KR20210080363A - resin composition - Google Patents

Abstract

(A) an epoxy resin, (B) an aromatic ring structure or an alicyclic structure in the molecule, and a molecular chain containing a hetero atom and not including an ester bond, a molecular chain having a thiol group at the terminal, and a molecular weight of 210 or more bifunctional thiol A compound and a bifunctional thiol compound having an aromatic ring structure or a heterocyclic structure in the molecule, and a molecular chain having a thiol group at the terminal, which may contain a hetero atom or does not contain an ester bond, and has a molecular weight of 210 or more It is a resin composition containing at least 1 sort(s) of bifunctional thiol compound selected from the group, (C) an amine compound, and (D) filler whose average particle diameter is 0.1 micrometer or more and 10 micrometers or less.

Description

resin composition

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

An adhesive or encapsulant that is thermosetted at a relatively low temperature, specifically, about 80° C., is used for assembling a structure when manufacturing an image sensor module used as a camera module for a mobile phone or a smartphone. Also in the manufacture of semiconductor devices including electronic components such as semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors, adhesives or encapsulants containing a resin composition thermosetting at a temperature of about 80 ° C. use is preferred.

In addition, an adhesive or encapsulant used in manufacturing an image sensor module or a semiconductor device is also required to have moisture resistance. Moreover, impact resistance with respect to a fall etc. is calculated|required by mobile devices, such as a mobile phone and a smart phone, and stress absorbing property is calculated|required of hardened|cured material, such as an adhesive agent used for semiconductor devices.

For example, in patent document 1, thermosetting at low temperature is possible, and it is excellent in tolerance also in the pressure cooker test (henceforth "PCT") which tests at 100 degreeC or more and high temperature and high humidity of 70% or more. As a liquid adhesive, the resin composition containing the thiol compound which has 4 thiol groups in a molecule|numerator is disclosed.

International Publication No. 2015/141347

However, in a resin composition in which the thiol compound is a polythiol compound having four thiol groups in its molecule as a main component, the crosslinking point increases, and the resulting cured product may be insufficient in stress absorption. In addition, adhesives and encapsulants used for assembling an image sensor module or a semiconductor device are required to have low viscosity change with respect to temperature change during application while also requiring moisture resistance after curing.

Accordingly, an object of the present invention is to provide a resin composition capable of curing at a low temperature, obtaining a cured product excellent in moisture resistance and stress absorption, and having good handleability during use.

Means for solving the above problems are as follows, and the present invention includes the following aspects.

[1] (A) an epoxy resin;

(B) a bifunctional thiol compound having an aromatic ring structure or an alicyclic structure in the molecule, and a molecular chain containing a hetero atom and not including an ester bond, having a thiol group at the terminal, and having a molecular weight of 210 or more, and an aroma in the molecule At least one selected from the group consisting of a ring structure or a heterocyclic structure and a bifunctional thiol compound having a molecular weight of 210 or more, including a molecular chain having a thiol group at the terminal, which may contain a hetero atom or does not contain an ester bond. and a bifunctional thiol compound of

(C) an amine compound;

(D) It is a resin composition containing the filler whose average particle diameters are 0.1 micrometer or more and 10 micrometers or less.

[2] In the above [1], wherein the component (B) is a bifunctional thiol compound comprising an alicyclic structure in the molecule, and a molecular chain having a thiol group at the terminal, which contains a thioether bond and does not contain an ester bond described resin composition.

[3] In the above [1], wherein the component (B) is a bifunctional thiol compound comprising an aromatic ring structure in the molecule, and a molecular chain having a thiol group at the terminal, including an ether bond but not an ester bond described resin composition.

[4] The resin composition according to the above [1], wherein the component (B) is a bifunctional thiol compound represented by the following formula (B-1), (B-2), or (B-3).

(in formula (B-1), n and m are each independently an integer of 1 to 3)

(In 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 formula (b-1). However, either R ¹ or R ² is a group represented by the following formula (b-1), ^{and either one of R 3} and R ⁴ is a group represented by the following formula (b-1))

(in formula (b-1), r is an integer of 1-3)

(In formula (B-3), G ₁ and G ₂ are each independently a _{divalent group bonded to -O- or -CH 2} -, and p and q are each independently an integer of 2 to 5)

[5] The resin composition according to the above [1], wherein the component (B) is a bifunctional thiol compound represented by the following formula (B-4) or (B-5).

(in formula (B-4), s and t are each independently an integer of 3 or 4)

(In 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 molecular weight of the component (A) is 240 to 1,000.

[7] In any one of [1] to [6] above, wherein the amine compound of component (C) is at least one amine compound selected from an imidazole compound, a tertiary amine compound, and an amine adduct. described resin composition.

[8] In any one of [1] to [7] above, wherein the total number of thiol groups in the bifunctional thiol compound of the component (B) is 20 to 100 when the total number of thiol groups in the resin composition is 100. described resin composition.

[9] The resin composition according to any one of [1] to [8], wherein the content of the filler of the component (D) is 5 to 70 mass% with respect to 100 mass% of the total amount of the resin composition.

[10] (E) The resin composition according to any one of [1] to [9], further comprising a stabilizer.

[11] The resin composition according to [10], wherein the stabilizer of the component (E) is at least one selected from the group consisting of a liquid boric acid ester compound, an aluminum chelate, and a barbituric acid.

