TW202028285A - Resin composition - Google Patents

Abstract

Provided is a resin composition containing: (A) an epoxy resin that does not contain an aromatic ring; (B) at least one type of a bifunctional thiol compound selected from the group consisting of a bifunctional thiol compound containing, in a molecule thereof, an aromatic ring structure or an alicyclic structure and a molecular chain that contains a hetero atom, that does not contain an ester bond, and that has a thiol group at a terminal thereof, and having a molecular weight of 210 or more, and a bifunctional thiol compound containing, in a molecule thereof, an aromatic ring structure or a heterocyclic structure and a molecular chain that may contain a hetero atom, that does not contain an ester bond, and that has a thiol group at a terminal thereof, and having a molecular weight of 210 or more; and (C) an amine compound.

Description

Resin composition

The present invention relates to a resin composition that can be used in applications requiring thermal curing at a relatively low temperature, specifically, thermal curing at about 80°C.

When manufacturing image sensor modules used as camera modules for mobile phones or smart phones, adhesives that are thermally cured at a relatively low temperature, specifically at a temperature of about 80°C are used. Even when manufacturing electronic parts such as semiconductor components, integrated circuits, large integrated circuits, transistors, triodes, diodes, capacitors, etc., it is preferable to use those that include heat hardening at a temperature of about 80°C. Adhesive for resin composition.

In addition, when two parts with different thermal expansion coefficients are joined by an adhesive, thermal stress may act on the joints due to changes in the surrounding temperature and cracks may occur. In the adhesive used to join these parts, flexibility that can follow the degree of thermal deformation of the parts is required, and a cured product with excellent stress relaxation is required even after the adhesive is cured.

For example, Patent Document 1 discloses a resin composition containing a thiol compound having two or more thiol groups in the molecule as a resin composition that can be thermally cured at a low temperature to obtain a cured product with a small elastic modulus. Prior Art Document Patent Document

Patent Document 1: International Publication No. 2012/093510

The problem to be solved by the invention

However, the thiol compound is an adhesive mainly composed of a polythiol compound having 3 or more thiol groups in the molecule, and there are more cross-linking points. Due to the residual stress in the resulting hardened material, it cannot follow the attached The thermal deformation of the body. In addition, a polythiol compound having two thiol groups in the molecule should be an alkyl group of 1,4-butane dithiol and 1,10-decane dithiol as disclosed in Patent Document 1. In the case of a bifunctional thiol compound having a thiol group at both ends, it has a low molecular weight and high volatility. Even when it is cured at a low temperature of about 80°C, voids exist in the resulting cured product, and the resulting cured product Possibility of reducing the physical properties of objects.

Therefore, the object of the present invention is to provide a resin composition which can be cured at low temperatures, does not impair physical properties, and obtains a cured product excellent in stress relaxation. Means to solve the problem

The means for solving the aforementioned problems are as follows, and the present invention includes the following aspects. [1] A resin composition comprising: (A) Epoxy resin without aromatic ring, (B) A bifunctional thiol compound, selected from: a molecular chain containing an aromatic ring structure or an alicyclic structure in the molecule, and a molecular chain with a thiol group at the end that contains a heteroatom but does not contain an ester bond, and has a molecular weight of 210 or more A thiol compound and a bifunctional thiol compound containing an aromatic ring structure or a heterocyclic structure in the molecule and a molecular chain with a thiol group at the end that may contain heteroatoms but no ester bond. The molecular weight is 210 or more. At least 1 type of group, and (C) Amine compounds. [2] The resin composition according to [1], wherein the component (B) is the second of a molecular chain containing an alicyclic structure and a thioether bond but no ester bond containing a thiol group at the end in the molecule Functional thiol compound. [3] The resin composition according to [1] above, wherein the component (B) is a bifunctional molecular chain containing an aromatic ring structure and an ether bond but no ester bond containing a thiol group at the end. Thiol compounds. [4] The resin composition according to [1], wherein the component (B) is a bifunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3) ,

(通式(B-1)中，n、m各自獨立地為1～3之整數)；

(In the general formula (B-1), n and m are each independently an integer of 1 to 3);

(通式(B-2)中，R¹ 、R² 、R³ 及R⁴ 各自獨立地係氫原子或下述通式(b-1)所示的基；惟，R¹ 及R² 之任一者係下述通式(b-1)所示的基，R³ 及R⁴ 之任一者係下述通式(b-1)所示的基)；

(In the general formula (B-2), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a group represented by the following general formula (b-1); however, R ¹ and R ^{2 are} Either one is a group represented by the following general formula (b-1), and any one of R ³ and R ⁴ is a group represented by the following general formula (b-1));

(通式(b-1)中，r為1～3之整數)；

(In the general formula (b-1), r is an integer of 1 to 3);

(通式(B-3)中，G₁ 、G₂ 各自獨立地係以-O-或-CH₂ -所鍵結的2價基，p、q各自獨立地為2～5之整數)。 [5]如前述[1]記載之樹脂組成物，其中前述(B)成分係下述通式(B-4)或(B-5)所示的2官能硫醇化合物，

(In the general formula (B-3), G ₁ and G ₂ are each independently a divalent group bonded by -O- or -CH ₂ -, and p and q are each independently an integer of 2 to 5). [5] The resin composition according to [1], wherein the component (B) is a bifunctional thiol compound represented by the following general formula (B-4) or (B-5),

