TWI816661B - Resin composition, adhesive for electronic component, semiconductor device, and electronic component - Google Patents

Abstract

An object of the present invention is to provide a resin composition which can be cured in a short time and has excellent drop impact resistance after curing, a semiconductor device having the cured product of the resin composition, and an electronic component. The resin composition includes (A) an epoxy resin, (B) a thiol-based curing agent, and (C) a talc, wherein the component (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the resin composition. Preferably, the resin composition further includes (D) a calcium carbonate and / or silica.

Description

Resin compositions, adhesives for electronic parts, semiconductor devices and electronic parts

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

The portable terminals used today are equipped with electronic components. There are many uses for such portable terminals and the like that require drop impact resistance.

Patent Document 1 proposes a thermosetting epoxy resin composition, which is characterized by containing micropolysiloxane in the thermosetting epoxy resin composition containing epoxy resin and its hardener for the purpose of improving drop impact resistance. Micro silicone gel beads.

However, the thermosetting epoxy resin composition, which is characterized by containing tiny polysiloxane gel beads, is improved by the viscoelastic properties of the resin. However, it cannot be cured in a short time at low temperatures and has a large thermal expansion coefficient. problem. Therefore, it is not suitable for use in adhesives for electronic parts (such as voice coil motors (VCM, used for camera focusing, etc.)) and adhesives for vibration modules.

[Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2015-887

The present invention was created in view of the above problems, and aims to provide a resin composition that can be cured in a short time and has excellent drop impact resistance after curing, and a semiconductor device containing a cured product of the resin composition. Electronic parts.

The present inventors conducted careful examinations to solve the above problems and found that a resin composition containing (A) epoxy resin, (B) thiol-based hardener, and a specific amount of (C) talc can be cured in a short time and Excellent drop impact resistance after hardening.

The present invention relates to a resin composition, an adhesive for electronic components, a semiconductor device, and an electronic component that solve the above-mentioned problems by having the following structures.

[1] A resin composition containing (A) epoxy resin, (B) thiol-based hardener and (C) talc, wherein the component (C) is 5 to 20 parts by mass based on 100 parts by mass of the resin composition. parts by mass.

[2] The resin composition as described in [1] above, further comprising (D) calcium carbonate and/or silicon oxide.

[3] The resin composition according to the above [2], wherein the total of component (C) and component (D) is 5 to 40 parts by mass relative to 100 parts by mass of the resin composition.

[4] The resin composition according to any one of [1] to [3] above, wherein the glass transition temperature (Tg) of the cured product of the resin composition is 25°C to 50°C.

[5] The resin composition according to any one of the above [1] to [4], wherein the component (B) contains a thiol compound without an ester bond in the molecule.

[6] An adhesive for electronic parts containing the resin composition described in any one of the above [1] to [5].

[7] A cured product of a resin composition containing (A) epoxy resin, (B) thiol-based hardener and (C) talc, wherein (C) component is 5 to 20 parts by mass.

[8] A semiconductor device including the cured product according to the above [7].

[9] An electronic component including the hardened material according to the above [7] or the semiconductor device according to the above [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 can be provided, which is a cured product including 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, which is a cured product including 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 contains (A) epoxy resin, (B) thiol hardener and (C) talc, wherein (C) component is 5 to 20 parts by mass relative to 100 parts by mass of the resin composition. .