[12] An adhesive comprising the resin composition according to any one of [1] to [11].

[13] A sealing material comprising the resin composition according to any one of [1] to [11].

[14] An image sensor module manufactured using the adhesive according to the above [12] or the encapsulant according to the above [13].

[15] A semiconductor device manufactured using the adhesive according to the above [12] or the encapsulant according to the above [13].

According to the present invention, it is possible to provide a resin composition which can be cured at a low temperature of about 80° C., a cured product excellent in moisture resistance and stress absorption properties is obtained, and has good handling properties during use.

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

The resin composition according to the first embodiment of the present invention,

(A) an epoxy resin;

(B) a bifunctional thiol compound having an aromatic ring structure or an alicyclic structure in the molecule, and a molecular chain containing a hetero atom and not including an ester bond, having a thiol group at the terminal, and having a molecular weight of 210 or more, and an aroma in the molecule At least one selected from the group consisting of a ring structure or a heterocyclic structure and a bifunctional thiol compound having a molecular weight of 210 or more, including a molecular chain having a thiol group at the terminal, which may contain a hetero atom or does not contain an ester bond. and a bifunctional thiol compound of

(C) an amine compound;

(D) The average particle diameter contains the filler which is 0.1 micrometer or more and 10 micrometers or less.

(A) component: epoxy resin

A resin composition contains an epoxy resin as (A) component. (A) Polyglycidyl ether obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol and resorcinol as the epoxy resin of component (A), 1,6-bis(2) ,3-epoxypropoxy) epoxy resin having a naphthalene skeleton such as naphthalene, epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin, cyclic aliphatic epoxy resin, urethane-modified epoxy resin, silicone-modified epoxy resin and the like. It is not limited to these resins. In order that the epoxy resin of (A) component may improve the moisture resistance of the hardened|cured material which consists of a resin composition, it is preferable that it is an epoxy resin which does not contain an ester bond. As such an epoxy resin, a bisphenol A epoxy resin, a bisphenol F type epoxy resin, etc. are mentioned, for example.

(A) The epoxy resin which does not contain an aromatic ring may be sufficient as the epoxy resin of a component. Here, the aromatic ring is a structure satisfying Hückel's rule, for example, a benzene ring. (A) As an epoxy resin which does not contain an aromatic ring as an epoxy resin of a component, a hydrogenated bisphenol type epoxy resin, an alicyclic epoxy resin, an alcohol ether type epoxy resin, an aliphatic epoxy resin, etc. are mentioned. It is not limited to these resins. Examples of such an epoxy resin include a hydrogenated bisphenol A-type epoxy resin, a hydrogenated bisphenol F-type epoxy resin, an epoxy-modified polybutadiene, and 1,4-cyclohexanedimethanol diglycidyl ether. (A) When using an epoxy resin not containing an aromatic ring as the component, the number of epoxy groups contained in the epoxy resin not containing an aromatic ring is, from the viewpoint of viscosity and adhesiveness, the total number of epoxy groups in the resin composition is 100 It is preferable that it is 20-100, it is more preferable that it is 40-100, and it is still more preferable that it is 50-100.

(A) As an epoxy resin of a component, the epoxy resin represented, for example by the following formula (A-1) is mentioned.

In formula (A-1), R<^5> is a C1-C15 linear or branched alkylene group, and w is an integer of 1-20.

The epoxy resin represented by the formula (A-1) may be an epoxy resin represented by the following formulas (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.

(A) The epoxy resin of the component may be an epoxy resin represented by the following formula (A-2), for example.

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

(A) It is preferable that weight average molecular weights are 240-1,000 from a viewpoint of balance of a viscosity and volatility of the epoxy resin of component. (A) As for the epoxy resin of component, Weight average molecular weight becomes like this. More preferably, it is 250-1,000, More preferably, it is 260-1,000, More preferably, it is 270-1,000. (A) When the weight average molecular weight of the epoxy resin of component is less than 240, volatility becomes high easily, and there exists a possibility that a void may generate|occur|produce in hardened|cured material. On the other hand, when the weight average molecular weight of the epoxy resin of (A) component exceeds 1,000, it may become high viscosity and workability|operativity may deteriorate. In this specification, a weight average molecular weight means the value using the analytical curve by standard polystyrene by the gel permeation chromatography method (GPC).

(B) component: bifunctional thiol compound

The (B) bifunctional thiol compound contained in the resin composition of one embodiment of the present invention has an aromatic ring structure or an alicyclic structure in the molecule, and a hetero atom and no ester bond. A molecular chain having a thiol group at the terminal. A bifunctional thiol compound having a molecular weight of 210 or more, and an aromatic ring structure or a heterocyclic structure in the molecule, and a molecular chain having a thiol group at the terminal, which may contain a hetero atom or does not contain an ester bond, , at least one type of bifunctional thiol compound selected from the group consisting of bifunctional thiol compounds having a molecular weight of 210 or more. (B) The bifunctional thiol compound of component can be obtained from Shikoku Chemical Industry Co., Ltd.

Since the bifunctional thiol compound of component (B) has a molecular weight of 210 or more and has low volatility, the bifunctional thiol compound does not volatilize when thermosetting the resin composition at a low temperature of, for example, 80° C., and generation of voids is suppressed It is possible to obtain a cured product maintaining physical properties. As for molecular weight, it is more preferable that it is 280 or more. Moreover, it is preferable from a sclerosis|hardenable viewpoint that molecular weight is 1,000 or less, and, as for the bifunctional thiol compound of (B) component, it is more preferable that it is 600 or less.