(通式(B-4)中，s、t各自獨立地為3或4之整數)；

(In the general formula (B-4), s and t are each independently an integer of 3 or 4);

(通式(B-5)中，u、v各自獨立地為3或4之整數)。 [6]如前述[1]～[5]中任一項記載之樹脂組成物，其中前述(A)成分之重量平均分子量為240～1,000。 [7]如[1]～[6]中任一項記載之樹脂組成物，其中前述(A)成分係下述式(A-1)或(A-2)所示的環氧樹脂，

(In the general formula (B-5), u and v are each independently an integer of 3 or 4). [6] The resin composition according to any one of [1] to [5], wherein the weight average molecular weight of the component (A) is 240 to 1,000. [7] The resin composition according to any one of [1] to [6], wherein the component (A) is an epoxy resin represented by the following formula (A-1) or (A-2),

(式(A-1)中，R⁵ 係碳數為1～15之直鏈狀或分支狀的伸烷基，w為1～20之整數)；

(In formula (A-1), R ⁵ is a linear or branched alkylene group having 1 to 15 carbon atoms, and w is an integer of 1 to 20);

(式(A-2)中，R⁶ ～R⁹ 各自獨立地為碳數1～3之直鏈狀或分支狀的烷基)。 [8]如前述[1]～[7]中任一項記載之樹脂組成物，其中前述(C)成分之胺化合物係由咪唑系化合物、三級胺系化合物及胺加成物所選出的至少1種胺化合物。 [9]如前述[1]～[8]中任一項記載之樹脂組成物，其中將樹脂組成物中的全部硫醇基之數當作100時，前述(B)成分之2官能硫醇化合物的硫醇基之總數為20～100。 [10]如前述[1]～[9]中任一項記載之樹脂組成物，其進一步包含(D)安定劑。 [11]如前述[10]記載之樹脂組成物，其中前述(D)成分之安定劑係選自由液狀硼酸酯化合物、鋁螯合物及巴比妥酸所成之群組的至少1者。 [12]一種接著劑，其包含如前述[1]～[11]中任一項記載之樹脂組成物。 [13]一種密封材，其包含如前述[1]～[11]中任一項記載之樹脂組成物。 [14]一種影像感測器模組，其係使用如前述[12]記載之接著劑或如前述[13]記載之密封材製造者。 [15]一種半導體裝置，其係使用如前述[12]記載之接著劑或如前述[13]記載之密封材製造者。

(In the formula (A-2), R ⁶ to R ⁹ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms). [8] The resin composition according to any one of [1] to [7], wherein the amine compound of the component (C) is selected from imidazole compounds, tertiary amine compounds and amine adducts At least one amine compound. [9] The resin composition according to any one of [1] to [8], wherein when the total number of thiol groups in the resin composition is regarded as 100, the bifunctional thiol of the component (B) The total number of thiol groups of the compound is 20-100. [10] The resin composition according to any one of [1] to [9], which further contains (D) a stabilizer. [11] The resin composition according to [10], wherein the stabilizer of the component (D) is at least 1 selected from the group consisting of a liquid borate compound, an aluminum chelate compound, and barbituric acid By. [12] An adhesive comprising the resin composition described in any one of [1] to [11] above. [13] A sealing material comprising the resin composition described in any one of [1] to [11] above. [14] An image sensor module using the adhesive as described in [12] above or the manufacturer of the sealing material as described in [13]. [15] A semiconductor device using the adhesive described in [12] above or the sealing material manufacturer described in [13] above.

Effects of the Invention According to the present invention, it is possible to provide a resin composition which can be thermally cured at a low temperature of about 80°C, does not impair physical properties, and obtains a cured product excellent in stress relaxation.

Implementation of the invention

Hereinafter, description will be made based on the embodiments of the resin composition, adhesive, sealing material, image sensor module, and semiconductor device of the present disclosure. However, the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following resin compositions, adhesives, sealing materials, image sensor modules, and semiconductor devices.

The resin composition of the first embodiment of the present invention includes: (A) Epoxy resin without aromatic ring, (B) A bifunctional thiol compound, selected from: a molecular chain containing an aromatic ring structure or an alicyclic structure in the molecule, and a molecular chain with a thiol group at the end that contains a heteroatom but does not contain an ester bond, and has a molecular weight of 210 or more A thiol compound and a bifunctional thiol compound containing an aromatic ring structure or a heterocyclic structure in the molecule and a molecular chain with a thiol group at the end that may contain heteroatoms but no ester bond. The molecular weight is 210 or more. At least 1 type of group, and (C) Amine compounds.

(A) Component: epoxy resin without aromatic ring The resin composition contains an epoxy resin not containing an aromatic ring as the (A) component. Since the epoxy resin does not contain an aromatic ring, the glass transition temperature (Tg) after curing of the resin composition is low, and the elastic coefficient becomes low. Therefore, when the adhesive containing the resin composition of the embodiment of the present invention has two different thermal expansion coefficients, even if the two parts connected due to the surrounding temperature change expand and contract due to their different thermal expansion coefficients, It also has the flexibility to follow the changes of parts, and has excellent stress relaxation.

Also, the aromatic ring system has a structure that satisfies the Huckel rule, for example, a benzene ring.

The weight average molecular weight of the epoxy resin of the component (A) is preferably 240 to 1,000. The weight average molecular weight of the epoxy resin of the aforementioned component (A) is more preferably 250 to 1,000, particularly preferably 260 to 1,000, and even more preferably 270 to 1,000. In this specification, the weight average molecular weight refers to the value of a calibration curve using standard polystyrene by gel permeation chromatography (GPC).

