Resin composition

Abstract

The resin composition comprises: (A) an epoxy resin; (B) at least one bifunctional thiol compound selected from the group consisting of bifunctional thiol compounds having an aromatic ring structure or an alicyclic structure in the molecule, a heteroatom, no ester bond, and a molecular chain having a thiol group at its terminal, and having a molecular weight of 210 or more; and bifunctional thiol compounds having an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain that may contain a heteroatom, no ester bond, and has a thiol group at its terminal, and having a molecular weight of 210 or more; (C) an amine compound; and (D) a filler having an average particle size of 0.1 μm or more and 10 μm or less.

Description

[Technical field]

[0001] The present invention relates to a resin composition that can be used in applications requiring heat curing at a relatively low temperature, specifically, at about 80°C. [Background technology]

[0002] In assembling a structure during the manufacture of an image sensor module used as a camera module for a mobile phone or smartphone, an adhesive or sealant that is thermoset at a relatively low temperature, specifically, at a temperature of about 80° C., is used. Also in the manufacture of semiconductor devices that include electronic components such as semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors, it is preferable to use an adhesive or sealant that contains a resin composition that is thermoset at a temperature of about 80° C.

[0003] In addition, adhesives or sealing materials used in manufacturing image sensor modules and semiconductor devices are also required to have moisture resistance. Furthermore, mobile devices such as mobile phones and smartphones are required to have impact resistance against drops, etc., and cured products such as adhesives used in semiconductor devices are required to have stress absorption properties.

[0004] For example, Patent Document 1 discloses a resin composition containing a thiol compound having four thiol groups in its molecule as a one-component adhesive that can be thermally cured at low temperatures and has excellent resistance even in a pressure cooker test (hereinafter also referred to as "PCT"), which is tested at high temperatures and high humidity of 100°C or higher and a humidity of 70% or higher. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2015 / 141347 Summary of the Invention [Problem to be solved by the invention]

[0006] However, resin compositions mainly composed of polythiol compounds having four thiol groups in a molecule have many crosslinking points, and the resulting cured product may have poor stress absorption. In addition, adhesives and sealants used in assembling image sensor modules and semiconductor devices are required to have moisture resistance after curing and to have small viscosity changes due to temperature changes during application.

[0007] Therefore, an object of the present invention is to provide a resin composition which can be cured at low temperatures, gives a cured product having excellent moisture resistance and stress absorption properties, and has good handleability during use. [Means for solving the problem]

[0008] The means for solving the above problems are as follows, and the present invention includes the following aspects. [1] (A) an epoxy resin; (B) at least one bifunctional thiol compound selected from the group consisting of bifunctional thiol compounds having an aromatic ring structure or an alicyclic structure in the molecule, a heteroatom, no ester bond, and a molecular chain having a thiol group at an end, and having a molecular weight of 210 or more, and bifunctional thiol compounds having an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain having a thiol group at an end, which may contain a heteroatom, no ester bond, and having a molecular weight of 210 or more; (C) an amine compound; (D) a filler having an average particle size of 0.1 μm or more and 10 μm or less. [2] The resin composition according to [1] above, wherein the component (B) is a bifunctional thiol compound that contains an alicyclic structure in the molecule and a molecular chain that contains a thioether bond, does not contain an ester bond, and has a thiol group at an end. [3] The resin composition according to [1] above, wherein the component (B) is a bifunctional thiol compound that contains an aromatic ring structure in the molecule and a molecular chain that contains an ether bond but not an ester bond and has a thiol group at an end. [4] The resin composition according to [1] above, wherein the component (B) is a bifunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3). [Chemical formula] (In general formula (B-1), n and m are each independently an integer from 1 to 3.)

[0009] [Chemical formula] (In 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, either one of R 1 and R 2 is a group represented by the following general formula (b-1), and either one of R 3 and R 4 is a group represented by the following general formula (b-1).) [Chemical formula] (In general formula (b-1), r is an integer from 1 to 3.)

[0010] [Chemical formula] (In general formula (B-3), G 1 , G 2 are each independently a divalent group bonded by -O- or -CH 2 -, and p and q are each independently an integer from 2 to 5.) [5] The resin composition according to [1] above, wherein the component (B) is a bifunctional thiol compound represented by the following general formula (B-4) or (B-5).

[0011] [Chemical formula] (In general formula (B-4), s and t are each independently an integer of 3 or 4.)

[0012] [Chemical formula] (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 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 amine compound of the component (C) is at least one amine compound selected from imidazole-based compounds, tertiary amine-based compounds, and amine adducts. [8] The resin composition according to any one of [1] to [7], wherein the total number of thiol groups of the bifunctional thiol compound of the component (B) is 20 to 100 when the total number of all thiol groups in the resin composition is 100. [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% by mass based on 100% by mass of the total amount of the resin composition.

[10] The resin composition according to any one of [1] to [9], further comprising (E) 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 liquid boric acid ester compounds, aluminum chelates, and 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

[12] or the sealing material according to

[13] .

