JP7166245B2 - Resin compositions, adhesives for electronic parts, semiconductor devices, and electronic parts - Google Patents

Description

The present invention relates to resin compositions, semiconductor devices, and electronic components. In particular, the present invention relates to a resin composition suitable as an adhesive for electronic parts, a semiconductor device containing a cured product of this resin composition, and an electronic part.

Mobile terminals and the like currently in use have built-in electronic components. There are many uses for mobile terminals and the like that require drop impact resistance.

A thermosetting epoxy resin composition containing microsilicone 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 improved by the viscoelastic properties of the resin, and has the problems of not curing in a short time at low temperature and having a large coefficient of thermal expansion. For this reason, it is not suitable for use as an adhesive for electronic parts (for example, voice coil motors (VCM, used for camera focusing, etc.), or as an adhesive for vibration modules.

JP-A-2015-887

The present invention has been made in view of the above problems, and provides 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 including the above.

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

The present invention relates to a resin composition, an adhesive for electronic parts, a semiconductor device, and an electronic part that solve the above problems by having the following constitutions.
[1] (A) epoxy resin,
(B) a thiol-based curing agent, and (C) talc,
A resin composition characterized in that component (C) is 5 to 20 parts by mass per 100 parts by mass of the resin composition.
[2] The resin composition according to [1] above, which further contains (D) calcium carbonate and/or silica.
[3] The resin composition according to [2] above, wherein the total amount of component (C) and component (D) is 5 to 40 parts by mass with respect to 100 parts by mass of the resin composition.
[4] The resin composition according to any one of [1] to [3] above, wherein a 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] above, wherein 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] above.
[7] (A) epoxy resin,
(B) a thiol-based curing agent, and (C) talc,
A cured product of a resin composition, wherein component (C) is 5 to 20 parts by mass per 100 parts by mass of the resin composition.
[8] A semiconductor device comprising the cured product according to [7] above.
[9] An electronic component comprising the cured product of [7] above or the semiconductor device of [8] above.

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

According to the present invention [8], it is possible to provide a highly reliable semiconductor device containing 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 [9], it is possible to provide a highly reliable electronic component containing 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) an epoxy resin,
(B) a thiol-based curing agent, and (C) talc,
Component (C) is characterized by being 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition.

The epoxy resin, which is the component (A), imparts curability, heat resistance, adhesiveness, and the like to the resin composition. Component (A) includes 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, and 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 component (A), an epoxy resin having a flexible skeleton is preferred. Examples of epoxy resins having a flexible skeleton include siloxane-modified epoxy resins. When using an epoxy resin having a bisphenol skeleton (e.g., bisphenol A type epoxy resin, bisphenol F type epoxy resin), it is preferable that the component (B) to be combined is a thiol-based curing agent having a flexible skeleton. At least one of the components (A) and (B) has a flexible skeleton, so that the cured product of the resin composition can have a glass transition temperature (Tg) of 25°C to 50°C. More specifically, [1] using an epoxy resin containing no benzene ring as the component (A), 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 can be reduced from 25°C to 50°C. °C. When an epoxy resin containing a benzene ring and an epoxy resin not containing a benzene ring are used together as component (A), component (B) may be appropriately selected according to the degree of combination. Similarly, when a thiol curing agent having a cyclic structure and a thiol curing agent not having a cyclic structure are used together as component (B), component (A) may be appropriately selected according to the degree of combination. When the Tg of the cured product of the resin composition is less than 25°C, the shear strength tends to be low, and when it exceeds 50°C, the shear strength is high but the peel strength tends to be low. Commercially available products of component (A) include Momentive Performance Materials Japan LLC siloxane-modified epoxy resin (product name: TSL9906), Nippon Steel Chemical bisphenol A type epoxy resin (product name: YD-128), new Nittetsu Chemical bisphenol F type epoxy resin (product name: YDF8170), DIC naphthalene type epoxy resin (product name: HP4032D), Mitsubishi Chemical aminophenol type epoxy resin (grade: JER630, JER630LSD) and the like. Component (A) may be used alone or in combination of two or more.