The epoxy resin of the aforementioned component (A) is preferably an epoxy resin that does not contain an ester bond in order to improve the moisture resistance of the cured product made of the resin composition.

The aforementioned (A) component is preferably an epoxy resin represented by the following formula (A-1), for example.

In the formula (A-1), R ⁵ is a linear or branched alkylene group having a carbon number of 1-15, and w is an integer of 1-20.

The epoxy resin represented by the aforementioned formula (A-1) is preferably an epoxy resin represented by the following formula (A-1-1) and/or (A-1-2).

In formula (A-1-1), x is an integer of 1-15.

In formula (A-1-2), y is an integer of 1-20.

The aforementioned (A) component is preferably an epoxy resin represented by the following formula (A-2), for example.

In formula (A-2), R ⁶ to R ⁹ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms.

The aforementioned component (A) can be used in addition to the resin composition represented by the aforementioned general formula (A-1) or (A-2), hydrogenated bisphenol epoxy resin, alicyclic epoxy resin, alcohol ether Type epoxy resin, aliphatic epoxy resin, cycloaliphatic epoxy resin, silicone epoxy resin, etc. Examples of such epoxy resins include hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, epoxy-modified polybutadiene, and 1,4-cyclohexanedimethanol diepoxy. Propyl ether and so on.

The resin composition of the present invention may further contain epoxy resins (aromatic ring-containing epoxy resins) other than the (A) component. (A) The total number of epoxy groups contained in the epoxy resin containing no aromatic ring of the component, when the total number of epoxy groups in the resin composition is regarded as 100, it is preferably 20-100, more preferably 40 ～100, particularly preferably 50～100. The number of epoxy groups contained in the epoxy resin containing no aromatic ring of the component (A) can be obtained by dividing the mass of the epoxy resin containing no aromatic ring of the component (A) by the difference of the component (A) Calculate the epoxy equivalent of the aromatic ring-containing epoxy resin. Moreover, the ratio of the epoxy group of the epoxy resin other than (A) component and (A) component can also be calculated using NMR. The number of all epoxy groups in the resin composition, when the epoxy resin containing no aromatic ring of the component (A) is included, the number of epoxy groups of the epoxy resin other than the component (A) can be determined by ( A) The mass of the epoxy resin other than the component is divided by the epoxy equivalent of the epoxy resin other than the (A) component, and the number of epoxy groups of the epoxy resin other than the (A) component can be calculated with (A) The sum of the number of epoxy groups not containing an aromatic ring of the components is regarded as the number of all epoxy groups in the resin composition.

(B) Component: Bifunctional thiol compound The (B) bifunctional thiol compound contained in the resin composition of one embodiment of the present invention is selected from those having an aromatic ring structure or an alicyclic structure in the molecule, and those having heteroatoms but no ester bonds at the ends. A thiol group molecular chain, a bifunctional thiol compound with a molecular weight of 210 or more, and a molecular chain containing an aromatic ring structure or a heterocyclic structure and a thiol group at the end that may contain heteroatoms but does not contain an ester bond in the molecule , At least one bifunctional thiol compound of the group of bifunctional thiol compounds with a molecular weight of 210 or more. (B) The bifunctional thiol compound of the component can be obtained from Shikoku Chemical Industry Co., Ltd.

(B) The bifunctional thiol compound of the component has a molecular weight of 210 or more. Due to its low volatility, for example, when the resin composition is thermally cured at a low temperature of 80°C, the bifunctional thiol compound does not volatilize and suppresses voids. The occurrence of hardened substance that maintains physical properties. The molecular weight is more preferably 280 or more. In addition, from the viewpoint of curability, the molecular weight of the bifunctional thiol compound of the component (B) is preferably 1,000 or less, and more preferably 600 or less.

The bifunctional thiol compound of the component (B) has heteroatoms and has good compatibility with the epoxy resin containing no aromatic ring of the component (A). For example, it is cured at a low temperature of 80°C to obtain a homogeneous cured product. (B) The aromatic ring structure of the component includes monocyclic aromatic ring structures with five or more members, such as cyclopentadiene, benzene, and the like. Examples of the alicyclic structure include monocyclic alicyclic structures with five or more members, such as cyclopentane and cyclohexene. The heterocyclic structure may be a monocyclic ring, a polycyclic ring, an alicyclic structure, an aromatic ring structure, or a condensed polycyclic structure. Examples of the heteroatom included in the molecular chain include sulfur (S) and oxygen (O) atoms, and it is preferable to include a thioether bond or ether bond in the molecular chain. From the viewpoint of compatibility with epoxy resin and low volatility, the bifunctional thiol compound of component (B) is preferably a heteroatom-based sulfur atom, that is, contains an alicyclic structure and contains thioether in the molecule A molecular chain with a thiol group at the end that does not contain an ester bond. In addition, the bifunctional thiol compound of the component (B) is preferably a heteroatom-based oxygen atom from the viewpoint of compatibility with epoxy resin and low volatility, that is, it contains an aromatic ring structure and contains A molecular chain with a thiol group at the end that does not contain an ether bond. From the viewpoint of adhesion strength to metals, the bifunctional thiol compound of the component (B) preferably contains an alicyclic structure and a molecule having a thiol group at the end that contains a thioether bond but does not contain an ester bond. chain.