The epoxy resin as component (A) imparts curability, heat resistance, adhesiveness, etc. to the resin composition. (A) Components include: 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 cyclic aliphatic epoxy resin, liquid fluorine type epoxy resin, liquid siloxane-based epoxy resin wait. The component (A) is preferably an epoxy resin with a soft skeleton. Examples of the epoxy resin having a soft skeleton include siloxane-modified epoxy resin. When using an epoxy resin with a bisphenol skeleton (for example, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin), the combined component (B) is a thiol-based hardener with a soft skeleton. For better. Since at least one of the component (A) and the component (B) has a soft 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, by [1] "Use an epoxy resin that does not contain a benzene ring as the (A) component, and use a thiol-based hardener with a cyclic structure as the (B) component", [2] "Use The glass transition temperature (Tg) of the cured product of the resin composition can be set by using an epoxy resin containing a benzene ring as the component (A) and using a thiol-based hardener without a cyclic structure as the component (B). is 25℃ to 50℃. When an epoxy resin containing a benzene ring and an epoxy resin not containing a benzene ring are used together as the component (A), the component (B) may be appropriately selected depending on the degree of their combined use. Similarly, when a mercaptan hardening agent having a cyclic structure and a mercaptan hardening agent not having a cyclic structure are used together as the component (B), the component (A) may be appropriately selected depending on the degree of the combination. If the Tg of the cured product of the resin composition is less than 25°C, the shear strength will tend to be low. If it exceeds 50°C, the shear strength will be high but the peel strength will tend to be low. Examples of commercially available products of component (A) include: siloxane-modified epoxy resin (product name: TSL9906) manufactured by Momentive Performance Materials Japan Contract Co., Ltd., bisphenol A-type epoxy resin (product name: YD) manufactured by Nippon Steel Chemical Co., Ltd. -128), Nippon Steel Chemical's bisphenol F-type epoxy resin (product name: YDF8170), DIC's naphthalene-type epoxy resin (product name: HP4032D), Mitsubishi Chemical's aminophenol-type epoxy resin (grade : JER630, JER630LSD), etc. (A) Component can be used individually or in combination of 2 or more types.

The thiol-based hardener as component (B) imparts low-temperature and short-time hardening properties to the resin composition. From the viewpoint of moisture resistance, component (B) is preferably a thiol compound represented by general formula (1):

(In the formula, 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 from 0 to 10).

More preferably, the four nitrogen atoms of the nitrogen-containing heterocyclic compound represented by chemical formula (2) or chemical formula (3) are respectively bonded with (-CH ₂ -CH ₂ -SH) or (-CH _{2 )} as functional groups. -CH ₂ -CH ₂ -SH) multifunctional nitrogen-containing heterocyclic compounds:

Moreover, component (B) may also be other thiol compounds without ester bonds in the molecule. This compound is represented by general formula (4):