The bifunctional thiol compound of component (B) has a hetero atom, and compatibility with the epoxy resin of component (A) is good, for example, by curing at a low temperature of 80° C., a homogeneous cured product is obtained. . (B) As for the aromatic ring structure of a component, a monocyclic aromatic ring structure more than 5-membered ring, for example, cyclopentadiene, benzene, etc. are mentioned. Examples of the alicyclic structure include monocyclic alicyclic structures of 5 or more membered rings, such as cyclopentane and cyclohexene. The heterocyclic structure may be monocyclic or polycyclic, may be an alicyclic structure having a hetero atom, may be an aromatic ring structure having a hetero atom, or may be a condensed polycyclic structure having a hetero atom. The hetero atom contained in the molecular chain includes, for example, sulfur (S) and oxygen (O) atoms, and it is preferable to include a thioether bond or an ether bond in the molecular chain. (B) The bifunctional thiol compound of component is from the viewpoint of compatibility with the epoxy resin and low volatility, that the hetero atom is a sulfur atom, that is, it contains an alicyclic structure and a thioether bond in the molecule and does not contain an ester bond. , it is preferable to include a molecular chain having a thiol group at the terminal. In addition, from the viewpoint of compatibility with the epoxy resin and low volatility, the bifunctional thiol compound of component (B) is one in which the hetero atom is an oxygen atom, that is, an aromatic ring structure in the molecule, an ether bond, and an ester bond It is preferable to include a molecular chain having a thiol group at the terminal. From the viewpoint of adhesive strength to metal, the bifunctional thiol compound of component (B) contains an alicyclic structure and a thioether bond in the molecule and does not contain an ester bond. It is preferable to include a molecular chain having a thiol group at the terminal. desirable.

In addition, since the bifunctional thiol compound of component (B) has two thiol groups, when the resin composition is cured, a cured product excellent in stress absorption properties can be obtained compared to a cured product mainly composed of a trifunctional or higher functional thiol compound.

In addition, since the bifunctional thiol compound of component (B) does not contain an ester bond in the molecule, it has high hydrolysis resistance even under high temperature and high humidity, such as an environment in PCT, so that the adhesive strength of the resulting cured product can be maintained. have.

(B) It is preferable that a component is a bifunctional thiol compound represented, for example by a following formula (B-1). The bifunctional thiol compound represented by (B-1) can be obtained from Shikoku Chemical Industry Co., Ltd.

In formula (B-1), n and m are each independently an integer of 1-3, and it is preferable that n and m are 2 respectively.

It is preferable that the bifunctional thiol compound represented by a formula (B-1) is a bifunctional thiol compound represented by a following formula (B-1-1).

(B) It is preferable that a component is a bifunctional thiol compound represented, for example by a following formula (B-2). The bifunctional thiol compound represented by (B-2) can be obtained from Shikoku Chemical Industry Co., Ltd.

In 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 formula (b-1). However, ^{either one of R 1} and R ² is a group represented by the following formula (b-1), ^{and either one of R 3} and R ⁴ is a group represented by the following formula (b-1).

In formula (b-1), r is an integer of 1-3, and it is preferable that it is 2.

It is preferable that the bifunctional thiol compound represented by Formula (B-2) is a bifunctional thiol compound represented by a following formula (B-2-1).

(B) It is preferable that a component is a bifunctional thiol compound represented, for example by a following formula (B-3). The bifunctional thiol compound represented by (B-3) can be obtained from Shikoku Chemical Industry Co., Ltd.

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

It is preferable that the bifunctional thiol compound represented by the said Formula (B-3) is a bifunctional thiol compound represented by a following formula (B-3-1).

It is preferable that the said (B) component is a bifunctional thiol compound represented, for example by a following formula (B-4). The bifunctional thiol compound represented by (B-4) can be obtained from Shikoku Chemical Industry Co., Ltd.

In formula (B-4), s and t are each independently the integer of 3 or 4, and it is preferable that it is 4.

It is preferable that the said (B) component is a bifunctional thiol compound represented, for example by a following formula (B-5). The bifunctional thiol compound represented by (B-5) can be obtained from Shikoku Chemical Industry Co., Ltd.

In formula (B-5), u and v are each independently the integer of 3 or 4, and it is preferable that it is 4.

The resin composition of one Embodiment of this invention WHEREIN: You may contain thiol compounds (monofunctional thiol compound, a bifunctional thiol compound, a trifunctional or more than trifunctional thiol compound) other than (B) component further. (B) When the number of the thiol groups contained in the bifunctional thiol compound of component makes the number of all thiol groups in a resin composition 100, it is preferable that it is 20-100, It is more preferable that it is 40-100, It is 50- 100 is more preferable. It is preferable that the equivalent ratio of the thiol groups of all thiol compounds to the epoxy groups of the epoxy resin contained in the resin composition (epoxy equivalent: thiol equivalent) is 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 with respect to the epoxy equivalent of the epoxy resin contained in the resin composition, unreacted epoxy resin or thiol compound remains in the cured product, so the resin composition The adhesive strength is lowered.