The thiol-based curing agent, which is the component (B), imparts low-temperature short-time curability to the resin composition. As component (B), from the viewpoint of moisture resistance, 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) A compound of formula (2) or formula (3) is preferred:

represented by, to each of the four nitrogen atoms of the nitrogen-containing heterocyclic compound, a functional group (—CH ₂ —CH ₂ —SH) or (—CH ₂ —CH ₂ —CH ₂ —SH) is a polyfunctional is more preferred.

Also, the component (B) may be another thiol compound that does not have an ester bond in its 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 ⁶ is represented by CnH2nSH (where n is 2 to 6). The thiol compound of general formula (4) preferably has n of 2 to 4 from the viewpoint of curability, and is a mercaptopropyl group with n of 3 from the viewpoint of the balance between the physical properties of the cured product and the curing speed. is preferred. The thiol compound of general formula (4) may have a single mercaptoalkyl group or a mixture of those having different numbers of mercaptoalkyl groups. The thiol compound of 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 (especially peel strength) after curing can be increased. Examples of the compound represented by formula (4) include pentaerythritol tripropanethiol (trade name: PEPT, manufactured by SC Organic Chemical Co., Ltd.), trimethylolpropane dipropanethiol, and the like. Of these, pentaerythritol trippropanethiol is particularly preferred. As other thiol compounds having no ester bond in the molecule, tri- or higher functional polythiol compounds 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-trithiundecane, 4,7- dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, tetrakis(mercaptomethylthiomethyl) Methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercapto methylthio)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-trithianone, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis (mercaptomethylthio)-1-thiapropyl)3,7-dithianone, 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(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-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, 3,7-bis[2-(1,3-dithietanyl)]methyl-1,9-dimercapto-2,4,6,8-tetrathianonan and other aliphatic polythiols Compound; 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-di Thiahexylthio]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-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiethane, 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)]- Polythiol having a cyclic structure such as 3-mercapto-2-thiapropylthio}-1,3-dithiolane compounds are included.

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) (trade name: PEMP) manufactured by SC Organic Chemical Co., Ltd., trimethylolpropane tris (3-mercaptopropionate) manufactured by SC Organic Chemical Co., Ltd. ( (trade name: TMMP), Showa Denko pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz MT PE1), etc.) contain an ester bond, which is easily hydrolyzed, resulting in moisture resistance. may be inferior to On the other hand, the (B) component containing no ester bond suppresses the decrease in strength after the moisture resistance test. The ratio of the compound having an ester bond in component (B) is preferably 50 parts by mass or less per 100 parts by mass of component (B). Commercially available products of component (B) include Shikoku Kasei Co., Ltd.'s thiol glycol uril derivative (trade name: TS-G (corresponding to chemical formula (2), thiol equivalent: 100 g / eq), C3 TS-G (chemical formula (3) equivalent to , thiol equivalent: 114 g / eq)) and SC Organic Chemical thiol compound pentaerythritol trippropanethiol (product name: PEPT (corresponding to three mercaptopropyl groups in general formula (4), thiol equivalent: 124 g /eq)). Acid anhydride-based and amine-based adhesives are difficult to cure at low temperatures, and these systems have a high glass transition temperature (Tg) (approximately 60° C. or higher), resulting in low peel strength. Component (B) may be used alone or in combination of two or more.

Talc, which is the component (C), imparts heat resistance, low thermal expansion, and impact resistance to the resin composition. Talc is a mineral belonging to silicate minerals, and has a plate-like shape, a high aspect ratio, and a layered structure. Minerals have the property (cleavability) of cracking in a specific direction, and in the case of talc, cleavage occurs between layers. Therefore, destruction of the cured product occurs as follows. it is conceivable that.

Observing the fracture surface of the cured product after the test in which the cured product was dropped and forcibly destroyed, the fracture surface was relatively flat in the system with less than 5 parts by mass of talc, indicating brittle fracture of the resin. It can be seen that there are many brittle fracture. Since this mode is seen when the fracture progresses at once, it is considered that the impact energy cannot be absorbed. 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 the talc absorbs the impact, it cleaves between the layers, and this part diverges the direction of the fracture progress, lengthens the fracture path, and absorbs the impact energy, so the drop impact resistance is improved. can guess. Since talc is used in the present invention, it is preferable to use component (B) that does not contain an ester bond. This is because a cured product of a resin composition containing an ester bond in the component (B) generates a hydrophilic portion due to hydrolysis of the ester bond, and the adhesiveness to the hydrophobic talc tends to decrease. In the present invention, the drop impact resistance is preferably 450 mm or more, more preferably 600 mm or more, in <measurement of drop impact resistance> described in Examples below.