(In the formula, 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 at least one of R ³ , R ⁴ , R ⁵ and R ⁶ The one is C _n H _2n SH (n is 2 to 6)). From the perspective of curability, the thiol compound of general formula (4) is preferably one in which n is 2 to 4; from the perspective of the balance between the physical properties of the cured product and the curing speed, the thiol compound in which n is 3 is preferred. Propyl is preferred. Moreover, the thiol compound of the general formula (4) may also be a mixture having a single or different number of mercaptoalkyl groups. From the perspective of curability, the thiol compound of general formula (4) is preferably one with 2 to 4 mercaptopropyl groups; from the perspective of the balance between the physical properties of the cured product and the curing speed, the thiol compound of general formula (4) is preferably one with mercaptopropyl groups. The one with 3 propyl groups is the best. Since this thiol compound itself has a very soft skeleton, it is effective when the elastic modulus of the cured product is to be lowered. By adding this thiol compound, the elastic modulus of the hardened product can be controlled, thereby improving the bonding strength (especially the peel strength) after hardening. Examples of the compound represented by formula (4) may include trimethylolpropane dipropanethiol, etc., in addition to neopentylerythritol tripropanethiol (trade name: PEPT, manufactured by SC Organic Chemical Co., Ltd.). Among these, neopentylerythritol tripropanethiol is particularly preferred. Other thiol compounds without ester bonds in the molecule can also be used in trifunctional or higher polythiol compounds with more than 2 sulfur bonds in the molecule. Examples of such thiol compounds include: 1,2,3-shen(mercaptomethylthio)propane, 1,2,3-shen(2-mercaptoethylthio)propane, and 1,2,3-shen(mercaptoethylthio)propane. (3-Mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithianoctane, 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, 4(mercaptomethylthiomethyl)methane, 4(2-mercaptoethylthiomethyl)methane, 4(3 -Mercaptopropylthiomethyl)methane, 1,1,3,3-(mercaptomethylthio)propane, 1,1,2,2-(mercaptomethylthio)ethane, 4, 6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 1,1,5,5-bis(mercaptomethylthio)-3-thiolatane, 1,1, 6,6-Si(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1, 7-dimercapto-2,6-dithiapane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithionane, 3-mercapto Methylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-4(mercaptomethylthio)-5-(3,3-bis(mercaptomethyl) (Sulfanylthio)-1-thiapropyl)3,7-dithianonane, Shen(2,2-bis(mercaptomethylthio)ethyl)methane, Shen(4,4-bis(mercapto) Methylthio)-2-thiabutyl)methane, 4(2,2-bis(mercaptomethylthio)ethyl)methane, 4(4,4-bis(mercaptomethylthio)-2 -Thiabutyl)methane, 3,5,9,11-(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5 ,9,11,15,17-lu(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2 -Bis(mercaptomethylthio)ethyl)-3,5,13,15-bis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexa Thiaheptadecane, 3,4,8,9-(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8 ,9,13,14-lu(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethyl thio)methyl]-3,4,12,13-(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylsulfanyl]-1,3-dithiacyclohexane, 4-[ 3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiapinethio]-6-mercaptomethylthio-1,3-dithiacyclohexane, 1, 1-bis[4-(6-mercaptomethylthio)-1,3-dithiacyclohexanylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4- (6-Mercaptomethylthio)-1,3-dithiacyclohexanylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis( Mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1,5-bis[4-(6-mercaptomethylthio)-1,3-dithiacyclohexane Methylthio]-3-[2-(1,3-dithiobutanyl)]methyl-2,4-dithiolan, 3-[2-(1,3-dithia cyclobutyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-( 1,3-dithietanyl)]methyl-3,5,13,15-(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12, 16-Hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-4(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-tetrathianonane and other aliphatic polythiol compounds; 4,6-bis{3-[2-(1,3-dithietanyl )]methyl-5-mercapto-2,4-dithiopentylthio}-1,3-dithiacyclohexane, 4,6-bis[4-(6-mercaptomethylthio) -1,3-dithialylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithialylthio]-1,3- Dithiane, 4-[3,4,8,9-(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercapto Methylthio-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-dithiohexylthio]-5-mercaptomethylthio Base-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4, 7-trithiocyl]-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-dithiadine, 2-[3,4,8,9-(mercaptomethylthio)-11-mercapto- 2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl Base-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithianoctyl]mercaptomethylthiomethyl-1,3-dithiacyclobutane, 4,5-Bis{1-[2-(1,3-dithiobutanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiolane , 4-{1-[2-(1,3-dithiobutanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethyl) thio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2-{bis[4-(5-mercaptomethylthio-1,3-di Thiolyl)thio]methyl}-1,3-dithialane, 4-[4-(5-mercaptomethylthio-1,3-dithiolanyl) )thio]-5-{1-[2-(1,3-dithiobutanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiocyclo Pentane and other polythiol compounds with ring structure.

Thiol-based hardeners without ester bonds are preferred because they are hydrophobic and have good wettability and excellent adhesion to hydrophobic talc. In addition, conventional thiol-based hardeners (for example, neopentylerythritol (3-mercaptopropionate) (trade name: PEMP) manufactured by SC Organic Chemicals, trimethylolpropane (trimethylolpropane) manufactured by SC Organic Chemicals ( 3-Mercaptopropionate) (trade name: TMMP), neopentylerythritol 4 (3-mercaptobutyrate) (trade name: Karenz MT PE1) manufactured by Showa Denko (trade name: Karenz MT PE1), etc.) all contain ester bonds. It is easily hydrolyzed, so it may have poor moisture resistance. On the other hand, the component (B) containing no ester bond can suppress the decrease in strength after the moisture resistance test. The proportion of the compound having an ester bond in the component (B) is preferably 50 parts by mass or less per 100 parts by mass of the component (B). Examples of commercially available products of component (B) include: thiol glycoluril derivative manufactured by Shikoku Chemical Industry Co., Ltd. [trade name: TS-G (equivalent to chemical formula (2), thiol equivalent: 100g/eq) , C3 TS-G (equivalent to chemical formula (3), thiol equivalent: 114g/eq)], thiol compound neopenterythritol tripropanethiol manufactured by SC Organic Chemicals [product name: PEPT (equivalent to general formula (4) ) has three mercaptopropyl groups, and the thiol equivalent is: 124g/eq)]. In addition, if it is an acid anhydride type or an amine type, it is difficult to harden at low temperature, and in these systems, the glass transition temperature (Tg) becomes high (approximately 60° C. or higher), so the peel strength becomes low. (B) Component may be used individually or in combination of 2 or more types.