[15] A semiconductor device manufactured using the adhesive according to

[12] or the sealing material according to

[13] . [Advantages of the Invention]

[0013] 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., which gives a cured product which has excellent moisture resistance and stress absorption properties, and which is easy to handle when used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, the resin composition, adhesive, encapsulant, image sensor module, and semiconductor device according to the present disclosure will be described based on their embodiments. However, the embodiments shown below are merely examples for embodying the technical concept of the present invention, and the present invention is not limited to the following resin composition, adhesive, encapsulant, image sensor module, and semiconductor device.

[0015] The resin composition according to the first embodiment of the present invention comprises: (A) an epoxy resin; (B) at least one bifunctional thiol compound selected from the group consisting of bifunctional thiol compounds having an aromatic ring structure or an alicyclic structure in the molecule, a heteroatom, no ester bond, and a molecular chain having a thiol group at an end, and having a molecular weight of 210 or more, and bifunctional thiol compounds having an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain having a thiol group at an end, which may contain a heteroatom, no ester bond, and having a molecular weight of 210 or more; (C) an amine compound; (D) a filler having an average particle size of 0.1 μm or more and 10 μm or less.

[0016] Component (A): Epoxy resin The resin composition contains an epoxy resin as component (A). Examples of the epoxy resin of component (A) include polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol with epichlorohydrin, epoxy resins having a naphthalene skeleton such as 1,6-bis(2,3-epoxypropoxy)naphthalene, epoxidized phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, cyclic aliphatic epoxy resins, urethane-modified epoxy resins, and silicone-modified epoxy resins. However, the epoxy resin is not limited to these resins. The epoxy resin of 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. Examples of such epoxy resins include bisphenol A type epoxy resins and bisphenol F type epoxy resins.

[0017] The epoxy resin of component (A) may be an epoxy resin that does not contain an aromatic ring. Here, the aromatic ring is a structure that satisfies the Huckel rule, for example, a benzene ring. As the epoxy resin of component (A), the epoxy resin that does not contain an aromatic ring may be hydrogenated bisphenol type epoxy resin, alicyclic epoxy resin, alcohol ether type epoxy resin, aliphatic epoxy resin, etc. However, it is not limited to these resins. As such epoxy resin, for example, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, epoxy modified polybutadiene, 1,4-cyclohexanedimethanol diglycidyl ether, etc. may be mentioned. When an epoxy resin that does not contain an aromatic ring is used as component (A), the number of epoxy groups contained in the epoxy resin that does not contain an aromatic ring is preferably 20 to 100, more preferably 40 to 100, and even more preferably 50 to 100, when the number of all epoxy groups in the resin composition is 100, from the viewpoint of viscosity and adhesiveness.

[0018] An example of the epoxy resin of the component (A) is an epoxy resin represented by the following formula (A-1).

[0019] [Chemistry]

[0020] In formula (A-1), R 5 is a linear or branched alkylene group having 1 to 15 carbon atoms, and w is an integer from 1 to 20.

[0021] The epoxy resin represented by formula (A-1) may be an epoxy resin represented by the following formula (A-1-1) and / or (A-1-2).

[0022] [Chemistry]

[0023] In formula (A-1-1), x is an integer from 1 to 15.

[0024] [Chemistry]

[0025] In formula (A-1-2), y is an integer from 1 to 20.

[0026] The epoxy resin of component (A) may be, for example, an epoxy resin represented by the following formula (A-2).

[0027] [Chemistry]

[0028] In formula (A-2), R 6 ~R 9 are each independently a linear or branched alkyl group having 1 to 3 carbon atoms.

[0029] From the viewpoint of the balance between viscosity and volatility, the epoxy resin of component (A) preferably has a weight average molecular weight of 240 to 1,000. The epoxy resin of component (A) more preferably has a weight average molecular weight of 250 to 1,000, even more preferably 260 to 1,000, and even more preferably 270 to 1,000. If the weight average molecular weight of the epoxy resin of component (A) is less than 240, it is likely to become highly volatile and voids may occur in the cured product. On the other hand, if the weight average molecular weight of the epoxy resin of component (A) exceeds 1,000, it may become highly viscous and workability may deteriorate. In this specification, the weight average molecular weight refers to a value obtained by using a calibration curve of standard polystyrene by gel permeation chromatography (GPC).

[0030] (B) Component: Bifunctional thiol compound The (B) bifunctional thiol compound contained in the resin composition of one embodiment of the present invention is at least one bifunctional thiol compound selected from the group consisting of bifunctional thiol compounds having an aromatic ring structure or an alicyclic structure in the molecule, a molecular chain containing a heteroatom, not containing an ester bond, and having a thiol group at the end, and having a molecular weight of 210 or more, and bifunctional thiol compounds having an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain containing a thiol group at the end, which may contain a heteroatom, not containing an ester bond, and having a molecular weight of 210 or more. The (B) component bifunctional thiol compound is available from Shikoku Chemical Industry Co., Ltd.