The shape of the talc powder as the component (C) is preferably plate-like or flat. The aspect ratio of the talc powder is preferably 5 or more and 20 or less. If the aspect ratio is less than 5, the above-mentioned breaking path will be short, and the impact energy cannot be sufficiently absorbed, which may result in poor drop impact resistance. If the aspect ratio exceeds 20, it may become difficult to uniformly disperse the component (C) in the resin composition. The aspect ratio is obtained by heating the cured product of the resin composition at 500 to 600 ° C., and observing the remainder (ash) of the cured product after thermal decomposition of the organic matter with a scanning electron microscope (SEM) on 50 pieces of talc powder. It can be obtained from the ratio of the average value of the major axis and the average value of the thickness. The average particle diameter (length in the plane direction) of the talc powder is not particularly limited, but it is preferable that it is 1 to 15 μm, which is useful for dispersibility of component (C) in the resin composition and low viscosity of the resin composition. from the viewpoint of, more preferably 1 to 10 μm. If it is less than 1 μm, the viscosity of the resin composition may increase and the workability of the resin composition may deteriorate. 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 the volume-based median diameter measured by the laser diffraction method. The average particle diameters of other components are also measured in the same manner. Commercially available products include talc manufactured by Matsumura Sangyo (product name: 5000PJ). Component (C) may be used alone or in combination of two or more. Note that [1] montmorillonite, which is a silicate mineral similar to talc, is not suitable as an electronic material because of its high impurity concentration and tends to swell, and [2] kaolinite has a high impurity concentration and a poor surface condition. , 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 (three layers: hydrophobic, hydrophilic, hydrophobic ), whereas talc is cleaved from the interface between the hydrophobic portions, mica is more likely to be cleaved from the interface between the hydrophilic layer and the hydrophobic layer. As a result, the hydrophilic portion appears at the interface, and the wettability with the resin deteriorates.

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 component (B) is preferably 0.5 to 2.5 equivalents, more preferably 0.6 to 1.8 equivalents, relative to 1 equivalent of epoxy component (A). The thiol equivalent of component (B) is the number obtained by dividing the molecular weight of component (B) by the number of thiol groups in one molecule. By setting the thiol equivalent weight of component (B) and the epoxy equivalent weight of component (A) within the ranges described above, it is possible to prevent insufficient hardness and insufficient toughness of the cured resin composition.

Component (C) is 5 to 20 parts by mass, preferably 5 to 15 parts by mass, per 100 parts by mass of the resin composition. If the component (C) is less than 5 parts by mass, the drop impact resistance will decrease. Also, from the viewpoint of drop impact resistance, component (C) is effective if it is 15 parts by mass, and the effect does not change even if it exceeds 15 parts by mass, but as component (C) increases, resin Problems such as the viscosity of the composition increasing and the thixotropy (thixotropic index) tending to change over time occur, resulting in poor workability and poor practicality. This is because the shape of (C) is plate-like or flat. Therefore, component (C) is 20 parts by mass or less, preferably 15 parts by mass or less.

It is preferable that the resin composition further contains (D) calcium carbonate and/or silica from the viewpoint of improving drop impact resistance. Mixing fillers with different particle shapes and properties may improve the dispersibility compared to dispersing the fillers alone. It is believed that the joint use of calcium carbonate and/or silica makes the dispersion state of the filler in the resin composition more uniform than that of talc alone, making it easier to improve drop impact resistance. From the viewpoint of moisture resistance, the component (D) is preferably calcium carbonate. When calcium carbonate is included as the component (D), the shear strength after a moisture resistance test (temperature: 85°C, humidity: 85%, 100 hours) is remarkably higher than when silica is included. This is because calcium carbonate is hydrophilic, and hydrophilic moieties do not occur in the cured product of the resin composition when component (B) does not contain an ester bond. It is considered that this is because the starting point of destruction is likely to be formed. On the other hand, silica is more hydrophobic than calcium carbonate, so it has good wettability with resin, and interfacial peeling easily occurs between the adherend and the cured product during the shear strength test. It is considered that the later shear strength becomes lower. Examples of commercially available calcium carbonate powder include calcium carbonate powder manufactured by Ube Materials (product name: CS4ND).