Talc as the component (C) imparts heat resistance, low thermal expansion, and impact resistance to the resin composition. Talc is a silicate mineral with a plate-like shape, a high aspect ratio, and a layered structure. Minerals have the property of breaking in specific directions (cleavage). When it is talc, cleavage will occur between the layers. Therefore, it is believed that the destruction of hardened materials occurs in the following manner.

After the test in which the hardened material was dropped and forcibly damaged, the cracked surface of the hardened material was observed. If the cracked surface was relatively flat in a system containing less than 5 parts by mass of talc, this indicates brittle damage of the resin. More. Brittle damage is considered to be a pattern seen when damage is carried out in one go, so it is unable to absorb the energy of the impact. On the other hand, the cured product of the resin composition of 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. It can be speculated that this is because talc produces cleavage between layers when absorbing impact. This part will diverge the direction of damage and lengthen the damage path. Therefore, it can absorb impact energy, thus improving the resistance to falling impacts. In addition, since talc is used in the present invention, component (B) is preferably one that does not contain an ester bond. The 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, so the adhesion to hydrophobic talc tends to decrease. In the present invention, regarding the drop impact resistance, in the "Measurement of Drop Impact Resistance" described in the Examples described below, the drop height is preferably 450 mm or more, and more preferably 600 mm or more.

The shape of the talc powder as component (C) is preferably plate-like or flat. The aspect ratio of the talc powder is preferably not less than 5 and not more than 20. If the aspect ratio is less than 5, the above-mentioned damage path becomes shorter and the impact energy cannot be fully absorbed, so the drop impact resistance may be poor. If the aspect ratio exceeds 20, it may become difficult to disperse the component (C) uniformly in the resin composition. The aspect ratio can be obtained as follows: The cured product of the resin composition is heated at 500 to 600°C to thermally decompose the organic matter, and the remaining portion (ash) of the cured product obtained by thermal decomposition is analyzed with a scanning electron microscope ( SEM) was used to observe 50 pieces of talc powder, and the aspect ratio was calculated from the ratio of the average length of the length to the average thickness. The average particle diameter (length in the plane direction) of the talc powder is not particularly limited, but from the viewpoint of the dispersibility of component (C) in the resin composition and the low viscosity of the resin composition, it is 1 to 15 μm. is preferably 1 to 10 μm. If it is less than 1 μm, the viscosity of the resin composition increases, and there is a risk of physical deterioration of the resin composition. If it exceeds 15 μm, it may become difficult to disperse the component (C) uniformly in the resin composition. Here, the average particle diameter of component (C) refers to the volume-based median diameter measured by laser diffraction method. The average particle diameters of other components are also measured in the same manner. Examples of commercially available products include talc produced by Matsumura Industrial Co., Ltd. (product name: 5000PJ). (C) Component can be used individually or in combination of 2 or more types. In addition, they are silicate minerals like talc. Among them: [1] Montmorillonite series is not suitable as an electronic material due to its high impurity concentration and is prone to swelling; [2] Kaolin series has high impurity concentration and its surface state is hydrophilic. The wetting between the hydrophobic part (silicate) and the hydrophilic part on the opposite side of the resin will become worse; [3] Mica, although its structure is similar to talc (3 layers: hydrophobic/hydrophilic/hydrophobic), but talc Cleavage occurs at the interface between the hydrophobic parts. In contrast, mica cleaves easily at the interface between the hydrophilic layer/hydrophobic layer. Therefore, the hydrophilic part appears at the interface, which affects the wettability of the resin. get worse.

From the viewpoint of the viscosity of the resin composition, the amount of component (A) is preferably 10 to 70 parts by mass relative to 100 parts by mass 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 epoxy equivalent of component (A). The thiol equivalent of component (B) refers to the number obtained by dividing the molecular weight of component (B) by "the number of thiol groups in 1 molecule". By setting the thiol equivalent of component (B) and the epoxy equivalent of component (A) within the above range, insufficient hardness and insufficient toughness of the cured resin composition can be prevented.