In addition, the bifunctional thiol compound of the component (B) has two thiol groups. Therefore, when the resin composition is cured, residual stress can be obtained compared to a cured product mainly composed of a thiol compound with more than trifunctional Small, hardened material that can follow the thermal deformation of the attached body and has excellent stress relaxation.

Furthermore, the bifunctional thiol compound of component (B) does not contain an ester bond in the molecule, so it is resistant to hydrolysis even under high temperature and humidity such as the pressure retort test (hereinafter also referred to as "PCT") High performance, can maintain the adhesive strength of the resulting hardened product.

The aforementioned (B) component is preferably a bifunctional thiol compound represented by the following general formula (B-1), for example. The bifunctional thiol compound system shown in (B-1) can be obtained from Shikoku Chemical Industry Co., Ltd.

In general formula (B-1), n and m are each independently an integer of 1 to 3, and n and m are each preferably 2.

The bifunctional thiol compound represented by the aforementioned general formula (B-1) is preferably a bifunctional thiol compound represented by the following general formula (B-1-1).

The aforementioned (B) component is preferably a bifunctional thiol compound represented by the following general formula (B-2), for example. The bifunctional thiol compound system shown in (B-2) can be obtained from Shikoku Chemical Industry Co., Ltd.

In the general formula (B-2), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a group represented by the following general formula (b-1); however, any of R ¹ and R ² One is a group represented by the following general formula (b-1), and any one of R ³ and R ⁴ is a group represented by the following general formula (b-1).

In the general formula (b-1), r is an integer of 1 to 3, and 2 is preferred.

The bifunctional thiol compound represented by the aforementioned general formula (B-2) is preferably a bifunctional thiol compound represented by the following general formula (B-2-1).

The aforementioned (B) component is preferably a bifunctional thiol compound represented by the following general formula (B-3), for example. The bifunctional thiol compound system shown in (B-3) can be obtained from Shikoku Chemical Industry Co., Ltd.

In the general formula (B-3), G ₁ and G ₂ are each independently a divalent group bonded by -O- or -CH ₂ -, and p and q are each independently an integer of 2-5. G ₁ and G _{2 are} preferably divalent groups bonded by -O-, and p and q are preferably 3 or 4, more preferably 4.

The bifunctional thiol compound represented by the aforementioned general formula (B-3) is preferably a bifunctional thiol compound represented by the following general formula (B-3-1).

The component (B) is preferably, for example, a bifunctional thiol compound represented by the following general formula (B-4). The bifunctional thiol compound system shown in (B-4) can be obtained from Shikoku Chemical Industry Co., Ltd.

In the general formula (B-4), s and t are each independently an integer of 3 or 4, and 4 is preferred.

The component (B) is preferably a bifunctional thiol compound represented by the following general formula (B-5), for example. The bifunctional thiol compound system shown in (B-5) can be obtained from Shikoku Chemical Industry Co., Ltd.

In the general formula (B-5), u and v are each independently an integer of 3 or 4, and 4 is preferred.

The resin composition of one embodiment of the present invention may further contain thiol compounds (monofunctional thiol compounds, bifunctional thiol compounds, and trifunctional or higher thiol compounds) other than the component (B). When the total number of thiol groups in the resin composition is regarded as 100, the total number of thiol groups contained in the bifunctional thiol compound of component (B) is preferably 20-100, more preferably 40-100, especially Preferably, it is 50-100. The number of thiol groups contained in the bifunctional thiol compound of component (B) can be determined by dividing the mass of the bifunctional thiol compound of component (B) by the sulfur of the bifunctional thiol compound of component (B) Calculated based on alcohol equivalent. Moreover, the ratio of the thiol group of (B) component and the thiol compound other than (B) component can also be calculated using NMR. When the total number of thiol groups in the resin composition contains thiol compounds other than the bifunctional thiol compound of component (B), the number of thiol groups of the thiol compound other than component (B) can be determined by Calculate by dividing the mass of thiol compounds other than component (B) by the equivalent of thiol groups of thiol compounds other than component (B). The number of thiol groups other than component (B) can be calculated by The sum of the thiol groups of the bifunctional thiol compound is regarded as the total number of thiol groups in the resin composition.

The equivalent ratio (epoxy equivalent: thiol equivalent) of the thiol groups of all thiol compounds relative to the epoxy groups of the epoxy resin contained in the resin composition is preferably 1:0.5 to 1:1.5. In the resin composition, if the thiol equivalent is less than 0.5 equivalent or more than 1.5 equivalent relative to the epoxy equivalent of the epoxy resin contained in the resin composition, the unreacted epoxy resin or thiol compound system It remains in the cured product, so the adhesive strength of the resin composition decreases.

(C)Component: Amine compound In the resin composition of one embodiment of the present invention, the amine compound of the component (C) is preferably at least one amine compound selected from an imidazole compound, a tertiary amine compound, and an amine adduct. The amine compound of the component (C) preferably has a function as a hardening accelerator of the epoxy resin. For example, the amine compound of the component (C) is preferably a solid that is insoluble at room temperature, and is solubilized by heating, and has a function as a hardening accelerator. Examples of such compounds include imidazole-based solids at room temperature Compound, or tertiary amine compound, solid dispersion type amine adduct series latent hardening accelerator, such as the reaction product of amine compound and epoxy compound (amine-epoxy adduct series latent hardening accelerator), amine The reaction product of compound and isocyanate compound or urea compound (urea type adduct series latent hardening accelerator), etc.