Examples of silica powder include colloidal silica, hydrophobic silica, fine silica, nanosilica, and the like. Note that the addition of silica may reduce the shear strength of the cured resin composition after a moisture absorption test, so caution is required.

The average particle size of component (D) is not particularly limited, but it is preferable that it is 0.1 to 15 μm from the viewpoint of dispersibility of component (D) in the resin composition and low viscosity of the resin composition. ,preferable. If it is less than 0.1 μm, the viscosity of the resin composition may increase and the workability of the resin composition may deteriorate. 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 powder (silica filler) includes Admatechs silica (product name: SO-E2, average particle size: 0.5 μm), Tatsumori silica (product name: MP-8FS, average particle size: 0.5 μm). 7 μm), DENKA silica (product name: FB-5D, average particle size: 5 μm), and the like. Component (D) may be used alone or in combination of two or more.

The total amount of component (C) and component (D) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the resin composition. If the total amount of component (C) and component (D) is less than 5 parts by mass, it falls outside the scope of the present invention and the drop impact resistance of the cured product is poor. 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 addition to the curing accelerator, the resin composition may further contain stabilizers, fillers other than components (C) and (D) (e.g., alumina), and stabilizers, as long as the objects of the present invention are not impaired. agents (e.g. organic acids, borate esters, metal chelates), carbon black, titanium black, silane coupling agents, ion trapping agents, leveling agents, antioxidants, antifoaming agents, stabilizing agents, other additives etc. can be blended. Further, the resin composition may be blended with a viscosity modifier, a flame retardant, a solvent, or the like.

A latent curing agent is preferred as the curing accelerator. 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; solid-dispersed amine adduct-based latent curing accelerators such as reaction products (amine-epoxy adduct); reaction products of amine compounds with isocyanate compounds or urea compounds (urea-type adducts); The curing accelerator can be combined with the component (B) to rapidly cure the resin composition at a low temperature.

The resin composition can be obtained, for example, by stirring, melting, mixing, and dispersing components (A) to (C) and other additives simultaneously or separately while optionally applying heat treatment. Equipment for mixing, stirring, dispersing, etc. is not particularly limited, but a Raikai machine equipped with a stirring and heating device, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like is used. be able to. Also, these devices may be used in combination as appropriate.

The resin composition thus obtained is thermosetting. Thermal curing of the resin composition is preferably carried out at 60 to 90° C. for 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 applications where high peel strength is not required, the scope of the present invention is not limited to this Tg.

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

Components (A), (B), and (C) are as described above, and it is also as described above that component (D) and other components may be added.

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

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

(A) Component siloxane skeleton epoxy resin is a siloxane skeleton epoxy resin (product name: TSL9906, epoxy equivalent: 181 g / eq) manufactured by Momentive Performance Materials Japan LLC.
For the bisphenol F type epoxy resin of component (A), Nippon Steel & Sumikin Chemical Co., Ltd. bisphenol F type epoxy resin (product name: YDF8170, epoxy equivalent: 158 g / eq),
(B) Component thiol 1 (C3 TS-G) is a glycoluril derivative manufactured by Shikoku Kasei Co., Ltd. (product name: C3 TS-G, thiol equivalent: 114 g / eq),
For the thiol 2 (PEMP) of component (B), pentaerythritol tetrakis (3-mercaptopropionate) manufactured by SC Organic Chemical (trade name: PEMP, thiol equivalent: 128 g/eq),
(B) component thiol 3 (PEPT) is pentaerythritol trippropanethiol (trade name: PEPT, thiol equivalent: 124 g/eq) manufactured by SC Organic Chemical Co., Ltd.;
For the acid anhydride of the component (B'), Hitachi Chemical acid anhydride (product name: HN5500, acid anhydride equivalent: 168 g/eq),
(B') The amine of the component is Nippon Kayaku's amine (product name: Kayahard AA, amine equivalent: 64 g / eq),
The talc of the component (C) is Matsumura Sangyo talc (product name: 5000PJ, average particle size: 4 μm),
(C') Component mica is Yamaguchi Mica mica (product name: SJ-005, average particle size: 5 μm),
(C') Barium sulfate of the component is barium sulfate manufactured by Sakai Chemical (product name: H, average particle size: 8 μm),
Calcium carbonate (product name: CS4ND, average particle size: 12 μm) manufactured by Ube Materials was used as the component (D) calcium carbonate, and silica manufactured by Admatechs (product name: SO-E2, average particle size: 0.1 μm) was used as silica. 5 μm),
The curing accelerator (Novacure) of other components includes a latent curing agent manufactured by Asahi Kasei E-Materials (product name: HXA9322HP, 2/3 (mass ratio), bisphenol A type / F type mixed epoxy resin (epoxy equivalent: 180 g / eq) latent curing agent, epoxy equivalent weight: 180 x 3/2 g/eq),
used.