The component (C) is 5 to 20 parts by mass, preferably 5 to 15 parts by mass, based on 100 parts by mass of the resin composition. If the content of component (C) is less than 5 parts by mass, the drop impact resistance will be reduced. Moreover, from the viewpoint of drop impact resistance, the effect is achieved when the component (C) is 15 parts by mass. Even if it exceeds 15 parts by mass, the effect does not change. However, as the component (C) increases, the resin composition The viscosity will increase, which will cause the problem that the so-called thixotropy (thixotropy index) will easily change over time, which will deteriorate the handleability and lead to lack of practicality. This is because the shape of (C) is plate-like or flat. Therefore, the component (C) is 20 parts by mass or less, preferably 15 parts by mass or less.

From the viewpoint of improving drop impact resistance, the resin composition preferably further contains (D) calcium carbonate and/or silicon oxide. Compared with dispersing a single filler, kneading fillers with different particle shapes/characteristics can improve dispersion. It is believed that the combined use of calcium carbonate and/or silicon oxide will make the dispersion state of the filler in the resin composition more uniform, making it easier to improve the drop impact resistance compared to using talc alone. From the viewpoint of moisture resistance, calcium carbonate is preferred as component (D). In addition, when component (D) contains calcium carbonate compared to when it contains silicon oxide, the shear strength after the humidity resistance test (temperature: 85°C, humidity: 85%, 100 hours) is significantly higher. . It is believed that this is because calcium carbonate is hydrophilic. Therefore, when component (B) does not contain an ester bond, the cured product of the resin composition will not produce hydrophilic parts. Therefore, during the shear strength test, it is easy to form a hydrophilic part in the cured product. Causes the starting point of agglomeration damage. In contrast, it is believed that silicon oxide is more hydrophobic than calcium carbonate, so it has good wettability with resin, and it is easy to create an interface between the adherend and the hardened object during the shear strength test. The shear strength after peeling and moisture resistance test becomes low. Examples of commercially available calcium carbonate powder include calcium carbonate powder manufactured by Ube Materials (product name: CS4ND).

Examples of silicon oxide powder include: colloidal silicon oxide, hydrophobic silicon oxide, fine silicon oxide, nanometer silicon oxide, etc. In addition, by adding silicon oxide, the shear strength of the cured resin composition after the moisture absorption test may be reduced, so please be careful.

Although the average particle diameter of component (D) is not particularly limited, from the viewpoint of dispersibility of component (D) in the resin composition and low viscosity of the resin composition, it is preferably 0.1 to 15 μm. If it is less than 0.1 μm, the viscosity of the resin composition increases, and there is a risk that the handleability of the resin composition may deteriorate. If it exceeds 15 μm, it may become difficult to disperse the component (D) uniformly in the resin composition. Commercially available calcium carbonate powder includes calcium carbonate powder manufactured by Ube Materials (product name: CS4ND, average particle size: 12 μm). Commercially available silicon oxide powder (silica filler) includes: silicon oxide manufactured by admatechs (product name: SO-E2, average particle size: 0.5 μm), silicon oxide manufactured by Longsen (product name: MP-8FS, average particle size: Particle size: 0.7 μm), DENKA silicon oxide (product name: FB-5D, average particle size: 5 μm), etc. (D) Component can be used individually or in combination of 2 or more types.

The total amount of component (C) and component (D) is preferably 5 to 40 parts by mass relative to 100 parts by mass of the resin composition. If the total amount of the component (C) and the component (D) is less than 5 parts by mass, it will fall outside the scope of the present invention, and the cured product will have poor drop impact resistance. 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 the hardening accelerator, a stabilizer and a filler (such as alumina) other than the component (C) and the component (D) may be further blended as necessary within the scope that does not impair the object of the present invention. ), stabilizers (such as organic acids, borate esters, metal chelates), carbon black, titanium black, silane coupling agents, ion collectors, leveling agents, antioxidants, defoaming agents, thixotropic agents, Other additives, etc. Moreover, a viscosity adjuster, a flame retardant, a solvent, etc. may also be blended into the resin composition.