As the imidazole compound, for example, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S- Tris, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-tris, isocyanuric acid adduct, 2-methylimidazole , 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitic acid ester, 1-cyanoethyl-2-phenylimidazole-trimellitic acid ester, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-(2-methylimidazolyl- (1)-Ethyl)-hexamethylene diacetamide, etc., but not limited to these.

Examples of tertiary amine compounds include dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, and dimethylaminopropylamine. Amine compounds such as aminoethylamine, diethylaminoethylamine, N-methylpiperidine, or such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl Imidazole compounds such as imidazole and 2-phenylimidazole have tertiary amine groups in the molecule, primary or secondary amines; such as 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol , 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxyl -3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy- 3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3 -Phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol , 2,4,6-ginseng (dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole , 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotine Acid, picolinic acid, N,N-dimethylglycine hydrazine, N,N-dimethylpropionate hydrazine, nicotinic acid hydrazine, isonicotinic acid hydrazine, etc. have three levels in the molecule Amino alcohols, phenols, mercaptans, carboxylic acids, hydrazines, etc. Examples of commercially available tertiary amine compounds include Fujicure FXR-1020 and Fujicure FXR-1020 (manufactured by T&K TOKA Co., Ltd.).

Examples of commercially available solid dispersion type amine adduct-based latent hardening accelerators include Novacure HXA9322HP (manufactured by Asahi Kasei Co., Ltd.), Fujicure FXR-1121 (manufactured by T&K TOKA Co., Ltd.), and Ajicure PN-23 , Ajicure PN-F (manufactured by Ajinomoto Precision Technology Co., Ltd.), etc. A more detailed example of the solid dispersion type amine adduct type latent hardening agent or latent hardening accelerator is based on the description in Japanese Patent Application Laid-Open No. 2014-77024.

The content of the amine compound of the component (C) contained in the resin composition varies with the type of amine compound. From the viewpoint of increasing the pot life, the (C) amine compound contained in the resin composition is preferably 0.1-40 parts by mass, more preferably 0.5-35 parts by mass relative to 100 parts by mass of the epoxy resin contained in the resin composition Parts by mass, particularly preferably 1.0-30 parts by mass. In addition, the component (C) is provided in the form of a dispersion dispersed in an epoxy resin. When using component (C) in this form, the amount of epoxy resin in which component (C) is dispersed is also included in the epoxy resin (component (A) and epoxy other than component (A) in the resin composition of the present invention) The amount of resin).

(D) Ingredient: stabilizer The resin composition of one embodiment of the present invention may contain the stabilizer of the component (D). Since the resin composition contains the stabilizer of component (D), the storage stability at room temperature (25°C) can be improved, and the pot life can be extended. As the stabilizer of the component (D), at least one selected from the group consisting of a liquid borate compound, aluminum chelate, and barbituric acid is preferred, because storage at room temperature (25°C) The effect of increasing stability is high.

As the liquid borate compound, for example, 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborocyclohexane), trimethyl borate, triboric acid can be used. Ethyl ester, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, tri-n-butyl borate Nonyl ester, tridecyl borate, tris(dodecyl) borate, tris(hexadecyl) borate, tris(octadecyl) borate, ginseng(2-ethylhexyloxy)borane, bis( 1,4,7,10-tetraoxaundecyl) (1,4,7,10,13-hexaoxatetradecyl) (1,4,7-trioxaundecyl)borane, Tribenzyl borate, triphenyl borate, tri-o-cresyl borate, tri-m-cresyl borate, triethanolamine borate. In addition, the liquid borate compound contained as the component (D) is preferable because it is liquid at normal temperature (25° C.) and can reduce the viscosity of the resin composition. When a liquid borate compound is contained in the resin composition as the component (D), it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and particularly preferably 0.1 relative to 100 parts by mass of the resin composition ～1 part by mass.

As the aluminum chelate compound, for example, aluminum triacetone acetone (for example, ALA manufactured by Kawaken Fine Chemical Co., Ltd.: aluminum chelate A) can be used. When an aluminum chelate compound is contained as the component (D), it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the resin composition.

When barbituric acid is contained as the component (D), it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and particularly preferably 0.1 to 1 part by mass relative to 100 parts by mass of the resin composition.

The resin composition of the present invention can optionally be used as (E) other components, and further contains inorganic fillers selected from silica, alumina, titania, magnesia, glass, talc, calcium carbonate, etc., acrylic resin, poly Silicone resin, polystyrene resin, polydivinylbenzene and other organic fillers, acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR) and other rubber fillers, carboxyl-terminated butadiene Nitrile rubber (CTBN) or polybutadiene and other flexible agents, silane coupling agents, ion trapping agents, leveling agents, antioxidants, defoamers and thixotropic agents form at least one additive. In addition, viscosity modifiers, flame retardants, solvents, etc. may be contained.

Manufacturing method of resin composition The resin composition system of one embodiment of the present invention can be produced by adding the aforementioned (A) component to (C) component and optionally (D) component, and kneading. The manufacturing method of the resin composition is not specifically limited. For example, the resin composition system of this embodiment can be mixed with a mixer such as a crusher, a ball mill, a three-roll mill, a compound mixer, a rotary mixer, or a twin-shaft mixer, and contains the aforementioned (A) component~ (C) Ingredients, as needed (D) Ingredients are manufactured. These ingredients can be mixed at the same time, or one part can be mixed first, and then the rest can be mixed. Moreover, it can also be used in combination with the above-mentioned apparatus suitably.