[Examples 1 to 12, Comparative Examples 1 to 8]
After mixing raw materials according to the formulations shown in Tables 1 to 3, the mixture was dispersed using a three-roll mill at room temperature 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>>
・Part 1: SUS substrate ・Part 2: Alumina chip Size 3mm x 1.5mm x 0.5mm

<<Method for measuring shear strength>>
(i) The prepared resin composition (sample) was applied as an adhesive onto a 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 placed in an oven heated to 80° C., and the sample was cured by heating for 30 minutes.
However, Comparative Example 7 was cured by heating at 150° C. for 60 minutes. Comparative Example 8 was cured by heating 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 leaving the test piece at a temperature of 85° C. and a humidity (RH) of 85% for 100 hours. Tables 1-3 show the results.

<Measurement of peel strength>
<<Members used to measure peel strength>>
・Member 1: SUS substrate ・Part 2: SUS ribbon, size: 5 mm × 15 mm × 0.02 mm

<<Method for measuring peel strength>>
(i) The prepared resin composition (sample) was applied as an adhesive onto a SUS substrate. The coating size was width: 5 mm x length: 15 mm x thickness: 0.1 mm.
(ii) A SUS ribbon was placed on the coated sample to obtain a test piece.
(iii) The test piece was placed in an oven heated to 80° C., and the sample was cured by heating for 30 minutes.
However, Comparative Example 7 was cured by heating at 150° C. for 60 minutes. Comparative Example 8 was cured by heating at 150° C. for 120 minutes.
(iv) After heat curing the sample, the test piece was taken out from the oven and peel strength was measured at room temperature using a tensile compression tester (manufactured by Minebea Co., Ltd.). The peel strength is preferably 1 N/mm or more, more preferably 5 N/mm or more. Tables 1-3 show the results.

<Measurement of drop impact resistance>
<<Members used for measurement of drop impact resistance test>>
・Member 1: SUS substrate ・Part 2: Ni-coated block, size: width: 9 mm x length: 9 mm x thickness: 4 mm

<<Measuring method of drop impact resistance test>>
(i) The prepared resin composition (sample) was applied as an adhesive onto a SUS substrate. The coating size was width: 9 mm x length: 9 mm x thickness: 0.3 mm.
(ii) A Ni-coated block was placed on the coated sample to obtain a test piece.
(iii) The test piece was placed in an oven heated to 80° C., and the sample was cured by heating for 30 minutes.
However, Comparative Example 7 was cured by heating at 150° C. for 60 minutes. Comparative Example 8 was cured by heating at 150° C. for 120 minutes.
(iv) After heating and curing the sample, remove the test piece from the oven and use a drop impact tester (manufactured by Hitachi Technology & Service Co., Ltd.) at room temperature to drop the Ni-coated block from the SUS plate. height. The drop height was started from 200 mm, increased by 100 mm up to 500 mm, and increased by 50 mm from 500 mm to perform the test. In addition, the number of drops was five times at each height, and if no peeling occurred, the test was performed at the next height. Two samples were tested (N=2). The drop impact resistance is preferably 450 mm or more. Tables 1-3 show the results. In addition, in the table, the numerical value obtained by rounding the average value of two samples to the third digit is described.

