, wherein the component (B) contains a thiol compound having no ester bond in the molecule. An adhesive for electronic parts comprising the resin composition according to any one of claims 1 to 5. (A) epoxy resin,
(B) including a thiol-based curing agent, and (C) talc,
The cured product of the resin composition, wherein the component (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition. A semiconductor device comprising the cured product according to claim 7. An electronic component comprising the cured product according to claim 7 or the semiconductor device according to claim 8.