The preferred hardening accelerator is latent hardener. The so-called latent hardening accelerator refers to a compound that is activated by heating in an inert state at room temperature to function as a hardening accelerator. Examples include: imidazole compounds that are solid at room temperature; amine compounds and epoxy compounds Solid dispersion type amine addition system latent hardening accelerator such as reaction products of compounds (amine-epoxy addition system); reaction products of amine compounds and isocyanate compounds or urea compounds (urea type addition system), etc. The hardening accelerator can be combined with component (B) to quickly harden the resin composition at 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 as necessary while subjecting them to heat treatment. Although the devices for mixing, stirring, dispersing, etc. are not particularly limited, crushers, Henschel mixers, three-roller mills, ball mills, planetary mixers, and bead mills equipped with stirring and heating devices can be used. wait. Furthermore, these devices can also be used in appropriate combinations.

The resin composition obtained in this way is thermosetting. Thermal hardening of the resin composition is preferably carried out at 60 to 90°C for 30 to 120 minutes.

As mentioned 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 also applications that do not require high peel strength, the scope of the present invention is not limited to this Tg.

[Hardened product of resin composition]

The cured material of the resin composition of the present invention includes: (A) epoxy resin, (B) thiol-based hardener and (C) talc, wherein (C) component is 5 parts per 100 parts by mass of the resin composition. to 20 parts by mass.

The (A) component, (B) component, and (C) component are as described above, and the same applies to the fact that (D) component and other components can be added.

[Semiconductor devices, electronic components]

Since the semiconductor device of the present invention contains a cured product of the above-mentioned resin composition, it has excellent drop impact resistance and high reliability.

Since the electronic component of the present invention contains the above-mentioned hardened material or the above-mentioned semiconductor device, it has excellent drop impact resistance and high reliability.

(Example)

In the following, the present invention is illustrated by examples, but the present invention is not limited to these examples. In addition, in the following examples, unless otherwise specified, parts and % mean parts by mass and % by mass.

The siloxane lattice epoxy resin of component (A) uses: siloxane lattice epoxy resin manufactured by Momentive Performance Materials Japan (product name: TSL9906, epoxy equivalent: 181g/eq); Phenol F type epoxy resin system uses: bisphenol F type epoxy resin manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. (product name: YDF8170, epoxy equivalent: 158g/eq); (B) thiol 1 (C3 TS-G) of the component ) system uses: glycoluril derivative manufactured by Shikoku Chemical Industry (product name: C3 TS-G, thiol equivalent: 114g/eq); (B) component thiol 2 (PEMP) system uses: SC Organic Neopenterythritol 4 (3-hydroxypropionate) chemically produced (trade name: PEMP, thiol equivalent: 128g/eq); (B) thiol 3 (PEPT) system used: SC Organic Chemicals Neopenterythritol tripropanethiol (trade name: PEPT, thiol equivalent: 124g/eq); (B') component of the acid anhydride system uses: Hitachi Chemical Anhydride (product name: HN5500, acid anhydride equivalent: 168g/eq) ); The amine system used in component (B'): Nippon Kayaku Co., Ltd.'s amine (product name: KAYAHARD AA, amine equivalent: 64g/eq); The talc system used in component (C): Talc manufactured by Matsumura Sangyo Co., Ltd. (product name: 5000PJ) , average particle size: 4 μm); (C') component mica used: mica manufactured by YAMAGUCHI MICA (product name: SJ-005, average particle size: 5 μm); (C') component barium sulfate used: Sakai Chemical Barium sulfate made from (product name: H, average particle size: 8 μm); calcium carbonate system for component (D) used: calcium carbonate made by Ube materials (product name: CS4ND, average particle size: 12 μm); silicon oxide system used: admatechs Made of silicon oxide (product name: SO-E2, average particle size: 0.5μm); the other components of the hardening accelerator (NOVACURE) are: latent hardener made by Asahi Kasei E-materials [product name: HXA9322HP, 2/3 ( Mass ratio) is a latent hardener for bisphenol A/F mixed epoxy resin (epoxy equivalent: 180g/eq), epoxy equivalent: 180×3/2g/eq].

[Examples 1 to 12, Comparative Examples 1 to 8]

The raw materials were mixed according to the preparation shown in Tables 1 to 3, and then dispersed using a three-roller mill at room temperature to prepare the resin compositions of Examples 1 to 12 and Comparative Examples 1 to 8.