(C) component: amine compound

In the resin composition of one embodiment of the present invention, the amine compound of component (C) is preferably at least one amine compound selected from an imidazole-based compound, a tertiary amine-based compound, and an amine adduct. (C) It is preferable that the amine compound of component has a function as a hardening accelerator of an epoxy resin. For example, the amine compound of component (C) is a solid insoluble at room temperature, and is preferably a compound that functions as a curing accelerator by solubilization by heating, for example, imidazole-based compounds that are solid at room temperature, tertiary amines compound, a solid dispersion type amine adduct-based latent curing accelerator, such as a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct-based latent curing accelerator), a reaction product of an amine compound and an isocyanate compound or a urea compound (Urea type adduct system latent hardening accelerator) etc. are mentioned.

Examples of the imidazole compound include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, and 2-phenyl-4-methyl. -5-Hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl -S-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine-isocyanuric acid adduct, 2-methylimidazole , 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1- Cyanoethyl-2-phenylimidazole trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-(2-methylimidazolyl-(1)-ethyl) -Adipoyldiamide, etc. may be mentioned, but are not limited thereto.

Examples of the tertiary amine compound include dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N- In molecules such as amine compounds such as methylpiperazine and imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole primary or secondary amines having a tertiary amino group; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-( 2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2- Hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxyl) -3-Phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4, 6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzoimidazole, 2-mercaptobenzoimidazole, 2-mer Captobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, and the like; and the like. Examples of commercially available tertiary amine compounds include Fujicure FXR-1030 and Fujicure FXR-1020 (manufactured by T&K TOKA Corporation).

Examples of commercially available solid dispersion type amine adduct latent curing accelerators include Novacure HXA9322HP (manufactured by Asahi Kasei Co., Ltd.), Fujicure FXR-1121 (manufactured by T&K TOKA Corporation), Amicure PN-23, Amicure PN- F (manufactured by Ajinomoto Fine Techno Co., Ltd.); and the like. The description of Unexamined-Japanese-Patent No. 2014-77024 is used as a more detailed example of a solid dispersion type amine adduct system latent hardening|curing agent or a latent hardening accelerator.

Content of the amine compound of (C)component contained in a resin composition changes with the kind of amine compound. From the viewpoint of lengthening the pot life, the (C) amine compound contained in the resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 35 parts by mass to 100 parts by mass of the epoxy resin contained in the resin composition. , More preferably, it is 1.0-30 mass parts. On the other hand, some of the components (C) are provided in the form of a dispersion dispersed in an epoxy resin. When using (C)component of such an aspect, the quantity of the epoxy resin in which (C)component is disperse|distributed is also contained in the quantity of the said (A) component in the resin composition of this invention.

(D) Ingredient: Filler

The filler of (D) component contained in the resin composition of one Embodiment of this invention has an average particle diameter of 0.1 micrometer or more and 10 micrometers or less, Preferably they are 0.1 micrometer or more and 8 micrometers or less, More preferably, they are 0.1 micrometer or more and 5 It is micrometer or less, More preferably, it is 0.1 micrometer or more and 3 micrometers or less. If the average particle diameter of the filler of the component (D) contained in the resin composition is 0.1 µm or more and 10 µm or less, even when the resin composition is used in a relatively high temperature environment, a decrease in the viscosity of the resin composition can be suppressed, and handleability is achieved. This is improved. (D) When the average particle diameter of the filler of component is less than 0.1 micrometer, a viscosity may rise and it may exert a bad influence on workability|operativity. (D) When the average particle diameter of the filler of a component exceeds 10 micrometers, the viscosity fall under heating becomes remarkable. The average particle diameter of the filler refers to a particle diameter (median diameter) at which the volume accumulation frequency on the small-diameter side in the volume-based particle size distribution by the laser diffraction scattering particle size distribution measurement method reaches 50%. When a commercially available filler is used, the average particle diameter of a filler can refer to the average particle diameter described in a catalog.

(D) To [ content of the filler of component / 100 mass % of whole quantity of a resin composition ], Preferably it is 5-70 mass %, More preferably, it is 8-60 mass %, More preferably, it is 10-50 mass %. (D) When content of the filler of component is less than 5 mass % with respect to 100 mass % of the total amount of resin composition, there is too little quantity of a filler, For example, under high temperature (under heating). When it becomes difficult to suppress a fall, and exceeds 70 mass %, there may be too many quantities of a filler, the viscosity of a resin composition may become high, and handleability may not be favorable.

The particle shape of the filler of component (D) will not be specifically limited if an average particle diameter is 0.1 micrometer or more and 10 micrometers or less, For example, a spherical shape or a scale-like thing can be used.

As long as the filler of component (D) has an average particle diameter of 0.1 µm or more and 10 µm or less, the material is not particularly limited, and it can be widely selected from fillers added to adhesive applications or encapsulant applications. Specifically, the filler which consists of inorganic substances, such as silica, alumina, titania, magnesia, and glass, is mentioned. Among these, the filler which consists of silica and alumina can be used preferably from a viewpoint of low thermal expansibility and low water absorption. (D) The filler of component may be used individually by 1 type, and may use 2 or more types together. Commercially available products include, for example, silica filler (product name: SOE2, manufactured by Admatex Corporation, average particle diameter: 0.5 µm), silica filler (product name: SE1050, manufactured by Admatex Corporation, average particle diameter: 0.3 µm), silica filler ( Product name: MP-8FS, manufactured by Tatsumori Corporation, average particle diameter: 0.7 µm), silica filler (product name: SOE5, manufactured by Admatex Corporation, average particle diameter: 1.5 µm), silica filler (product name: FB5SDX, manufactured by Electrochemical Industries, Ltd.) , average particle diameter: 5 μm), silica filler (product name: BSP6, manufactured by Tatsumori Corporation, average particle diameter: 5 μm), silica filler (product name: FB7SDX, manufactured by Electrochemical Industries, Ltd., average particle diameter: 7 μm), etc. have.