Adhesive The adhesive of one embodiment of the present invention uses the above-mentioned resin composition. The adhesive system of one embodiment of the present invention can be cured at a low temperature without impairing physical properties, and a cured product with excellent stress relaxation can be obtained. For example, when the adhesive of one embodiment of the present invention is used to join two parts with different thermal expansion coefficients, even when the parts are thermally deformed due to changes in the surrounding temperature, they have flexibility that can follow the thermal deformation of the parts. As a specific thermal curing condition, for example, 60°C or more and 120°C or less.

Sealing material The sealing material of one embodiment of the present invention uses the above-mentioned resin composition. The sealing material of one embodiment of the present invention can be cured at low temperature without impairing physical properties, and can obtain a cured product with excellent stress relaxation. For example, when the sealing material of one embodiment of the present invention is used to seal the gap between two parts, even when the parts are thermally deformed due to changes in the surrounding temperature, they have flexibility that can follow the thermal deformation of the parts. As a specific thermal curing condition, for example, 60°C or more and 120°C or less.

Image sensor module The image sensor module of one embodiment of the present invention is formed using an adhesive or sealing material containing the aforementioned resin composition. The image sensor modules also include the camera modules of mobile phones or smart phones. The resin composition of one embodiment of the present invention can be cured at low temperatures without impairing physical properties and can obtain a cured product with excellent stress relaxation. Therefore, it can be suitably used as a resin composition contained in an adhesive or a sealing material. The agent or sealing material is used in the assembly of image sensor modules that require curing at a low temperature of about 80°C.

Semiconductor device The semiconductor device of one embodiment of the present invention is formed using an adhesive or sealing material containing the aforementioned resin composition. A semiconductor device refers to the entire device that can use the characteristics of a semiconductor to function, including electronic parts, semiconductor circuits, modules incorporating these, and electronic equipment. The resin composition of one embodiment of the present invention can be cured at a low temperature of about 80°C without impairing physical properties, and a cured product with excellent stress relaxation can be obtained. Therefore, it can be suitably used as a resin composition contained in an adhesive or a sealing material. The adhesive or sealing material is used in the assembly of image sensor modules that require hardening at low temperatures. Example

Hereinafter, the present invention will be specifically explained with examples. The present invention is not limited to these embodiments.

Examples and comparative examples With the formulation shown in the following Tables 1-3, each component was mixed and the resin composition was prepared. In addition, in the following table, the numbers which show the blending ratio of (A) component-(E) component, and all represent mass parts. The components in Tables 1 to 3 are as follows.

Epoxy resin (A) component: epoxy resin without aromatic ring (A1) YX8000: hydrogenated bisphenol A epoxy resin, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 410, epoxy equivalent: 205 g/eq. (A2) YX7400: represented by the general formula (A-1-1), the epoxy resin in which x in the general formula (A-1-1) is 10.3, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 870, epoxy Equivalent: 435g/eq. (A3) CDMDG: 1,4-cyclohexanedimethanol diglycidyl ether, manufactured by Showa Denko Co., Ltd., weight average molecular weight 264, epoxy equivalent: 132 g/eq. (A4) Adk Lizer (registered trademark) BF1000: Epoxy modified polybutadiene (the side chain of 1,2-polybutadiene is epoxidized), ADEKA Co., Ltd., weight average molecular weight 1,500, epoxy equivalent : 178g/eq. (A5) TSL9906: It is represented by general formula (A-2). R ⁶ to R ^{9 in} general formula (A-2) are epoxy resins of methyl, manufactured by Momentive Performance Materials Co., Ltd., weight average molecular weight 296, epoxy The equivalent is 181g/eq. (A') component: epoxy resin containing aromatic ring (A'6) EXA-850CRP (EPICLON): bisphenol A epoxy resin, DIC Co., Ltd., weight average molecular weight: 344, epoxy equivalent 172g/eq .

Thiol compound (B) Component: Bifunctional thiol compound (B1) Thiol compound 1: A bifunctional thiol compound represented by general formula (B-1-1), manufactured by Shikoku Chemical Industry Co., Ltd., molecular weight 389, thiol equivalent: 211 g/eq. (B2) Thiol compound 2: A bifunctional thiol compound represented by general formula (B-2-1), manufactured by Shikoku Chemical Industry Co., Ltd., molecular weight 445, thiol equivalent: 243 g/eq. (B3) Thiol compound 3: A bifunctional thiol compound represented by general formula (B-3-1), manufactured by Shikoku Chemical Industry Co., Ltd., molecular weight 286, thiol equivalent: 159 g/eq. (B’) Thiol compounds other than component (B) (B'4) 3,6-dioxa-1,8-octane dithiol (1,8-dimercapto-3,6-dioxaoctane): manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 182, The mercaptan equivalent is 91g/eq. (B'5) 1,10-decane dithiol: manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 206, and mercaptan equivalent 103 g/eq. (B'6) EPMG-4: Tetraethylene glycol bis(3-mercaptopropionate), manufactured by SC Organic Chemical Co., Ltd., molecular weight 372, mercaptan equivalent 186 g/eq. (B'7) PEMP: Pentaerythritol 4 (3-mercaptopropionate) (PEMP), manufactured by SC Organic Chemical Co., Ltd., molecular weight 489, mercaptan equivalent 122 g/eq. (B'8) C3 TS-G: 1,3,4,6-4-(3-mercaptopropyl)glycuril, manufactured by Shikoku Chemical Industry Co., Ltd., molecular weight 432, mercaptan equivalent 114g/eq.