<Measurement of glass transition temperature (Tg)>
The glass transition temperature (Tg) of the prepared resin composition was measured using dynamic viscoelasticity measurement (DMA). A coating film was formed by coating a resin composition on a glass plate having a release agent applied to the surface so that the film thickness after heat curing was 250±100 μm, and heat curing was performed 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 size (5 mm×40 mm) with a cutter. The cut end was smoothed with sandpaper. This coating film was measured using DMS6100 manufactured by SII Nanotechnology Co., Ltd. (heating rate: 3° C./min, measurement range: −40 to 220° C.). The peak temperature of tan δ was read and taken as Tg. Tables 1-3 show the results.

As can be seen from Tables 1 to 3, all of Examples 1 to 12 using resin compositions containing components (A) to (C) exhibited good shear strength and drop impact resistance. Furthermore, 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 (temperature: 85 ° C., humidity: 85%, 100 hours) of Example 5 was 100 N, and the shear strength of Example 7 was , 30N, and Example 5 was higher. Further, the shear strength after the moisture resistance test of Example 12 using only a thiol compound having an ester bond as the component (B) was 10 N, while the shear strength after the moisture resistance test of Example 1 was 60 N. The shear strength of Example 11 after the moisture resistance test was 50 N, and the shear strength was high even after the moisture resistance test. On the other hand, Comparative Example 1, which contained too little component (C), had poor drop impact resistance. In Comparative Example 2, which contained too much component (C), the rate of change over time in the thixotropic index was too large, and was judged to be impractical. The rate of change of the thixotropic index was 50%). Comparative Example 3, in which mica was used instead of component (C), had low peel strength and poor drop impact resistance. Comparative Example 4 in which barium sulfate was used instead of component (C) and Comparative Example 5 in which calcium carbonate (D) was used without component (C) had poor drop impact resistance. Comparative Example 6 using (D) silica without using component (C), Comparative Example 7 using acid anhydride instead of component (B), using amine instead of component (B) In Comparative Example 8, the peel strength was low, the curing temperature was high, and the drop impact resistance was poor, possibly due to the effects of high internal stress.

INDUSTRIAL APPLICABILITY The resin composition of the present invention is very useful because it can be cured in a short period of time and has excellent drop impact resistance after curing. In addition, semiconductor devices and electronic components containing the cured product of this resin composition are excellent in drop impact resistance and highly reliable.

Claims (8)

(A) an epoxy resin,
(B) 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) Compound,
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 a thiol compound represented by C ⁿ H 2n SH (n is 2 to 6 ₎ ; _and
Trifunctional or higher polythiol compound having two or more sulfide bonds in the molecule and no ester bond in the molecule
A thiol-based curing agent that does not have an ester bond, and (C) talc, including those selected from the group consisting of
A resin composition for electronic parts, wherein component (C) is 5 to 20 parts by mass per 100 parts by mass of the resin composition.
However, the component (B) is an oligomer having a basic skeleton having a structure represented by the following formula:

and 1,3-dimercaptopropane. Further, (D) contains calcium carbonate and/or silica, and the total amount of components (C) and (D) is 5 to 40 parts by mass with respect to 100 parts by mass of the resin composition. The resin composition for electronic parts described above. 3. The resin composition for electronic parts according to claim 1 , wherein a cured product of the resin composition has a glass transition temperature (Tg) of 25.degree. C. to 50.degree. Claim 1, wherein the component (B) is selected from the group consisting of a thiol compound represented by the chemical formula (3) and a thiol compound having no ester bond in the molecule represented by the general formula (4). 4. The resin composition for electronic parts according to any one of 1 to 3 .

An adhesive for electronic parts, comprising the resin composition for electronic parts according to any one of claims 1 to 4 . (A) an epoxy resin,
(B) 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) Compound,
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 a thiol compound represented by C ⁿ H 2n SH (n is 2 to 6 ₎ ; _and
Trifunctional or higher polythiol compound having two or more sulfide bonds in the molecule and no ester bond in the molecule
A thiol-based curing agent that does not have an ester bond, and (C) talc, including those selected from the group consisting of
A cured product of a resin composition for electronic parts, wherein the component (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition.
However, the component (B) is an oligomer having a basic skeleton having a structure represented by the following formula:

and 1,3-dimercaptopropane. A semiconductor device comprising the cured product according to claim 6 . An electronic component comprising the cured product according to claim 6 or the semiconductor device according to claim 7 .