(E) Ingredient: Stabilizer

The resin composition of one Embodiment of this invention may contain the stabilizer of (E) component. The resin composition can improve the storage stability in normal temperature (25 degreeC) and can lengthen a pot life by including the stabilizer of (E) component. (E) As a stabilizer of component, at least 1 selected from the group which consists of a liquid boric acid ester compound, an aluminum chelate, and barbituric acid is preferable because the effect of improving the storage stability at normal temperature (25 degreeC) is high.

Examples of the liquid boric acid ester compound include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, Triisopropylborate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate , trioctadecyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1 ,4,7-trioxaundecyl)borane, tribenzylborate, triphenylborate, tri-o-tolylborate, tri-m-tolylborate, and triethanolamineborate may be used.

On the other hand, since the liquid boric acid ester compound contained as (E) component is liquid at normal temperature (25 degreeC), since it can suppress low the viscosity of a resin composition, it is preferable.

(E) When making a resin composition contain a liquid boric acid ester compound as a component, it is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of resin compositions, It is more preferable that it is 0.03-3 mass parts, It is 0.1-1 mass part more preferably.

As the aluminum chelate, for example, aluminum trisacetylacetate (eg, ALA manufactured by Kawaken Fine Chemicals Co., Ltd.: aluminum chelate A) can be used.

(E) When making an aluminum chelate contain as a component, it is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of resin compositions, It is more preferable that it is 0.05-5 mass parts, It is still more preferable that it is 0.1-3 mass parts.

(E) When containing barbituric acid as a component, it is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of resin compositions, It is more preferable that it is 0.05-3 mass parts, It is still more preferable that it is 0.1-1 mass part.

The resin composition of one embodiment of the present invention further, if necessary, (F) at least one selected from the group consisting of a silane coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, and a thixotropic agent as another component You may contain an additive. Moreover, you may contain a viscosity modifier, a flame retardant, or a solvent.

Viscosity of the resin composition

The resin composition of one embodiment of the present invention is applied by a dispenser. In general, the discharge part of the dispenser is heated. A cooling system may not be installed in the discharge part of the dispenser. In such a case, even if it is apply|coating at 30 degreeC at first, the discharge part may become 40 degreeC or more with the lapse of time. It is preferable that the resin composition of one Embodiment of this invention has a viscosity in 30 degreeC of 0.05-100 Pa.s, More preferably, it is 0.05-80 Pa.s, More preferably, it is 0.1-70 Pa.s. When the viscosity at 30°C of the resin composition is in the range of 0.05 to 100 Pa·s, the handleability of the resin composition around room temperature is good, and it becomes a suitable viscosity when assembling an image sensor module or a semiconductor device. The viscosity at 30°C is evaluated using a viscoelastic measuring device (rheometer) (for example, TA Instruments Japan Co., Ltd. product number: ARES-G2), and evaluation in the Examples described later. It can be measured based on the method.

It is preferable that the resin composition of one Embodiment of this invention has the viscosity in 50 degreeC measured with the rheometer mentioned above 0.05-100 Pa.s, More preferably, 0.05-80 Pa.s, More preferably, 0.1- 70 Pa·s. If the viscosity at 50°C of the resin composition is in the range of 0.05 to 100 Pa·s, the handleability of the resin composition is good even when the resin composition is used in a relatively high temperature environment, and the viscosity is suitable for assembling an image sensor module or a semiconductor device. becomes

As for the resin composition of one Embodiment of this invention, it is preferable that the ratio (30 degreeC viscosity/50 degreeC viscosity) of the viscosity in 50 degreeC of a resin composition and the viscosity in 30 degreeC is 1-4, more Preferably it is 1-3.5, More preferably, it is 1-3. If the ratio of the viscosity at 50°C of the resin composition and the viscosity at 30°C (viscosity at 30°C/viscosity at 50°C) is 1 to 4, even if a change occurs to some extent in the temperature at which the resin composition is used, the There is no need to change handling conditions such as discharge conditions of the panther, and handling properties are good.

Stress absorption (difference in glass transition temperature (Tg) (ΔTg))

The stress absorption property of the hardened|cured material of a resin composition can use the difference (ΔTg) between the loss elastic modulus (Tg1) (°C) and the loss tangent (Tg2) (°C) as an index. In this specification, the loss elastic modulus (Tg1) is the peak temperature of the loss elastic modulus (if there are a plurality of local maximums, the temperature of the maximum value among them), and the loss tangent (Tg2) is the peak temperature of the loss tangent (with a plurality of local maximums). in this case, the temperature at the maximum of these). Whereas the loss modulus (Tg1) indicates the temperature at which the cured resin starts to change from the glass region to the glass transition region, the loss tangent (Tg2) indicates that the physical properties of the cured resin are intermediate between the glass region and the rubber region, In addition, the temperature at which the cured resin material has the highest ability to absorb stress given from the outside by deforming it. Therefore, it can be said that the larger the temperature difference between the loss elastic modulus (Tg1) and the loss tangent (Tg2) is, the wider the glass transition region is and the easier it is to absorb stress in a wide temperature region. The loss elastic modulus Tg1 and the loss tangent Tg2 can be mechanically calculated by measurement with a dynamic viscoelasticity measuring apparatus (DMA), a rheometer, or the like. On the other hand, when measured by DMA, the loss modulus is represented by E'' and the loss tangent is represented by tan?