(C)Component: Amine compound (C1) HXA9322HP: solid dispersion type amine adduct series latent hardening accelerator (microcapsule type imidazole adduct), manufactured by Asahi Kasei Co., Ltd., 1/3 of the weight is microcapsule type imidazole adduct, 2/ 3 is a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, with an epoxy equivalent of 180 g/eq. (C2) FXR1121 (Fujicure): solid dispersion type amine adduct, manufactured by T&K TOKA Co., Ltd. (C3) FXR1020 (Fujicure), tertiary amine compound, manufactured by T&K TOKA Co., Ltd.

(D) Ingredient: stabilizer (D1) TIPB: Triisopropyl borate, manufactured by Tokyo Chemical Industry Co., Ltd.

(E) Other ingredients (E1) SOE5: Silica filler, manufactured by ADMATECHS Co., Ltd. (E2) KBM403: 3-glycidoxypropyltrimethoxysilane (silane coupling agent), manufactured by Shin-Etsu Chemical Co., Ltd.

Evaluation method volatility Measure the weight of a metal container with a diameter of 5 cm and a depth of 0.5 cm. To this, 1.0 g of the thiol compound was added to the standard, and the lid was not closed, and it was placed in an oven at 80°C for 1 hour. After being left to cool, the weight of the metal container is measured, and the volatile content from the mercaptan resin is measured. As a result, the volatile content of 1,10-decane dithiol is 11%, and the volatile content of 3,6-dioxa-1,8-octane dithiol is 27%. Relative to this, it contains thiol compounds. The volatile content of other mercaptan resins 1, 2, and 3 are all below 1%.

Then intensity The adhesive strength (shear strength) of the prepared resin composition was measured by the following procedure. The results are shown in the table below. (1) The sample is printed on a 3cm×4cm SUS (Steel Special Use Stainless) 304 plate with a size of 2mmφ, (2) On the printed sample, 1.5mm×3mm aluminum fragments are placed. Using a blower dryer, it was heat-cured at 80°C for 180 minutes. (3) The shear strength was measured with a desktop universal testing machine (AIKOH ENGINEERING (1605HTP) manufactured by Co., Ltd.). Table 1 describes the resin compositions of the respective Examples and Comparative Examples with adhesive strengths of 90N or more and 180N or less. Table 2. The resin composition of each Example and Comparative Example whose adhesive strength is less than 90N is described in Table 3. The resin composition of each Example and Comparative Example whose adhesive strength exceeds 180N is described in Table 3.

Warpage To each of the epoxy resins shown in Tables 1 to 3, in order to suppress the sag, 0.6 parts of the thixotropic agent R805 manufactured by Japan AEROSIL was added, and other components were mixed as shown in Tables 1 to 3 to prepare a resin composition. In addition, in the following table, the numbers which show the blending ratio of (A) component-(E) component all show mass parts. The prepared resin composition was applied to a polyimide film (Kapton film: thickness 5μm) manufactured by Toray-DuPont Co., Ltd., and a square hole plate of 2cm×2cm and thickness 125μm (Ube Industries Co., Ltd. Make Upilex film) for stencil printing. After heat-curing at 80°C for 180 minutes, it was left at 25°C for 1 night. Cut out the printed part of the cured product to make a 2cm×2cm sample. Measure the convex surface with a measuring microscope, and use the distance from the horizontal plane to the maximum height as the amount of warpage. From the viewpoint of stress relaxation, the amount of warpage is preferably 4.0 mm or less.

Hydrolysis resistance When a compound containing an ester bond is included in the resin composition, it is hydrolyzed under high temperature and high humidity, and the cured resin of the composition of Comparative Examples 3 and 4 (sample after measuring the amount of warpage) is kept under PCT conditions (121°C). (2 atm) for 10 hours, as a result, the cured resin system was liquefied and the hydrolysis resistance was poor. On the other hand, in the composition systems of Examples 16 and 17, no abnormality was observed in the appearance of the cured resin.

The cured product obtained from the resin composition of Examples 1-20 has good hydrolysis resistance and low volatility, and voids do not exist in the cured product after curing.

As shown in Table 1, the warpage of the cured product obtained from the resin composition of Examples 1 to 11 whose adhesive strength of the resin composition is 90N to 180N is 2.1 mm or less. Compared with Comparative Example 1, the warpage is inhibition. From this result, it can be confirmed that the resin composition of Examples 1 to 11 has low residual stress and can follow two parts with different thermal expansion coefficients even if the two parts expand and contract due to changes in the surrounding temperature. The flexibility of the changes of the two parts and excellent stress relaxation. On the other hand, the cured product obtained from the resin composition of Comparative Example 1 in which the adhesive strength of the resin composition is 90N to 180N has a warpage exceeding 2.1 mm. In addition, the thiol compound contained in the resin composition of Comparative Example 1 has a small molecular weight and is volatile, and bubbles are generated in the resin composition during curing, and voids are present in the resulting cured product. In addition, Example 5 and Example 11 are examples in which an aromatic ring-containing epoxy resin is used in combination, but the adhesion strength and the suppression of warpage are both good.