〈Measurement of shear strength〉

"Components used in the determination of shear strength"

‧Component 1: SUS substrate

‧Part 2: Alumina sheet size 3mm×1.5mm×0.5mm

"Method for determination of shear strength"

(i) Coat the prepared resin composition (sample) on the SUS substrate as an adhesive. The coating size is 3mm×1.5mm×0.06mm.

(ii) Place an alumina sheet on the coated sample to serve as a test piece.

(iii) Put the test piece into a furnace heated to 80°C, and heat and harden the sample for 30 minutes.

However, Comparative Example 7 was heated and hardened at 150°C for 60 minutes. Comparative Example 8 was heated and hardened at 150°C for 120 minutes.

(iv) After heating and hardening the sample, the test piece was taken out of the furnace and the shear strength was measured at room temperature using a universal push-pull force testing machine (manufactured by Dage Corporation).

Furthermore, the shear strength after the moisture absorption test is the shear strength measured at room temperature after leaving the test piece at a temperature of 85°C and a humidity (RH) of 85% for 100 hours. The results are shown in Tables 1 to 3.

〈Measurement of Peel Strength〉

"Components used in the measurement of peel strength"

‧Component 1: SUS substrate

‧Part 2: SUS strap, size: 5mm×15mm×0.02mm

"Method for determination of peel strength"

(i) Coat the prepared resin composition (sample) on the SUS substrate as an adhesive. The coating dimensions are width: 5mm × length: 15mm × thickness: 0.1mm.

(ii) Place the SUS tape on the coated sample to serve as a test piece.

(iii) Put the test piece into a furnace heated to 80°C, and heat and harden the sample for 30 minutes.

However, Comparative Example 7 was heated and hardened at 150°C for 60 minutes. Comparative Example 8 was heated and hardened at 150°C for 120 minutes.

(iv) After heating and hardening the sample, the test piece was taken out of the furnace and the peel strength was measured using a tensile and compression testing machine (manufactured by Minebea Co., Ltd.) at room temperature. The peel strength is preferably 1 N/mm or more, and more preferably 5 N/mm or more. The results are shown in Tables 1 to 3.

〈Measurement of drop impact resistance〉

"Components used in the determination of drop impact resistance test"

‧Component 1: SUS substrate

‧Part 2: Ni coat block, size: width: 9mm×length: 9mm×thickness: 4mm

"Measurement Method of Drop Impact Resistance Test"

(i) Coat the prepared resin composition (sample) on the SUS substrate as an adhesive. The coating size is width: 9mm × length: 9mm × thickness: 0.3mm.

(ii) Place a nickel-plated block on the coated sample to serve as a test piece.

(iii) Put the test piece into a furnace heated to 80°C, and heat and harden the sample for 30 minutes.

However, Comparative Example 7 was heated and hardened at 150°C for 60 minutes. Comparative Example 8 was heated and hardened at 150°C for 120 minutes.

(iv) After heating and hardening the sample, the test piece was taken out of the furnace and a drop impact tester (manufactured by Hitachi Technologies and Services) was used at room temperature. The height at which the nickel plating block was peeled off from the SUS plate was taken as the drop height. The drop height was tested by increasing the height by 100mm each time from 200mm to 500mm, and above 500mm by increasing the height by 50mm each time. In addition, the number of drops is 5 times at each height. If it does not peel off, the test is carried out at the next height. The test was conducted with 2 samples (N=2). The drop impact resistance is preferably above 450mm. The results are shown in Tables 1 to 3. In addition, the table records the value obtained by rounding off the third digit of the average value of two samples.

〈Measurement of glass transition temperature (Tg)〉

Dynamic viscoelasticity measurement (DMA) was used to measure the glass transition temperature (Tg) of the produced resin composition. The resin composition was applied to the glass plate to which the release agent was applied on the surface so that the film thickness after heat curing would be 250 ± 100 μm to form a coating film, and the coating film was heated and cured at 80° C. for 30 minutes. After the coating film was peeled off from the glass plate at room temperature, it was cut into predetermined sizes (5 mm × 40 mm) with a cutter. Also, use sandpaper to smooth the cuts. This coating film was measured using DMS6100 manufactured by SII Nano Technology (heating rate: 3°C/min, measurement range: -40 to 220°C). Read the peak temperature of tan δ as Tg. The results are shown in Tables 1 to 3.