In the resin composition of one embodiment of the present invention, the temperature difference between the loss elastic modulus E'' (Tg1) and the loss tangent tanδ (Tg2) measured by DMA of the cured product is preferably 10° C. or more, and more preferably 12° C. or more, , more preferably 14°C or higher. In addition, when the glass transition region is too wide, the stress absorption is relatively lowered. Therefore, the temperature difference is preferably 50°C or less, more preferably 40°C or less, and still more preferably 30°C or less.

The loss modulus (Tg1) (°C) and loss tangent (Tg2) (°C) of the cured product obtained by curing the resin composition of one embodiment of the present invention is, for example, a dynamic viscoelasticity measuring device (eg, SI Nanotechnology). Manufactured by the Company, product name: DMS6100) can be used for measurement. The temperature increase rate can be, for example, 1 to 5°C/min.

Method for producing a resin composition

The resin composition of one Embodiment of this invention can be manufactured by adding the said (A) component - (D) component, and (E) component as needed, and kneading|mixing. The manufacturing method of a resin composition is not specifically limited. For example, the resin composition according to the present embodiment is a raw material containing the component (A) to component (D) and, if necessary, component (E) is mixed with a grinding machine, a pot mill, a three-roll mill, a hybrid mixer, and a rotary type. It can manufacture by mixing with mixers, such as a mixer or a twin-screw mixer. These components may be mixed simultaneously, a part may be mixed first, and may be mixed later. Moreover, you may use combining the said apparatus suitably.

glue

The adhesive of one embodiment of the present invention uses the above-described resin composition. The adhesive of one embodiment of the present invention has good handling properties during use, can be cured at low temperature, does not impair physical properties, and can obtain a cured product excellent in stress absorption. As specific thermosetting conditions, they are 60 degreeC or more and 120 degrees C or less, for example.

encapsulant

The encapsulant of one embodiment of the present invention uses the above-described resin composition. The encapsulant of one embodiment of the present invention has good handling properties during use, can be cured at a low temperature, does not impair physical properties, and can obtain a cured product excellent in stress absorption. As specific thermosetting conditions, they are 60 degreeC or more and 120 degrees C or less, for example.

image sensor module

An image sensor module according to an embodiment of the present invention is formed using an adhesive or an encapsulant including the above-described resin composition. The image sensor module also includes the camera module of a mobile phone or smartphone. The resin composition of one embodiment of the present invention has good handleability when used, can be cured at a low temperature, does not impair physical properties, and can obtain a cured product excellent in stress absorption. It can be preferably used as a resin composition included in an adhesive or encapsulant used for assembling an image sensor module requiring curing.

semiconductor device

The semiconductor device of one embodiment of the present invention is formed using an adhesive or encapsulant containing the above-described resin composition. A semiconductor device refers to an overall device that can function by using semiconductor characteristics, and includes electronic components, semiconductor circuits, modules, electronic devices, and the like in which they are inserted. The resin composition of one embodiment of the present invention has good handling properties when used, can be cured at a low temperature of about 80° C., does not impair physical properties, and can obtain a cured product excellent in stress absorption, so It can be preferably used as a resin composition included in an adhesive or encapsulant used for assembling an image sensor module requiring curing.

Example

Hereinafter, the present invention will be specifically described by way of Examples. The present invention is not limited to these examples.

Examples and Comparative Examples

Each component was mixed by the compounding shown in following Table 1 or 2, and the resin composition was prepared. In addition, in the following table|surface, all the numbers which show the compounding ratio of (A) component - (F) component have shown the mass part. Each component in Table 1 or 2 is as follows.

(A) component: epoxy resin

(A1) EPICLON EXA-850CRP: bisphenol A epoxy resin, DIC Corporation, weight average molecular weight: 344, epoxy equivalent: 172 g/eq.

(A2) YDF8170: Bisphenol F-type epoxy resin, Nittetsu Chemicals & Materials Co., Ltd., weight average molecular weight: 316, epoxy equivalent: 158 g/eq.

(A3) YX8000: Hydrogenated bisphenol A epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., weight average molecular weight 410, epoxy equivalent: 205 g/eq.

(A4) YX7400: Epoxy resin represented by formula (A-1-1) and x in formula (A-1-1) is 10.3, manufactured by Mitsubishi Chemical Co., Ltd., weight average molecular weight 870, epoxy equivalent: 435 g/eq.

(A5) TSL9906: Epoxy resin represented by Formula (A-2), wherein R ^{6 to R 9} in Formula (A-2) are methyl groups, manufactured by Momentive Performance Materials, weight average molecular weight 296, epoxy equivalent 181 g/eq.

thiol compound

(B) component: bifunctional thiol compound

(B1) Thiol compound 1: A bifunctional thiol compound represented by formula (B-1-1), manufactured by Shikoku Chemical Industries, Ltd., molecular weight 389, thiol equivalent: 211 g/eq.