As shown in Table 2, the warpage of the cured product obtained from the resin compositions of Examples 12 to 14 whose adhesive strength of the resin composition is less than 90N is 1.2 mm or less. Compared with Comparative Examples 2 and 3, the warpage suppressed. From this result, it can be confirmed that the residual stress is small. After two parts with different thermal expansion coefficients are attached, even when the two parts expand and contract due to changes in the surrounding temperature, they have flexibility and stress that can follow the changes of the two parts. Excellent relaxation. On the other hand, the cured products obtained from the resin compositions of Comparative Examples 2 and 3 in which the adhesive strength of the resin composition did not reach 90N had a warpage exceeding 1.2 mm. In addition, the thiol compound contained in the resin composition of Comparative Example 2 has a small molecular weight and is volatile, and bubbles are generated in the resin composition during curing, and voids are present in the resulting cured product. Since the thiol compound contained in the resin composition of Comparative Example 3 contains an ester bond, the possibility of hydrolysis is high, and the adhesive strength under high temperature and high humidity is predicted to decrease. In addition, Example 14 is an example in which two types of (A) components are used in combination, but the adhesion strength and the suppression of warpage are both good.

As shown in Table 3, the warpage of the cured product obtained from the resin composition of Examples 15 to 20 whose adhesive strength of the resin composition exceeded 180N was less than 4.0 mm. Compared with Comparative Examples 4 and 5, the warpage was inhibition. From this result, it can be confirmed that the residual stress is small. After two parts with different thermal expansion coefficients are attached, even when the two parts expand and contract due to changes in the surrounding temperature, they have flexibility and stress that can follow the changes of the two parts. Excellent relaxation. On the other hand, the cured product obtained from the resin composition of Comparative Examples 4 and 5 in which the adhesive strength of the resin composition exceeded 180N became larger with a warpage of more than 4.0 mm. According to this result, the cured product obtained from the resin composition of Comparative Examples 4 and 5 has residual stress, and it is predicted that the softness will not follow the change of the two parts due to the influence of temperature when the two parts are connected. In addition, since the thiol compound contained in the resin composition of Comparative Example 5 contains an ester bond, the possibility of hydrolysis is high, and the adhesive strength under high temperature and high humidity is predicted to decrease. In addition, Examples 16 to 19 are examples in which the (B) component and the thiol compound other than the (B) component are used in combination, but the adhesion strength and the suppression of warpage are both good.

Claims (15)

A resin composition comprising: (A) Epoxy resin without aromatic ring, (B) A bifunctional thiol compound, selected from: a molecular chain containing an aromatic ring structure or an alicyclic structure in the molecule, and a molecular chain with a thiol group at the end that contains a heteroatom but does not contain an ester bond, and has a molecular weight of 210 or more A thiol compound and a bifunctional thiol compound containing an aromatic ring structure or a heterocyclic structure in the molecule and a molecular chain with a thiol group at the end that may contain heteroatoms but no ester bond. The molecular weight is 210 or more. At least 1 type of group, and (C) Amine compounds. The resin composition of claim 1, wherein the aforementioned component (B) is a bifunctional thiol compound having an alicyclic structure and a molecular chain containing a thioether bond but no ester bond and having a thiol group at the end in the molecule. The resin composition of claim 1, wherein the aforementioned component (B) is a bifunctional thiol compound having an aromatic ring structure and a molecular chain having an ether bond but no ester bond and having a thiol group at the end in the molecule. The resin composition of claim 1, wherein the aforementioned component (B) is a bifunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3),

(In the general formula (B-1), n and m are each independently an integer of 1 to 3);

(In the general formula (B-2), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a group represented by the following general formula (b-1); however, R ¹ and R ^{2 are} Either one is a group represented by the following general formula (b-1), and any one of R ³ and R ⁴ is a group represented by the following general formula (b-1));

(In the general formula (b-1), r is an integer of 1 to 3);

(In the general formula (B-3), G ₁ and G ₂ are each independently a divalent group bonded by -O- or -CH ₂ -, and p and q are each independently an integer of 2 to 5). The resin composition of claim 1, wherein the aforementioned component (B) is a bifunctional thiol compound represented by the following general formula (B-4) or (B-5),

(In the general formula (B-4), s and t are each independently an integer of 3 or 4);

(In the general formula (B-5), u and v are each independently an integer of 3 or 4). The resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the aforementioned (A) component is 240 to 1,000. The resin composition according to any one of claims 1 to 6, wherein the aforementioned component (A) is an epoxy resin represented by the following formula (A-1) or (A-2),

(In formula (A-1), R ⁵ is a linear or branched alkylene group having 1 to 15 carbon atoms, and w is an integer of 1 to 20);

(In the formula (A-2), R ⁶ to R ⁹ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms). The resin composition according to any one of claims 1 to 7, wherein the amine compound of the component (C) is at least one amine compound selected from an imidazole compound, a tertiary amine compound, and an amine adduct. The resin composition of any one of claims 1 to 8, wherein when the total number of thiol groups in the resin composition is regarded as 100, the total number of thiol groups of the bifunctional thiol compound of component (B) It is 20-100. The resin composition according to any one of claims 1 to 9, which further contains (D) a stabilizer. The resin composition of claim 10, wherein the stabilizer of the aforementioned component (D) is at least one selected from the group consisting of a liquid borate compound, an aluminum chelate compound, and barbituric acid. An adhesive comprising the resin composition according to any one of claims 1-11. A sealing material comprising the resin composition according to any one of claims 1 to 11. An image sensor module, which is manufactured by using an adhesive such as claim 12 or a sealing material such as claim 13. A semiconductor device that is manufactured by using an adhesive such as claim 12 or a sealing material such as claim 13.