As can be seen from Tables 1 to 3, Examples 1 to 12 using resin compositions containing components (A) to (C) all have good shear strength and drop impact resistance. Furthermore, in Examples 1 to 9, 11, and 12, the peel strength was high. In addition, although it is not shown in Table 1, the shear strength after the humidity resistance test (temperature: 85°C, humidity: 85%, 100 hours) of Example 5 is 100N, and the shear strength of Example 7 is 30N. It is higher than Example 5. Moreover, 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. In contrast, the shear strength after the moisture resistance test of Example 1 is 60N, the shear strength after the moisture resistance test of Example 11 is 50N, and the shear strength after the moisture resistance test is still high. On the other hand, Comparative Example 1 with too little component (C) had poor drop impact resistance. (C) Comparative Example 2, which contains too many ingredients, was judged to lack practicality because the rate of change of the rheometry index over time was too large and was not evaluated (although it is not shown in the table, the rate of change of the rheometry index after 24 hours is 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 using barium sulfate instead of component (C) and Comparative Example 5 using (D) calcium carbonate without using component (C) showed poor drop impact resistance. Comparative Example 6 using (D) silicon oxide without using (C) component, Comparative Example 7 using acid anhydride instead of (B) component, and Comparative Example 8 using amine instead of (B) component may be due to low peel strength. Due to the high hardening temperature and large internal stress, the drop impact resistance is also poor.

The resin composition of the present invention can be cured in a short time and has excellent drop impact resistance after curing, so it is very useful. Furthermore, semiconductor devices and electronic components containing cured materials of this resin composition have excellent drop impact resistance and are highly reliable.

Claims (8)

A resin composition for electronic parts, comprising: (A) an epoxy resin, (B) a thiol compound represented by the general formula (1), a thiol compound represented by the general formula (4), and a molecule selected from the group consisting of: Thiol-based hardeners without ester bonds, and (C) talc, which are a group of trifunctional or more polythiol compounds that do not have ester bonds and have two or more sulfur bonds in the molecule,

In the formula, R ¹ and R ² are each independently hydrogen, an alkyl group with 1 to 10 carbon atoms, or a phenyl group, and n is an integer from 0 to 10;

In the formula, 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 at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is C _n H _2n SH (n is 2 to 6). The component (C) is 5 to 20 parts by mass relative to 100 parts by mass of the resin composition for electronic parts; however, the component (B) mentioned above is excluded. 1,3- Dimercaptopropane. The resin composition for electronic parts as described in item 1 of the patent application further contains (D) calcium carbonate and/or silicon oxide, wherein, relative to 100 parts by mass of the resin composition for electronic parts, the component (C) is the same as (D) The total amount of components is 5 to 40 parts by mass. The resin composition for electronic parts as described in claim 1 or 2, wherein the glass transition temperature (Tg) of the cured product of the resin composition for electronic parts is 25°C to 50°C. The resin composition for electronic parts as described in Item 1 or 2 of the patent application, wherein the component (B) includes: a thiol compound represented by the general formula (3), and a thiol compound represented by the general formula (4). A group of thiol compounds without ester bonds in the molecule;

An adhesive for electronic parts includes: the resin composition for electronic parts described in any one of items 1 to 4 of the patent application scope. A cured product of a resin composition for electronic parts, containing: (A) an epoxy resin, (B) a thiol compound selected from the group consisting of a thiol compound represented by general formula (1) and a thiol compound represented by general formula (4) , and thiol-based hardeners without ester bonds, which are a group of trifunctional or higher polythiol compounds that have no ester bonds in the molecule and have two or more sulfur bonds in the molecule, and (C) talc,

In the formula, R ¹ and R ² are each independently hydrogen, an alkyl group with 1 to 10 carbon atoms, or a phenyl group, and n is an integer from 0 to 10;

In the formula, 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 at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is C _n H _2n SH (n is 2 to 6). The component (C) is 5 to 20 parts by mass relative to 100 parts by mass of the resin composition for electronic parts; however, the component (B) mentioned above is excluded 1,3- Dimercaptopropane. A semiconductor device including the hardened object described in Item 6 of the patent application. An electronic component, including the hardware described in item 6 of the patent application scope chemical or semiconductor device described in Item 7 of the patent application scope.