(B2) thiol compound 2: bifunctional thiol compound represented by 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 the formula (B-3-1), manufactured by Shikoku Chemical Industries, Ltd., molecular weight 286, thiol equivalent: 159 g/eq.

(B') (B) thiol compounds other than the component

(B'4) DMDO: 3,6-dioxa-1,8-octane dithiol (1,8-dimercapto-3,6-dioxaoctane), manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 182, thiol equivalent 91 g /eq.

(B'5) 1,10-decanedithiol, Tokyo Chemical Industry Co., Ltd. make, molecular weight 206, thiol equivalent 103 g/eq.

(B'6) EPMG-4: tetraethylene glycol bis(3-mercaptopropionate), manufactured by SC Organic Chemical Co., Ltd., molecular weight 372, thiol equivalent 186 g/eq.

(B'7) PEMP: pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), SC Organic Chemical Co., Ltd. make, molecular weight 489, thiol equivalent 122 g/eq.

(B'8) C3 TS-G: 1,3,4,6-tetrakis (3-mercaptopropyl) glycoluril, manufactured by Shikoku Chemical Industries, Ltd., molecular weight 432, thiol equivalent 114 g/eq.

(C) component: amine compound

(C1) Fujicure FXR-1121: Solid dispersion type amine adduct, manufactured by T&K TOKA Corporation.

(C2) HXA9322HP: solid dispersion type amine adduct latent curing catalyst (microcapsule type imidazole adduct), manufactured by Asahi Kasei Co., Ltd., 1/3 of the weight is microcapsule type imidazole adduct, 2/trivalent bisphenol A mixture of A-type epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent 180g/eq.

(C3) Fujicure FXR-1020, a tertiary amine compound, manufactured by T&K TOKA Corporation.

(D) Ingredient: Filler

(D1) SOE5: Silica filler, manufactured by Admatex Co., Ltd., average particle diameter of 1.5 µm.

(D2) BSP6: Silica filler, manufactured by Tatsumori Co., Ltd., average particle diameter of 5 µm.

(D') fillers other than the (D) component

(D'3) MSV-25G: Silica filler, manufactured by Tatsumori Co., Ltd., average particle diameter of 25 µm.

(E) Ingredient: Stabilizer

(E1) TIPB: triisopropyl borate, manufactured by Tokyo Chemical Industry Co., Ltd.

(F) other ingredients

(F1) KBM403: 3-glycidoxypropyl trimethoxysilane (silane coupling agent), manufactured by Shin-Etsu Chemical Co., Ltd.

Assessment Methods

volatility

A metal container having a diameter of 5 cm and a depth of 0.5 cm is measured. 1.0 g of the thiol compound was added thereto, and it was left to stand in an oven at 80° C. without a lid for 1 hour. After standing to cool, the weight of the metal container was measured and the volatile matter from the thiol resin was measured. As a result, the volatile content of 1,10-decanedithiol is 11% and the volatile content of 3,6-dioxa-1,8-octanedithiol is 27%, compared to that containing thiol compounds 1, 2 and 3 All of the volatile matter of the thiol resin outside was 1% or less.

measurement of viscosity

The viscosity of the resin composition of an Example and a comparative example was heated up from 25 degreeC, and the viscosity (Pa*s) in 30 degreeC and the viscosity (Pa*s) in 50 degreeC were measured. For the measurement, a viscoelastic measuring device (rheometer) (manufactured by Thermo Fisher Scientific Co., Ltd., product number: MARS60) was used. Measurement conditions are shown below. Moreover, ratio (30 degreeC viscosity/50 degreeC viscosity) of the viscosity of 30 degreeC with respect to the 50 degreeC viscosity of the resin composition was calculated|required. Ratio of this viscosity is preferable in it being 1-4, more preferably in it being 1-3.8, still more preferable in it being 1-3.5, and still more preferable in it being 1-3.

Plate diameter: 35 mmφ (parallel type)

Frequency: 1Hz

Distortion: 0.5

Temperature increase rate: 3°C/min

Gap: 500 μm

Calculation of difference (ΔTg) in glass transition temperature (Tg)

Loss tangent to loss modulus E'' (Tg1) (°C) of cured products obtained by curing the resin compositions of Examples and Comparative Examples using a dynamic viscoelasticity measuring device (DMA) (manufactured by SI Nanotechnology Co., Ltd., product name: DMS6100) The tan δ°C was measured. Prepare two glass plates to which Teflon (registered trademark) tape is affixed, and place a 125 µm spacer film and a resin composition on the Teflon (registered trademark) tape surface of one glass plate, and Teflon (registered trademark) tape surfaces Further, one glass plate was placed so as to oppose, and a cured product having a thickness of about 130 μm was obtained by heat curing at 80° C. 180 min with a blow dryer. Moreover, when the obtained hardened|cured material was brittle, the thickness of a spacer film was changed suitably, and hardened|cured material was produced. After peeling this hardened|cured material from a glass plate, the test piece (10+/-0.5 mm x 40+/-1 mm) was cut out from the hardened|cured material, and the width|variety and thickness of the test piece were measured. Then, it measured using the above-mentioned dynamic viscoelasticity measuring apparatus (temperature increase rate: 3 degreeC/min, frequency: 10 Hz, measurement range: -40 to 150 degreeC, strain amplitude 5.0 micrometers, tensile method). The peak temperature of tan δ (loss tangent) (when there are a plurality of local maximums, the temperature of the maximum value among them) was read, and it was set as the glass transition temperature (Tg2). In addition, the peak temperature of loss elastic modulus E'' (when there are two or more local maximums, the temperature of the maximum value among these) was read, and it was set as the glass transition temperature (Tg1). ΔTg(°C), which is the difference between the glass transition temperature (Tg1) (°C) and the glass transition temperature (Tg2) (°C), was calculated. ΔTg is preferably 12°C or higher.

hydrolysis resistance

Under the same conditions as the above DMA measurement, a cured product having a thickness of about 130 μm was produced. When the resin composition contains a compound containing an ester bond, it is hydrolyzed at high temperature and high humidity, and the cured resin of the compositions of Comparative Examples 5 and 6 was placed under PCT conditions (121° C., 2 atm) for 10 hours. The cured resin was liquefied and had poor hydrolysis resistance. On the other hand, in the compositions of Examples 15 and 16, which included a thiol compound including an ester bond in the resin composition, but in which the bifunctional thiol compound according to the present invention was used in combination, no abnormality was found in the appearance of the cured resin.

The cured products obtained from the resin compositions of Examples 1 to 20 had good hydrolysis resistance and low volatility, and no voids were mixed in the cured products after curing. Moreover, since the ratio (30 degreeC viscosity/50 degreeC viscosity) of the 30 degreeC viscosity with respect to the 50 degreeC viscosity of the resin composition of Examples 1-20 is 1-4, the environmental atmosphere using a resin composition Regardless, it was confirmed that the handleability of the resin composition was good. Further, it was confirmed that the cured product obtained by curing the resin compositions of Examples 1 to 20 had a ΔTg of 12° C. or higher, a large glass transition region, and excellent stress absorption.

The cured products obtained from the resin compositions of Comparative Examples 5 and 6 were easily hydrolyzed because the resin composition contained a compound containing an ester bond, and moisture resistance was not improved. Moreover, voids were mixed in the hardened|cured material obtained by hardening|curing the resin composition of Comparative Examples 3 and 4. In the resin compositions of Comparative Examples 1 to 6, the ratio of the viscosity at 30°C to the viscosity at 50°C (viscosity at 30°C/viscosity at 50°C) is 4 or more, so it is difficult to handle depending on the environmental temperature. there was. In addition, it was confirmed that the cured product obtained by curing the resin composition of Comparative Example 6 had a ΔTg of about 10° C., a narrow glass transition region compared to other compositions, and poor stress absorption.

Claims (15)

(A) an epoxy resin;
(B) a bifunctional thiol compound having an aromatic ring structure or an alicyclic structure in the molecule, and a molecular chain containing a hetero atom and not including an ester bond, having a thiol group at the terminal, and having a molecular weight of 210 or more, and an aromatic in the molecule At least one selected from the group consisting of a ring structure or a heterocyclic structure and a bifunctional thiol compound having a molecular weight of 210 or more, including a molecular chain having a thiol group at the terminal, which may contain a hetero atom or does not contain an ester bond. and a bifunctional thiol compound of
(C) an amine compound;
(D) The resin composition containing the filler whose average particle diameter is 0.1 micrometer or more and 10 micrometers or less. The method of claim 1,
The resin composition wherein the component (B) is a bifunctional thiol compound comprising an alicyclic structure and a molecular chain containing a thioether bond but not an ester bond and having a thiol group at a terminal in the molecule. The method of claim 1,
The resin composition wherein the component (B) is a bifunctional thiol compound comprising an aromatic ring structure in a molecule and a molecular chain having a thiol group at the terminal, including an ether bond but not an ester bond. The method of claim 1,
A resin composition wherein the component (B) is a bifunctional thiol compound represented by the following formula (B-1), (B-2), or (B-3):

(in formula (B-1), n and m are each independently an integer of 1 to 3)

(In 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 formula (b-1); provided that either ^{R 1} or R ^{2 is} is a group represented by the following formula (b-1), ^{and either one of R 3} and R ⁴ is a group represented by the following formula (b-1))

(in formula (b-1), r is an integer of 1-3)

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

(in formula (B-4), s and t are each independently an integer of 3 or 4)

(In formula (B-5), u and v are each independently an integer of 3 or 4). 6. The method according to any one of claims 1 to 5,
The resin composition whose weight average molecular weights of the said (A) component are 240-1,000. 7. The method according to any one of claims 1 to 6,
The resin composition 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. 8. The method according to any one of claims 1 to 7,
A resin composition in which the total number of thiol groups in the bifunctional thiol compound of the component (B) is 20 to 100 when the total number of thiol groups in the resin composition is 100. 9. The method according to any one of claims 1 to 8,
The resin composition whose content of the filler of the said (D) component is 5-70 mass % with respect to 100 mass % of whole amounts of a resin composition. 10. The method according to any one of claims 1 to 9,
(E) A resin composition further comprising a stabilizer. 11. The method of claim 10,
The resin composition wherein the stabilizer of the component (E) is at least one selected from the group consisting of a liquid boric acid ester compound, an aluminum chelate, and a barbituric acid. An adhesive comprising the resin composition of any one of claims 1 to 11. An encapsulant comprising the resin composition of any one of claims 1 to 11. An image sensor module manufactured using the adhesive of claim 12 or the encapsulant of claim 13. A semiconductor device manufactured using the adhesive of claim 12 or the encapsulant of claim 13.