[0031] The bifunctional thiol compound of component (B) has a molecular weight of 210 or more and low volatility, so that when the resin composition is thermally cured at a low temperature of, for example, 80°C, the bifunctional thiol compound does not volatilize, the generation of voids is suppressed, and a cured product that maintains its physical properties can be obtained. The molecular weight is more preferably 280 or more. In addition, from the viewpoint of curability, the bifunctional thiol compound of component (B) preferably has a molecular weight of 1,000 or less, more preferably 600 or less.

[0032] The bifunctional thiol compound of the component (B) has a heteroatom and has good compatibility with the epoxy resin of the component (A), and can obtain a homogeneous cured product by curing at a low temperature of, for example, 80°C. The aromatic ring structure of the component (B) is a monocyclic aromatic ring structure having 5 or more members, such as cyclopentadiene and benzene. The alicyclic structure is a monocyclic alicyclic structure having 5 or more members, such as cyclopentane and cyclohexene. The heterocyclic structure may be a monocyclic or polycyclic structure, may be an alicyclic structure having a heteroatom, may be an aromatic ring structure having a heteroatom, or may be a condensed polycyclic structure having a heteroatom. The heteroatom contained in the molecular chain is, for example, a sulfur (S) or oxygen (O) atom, and it is preferable that the molecular chain contains a thioether bond or an ether bond. From the viewpoint of compatibility with epoxy resins and low volatility, the bifunctional thiol compound of the component (B) preferably has a sulfur atom as the heteroatom, i.e., has an alicyclic structure in the molecule, a thioether bond, no ester bond, and a molecular chain having a thiol group at the end. Also, from the viewpoint of compatibility with epoxy resins and low volatility, the bifunctional thiol compound of the component (B) preferably has an oxygen atom as the heteroatom, i.e., has an aromatic ring structure in the molecule, a thiol group at the end, no ester bond, and a molecular chain having an ether bond, no ester bond, and a thiol group at the end. From the viewpoint of adhesive strength to metals, the bifunctional thiol compound of the component (B) more preferably has an alicyclic structure in the molecule, a thioether bond, and a molecular chain having a thiol group at the end, no ester bond, and a molecular chain having an alicyclic structure in the molecule, a thioether bond, and a thiol group at the end, no ester bond.

[0033] In addition, since the bifunctional thiol compound of component (B) has two thiol groups, when the resin composition is cured, a cured product having superior stress absorption properties can be obtained compared to a cured product mainly composed of a trifunctional or higher thiol compound.

[0034] Furthermore, 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 conditions such as those in PCT, and can maintain the adhesive strength of the resulting cured product.

[0035] The component (B) is preferably, for example, a bifunctional thiol compound represented by the following general formula (B-1): The bifunctional thiol compound represented by (B-1) is available from Shikoku Chemical Industries Co., Ltd.

[0036] [ka]

[0037] In formula (B-1), n ​​and m each independently represent an integer of 1 to 3, and it is preferable that n and m each are 2.

[0038] The bifunctional thiol compound represented by general formula (B-1) is preferably a bifunctional thiol compound represented by the following general formula (B-1-1).

[0039] [ka]

[0040] The component (B) is preferably, for example, a bifunctional thiol compound represented by the following general formula (B-2): The bifunctional thiol compound represented by (B-2) is available from Shikoku Chemical Industries Co., Ltd.

[0041] [ka]

[0042] In 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): 1 and R 2 is a group represented by the following general formula (b-1), 3 and R 4 is a group represented by the following general formula (b-1).

[0043] [ka]

[0044] In the general formula (b-1), r is an integer of 1 to 3, and is preferably 2.

[0045] The bifunctional thiol compound represented by general formula (B-2) is preferably a bifunctional thiol compound represented by the following general formula (B-2-1).

[0046] [ka]

[0047] The component (B) is preferably, for example, a bifunctional thiol compound represented by the following general formula (B-3): The bifunctional thiol compound represented by (B-3) is available from Shikoku Chemical Industries Co., Ltd.

[0048] [ka]

[0049] In general formula (B-3), G 1 , G 2 each independently represents -O- or -CH 2 G is a divalent group bonded with -, and p and q are each independently an integer of 2 to 5. 1 , G 2 is preferably a divalent group bonded via --O--, and p and q are preferably 3 or 4, and more preferably 4.

[0050] The bifunctional thiol compound represented by the general formula (B-3) is preferably a bifunctional thiol compound represented by the following general formula (B-3-1).

[0051] [ka]

[0052] The component (B) is preferably a bifunctional thiol compound represented by, for example, the following general formula (B-4). The bifunctional thiol compound represented by (B-4) can be obtained from Shikoku Kasei Kogyo Co., Ltd.

[0053]

Chemical formula

[0054] In the general formula (B-4), s and t are each independently an integer of 3 or 4, and preferably 4.

[0055] The component (B) is preferably a bifunctional thiol compound represented by, for example, the following general formula (B-5). The bifunctional thiol compound represented by (B-5) can be obtained from Shikoku Kasei Kogyo Co., Ltd.

[0056]

Chemical formula

[0057] In the general formula (B-5), u and v are each independently an integer of 3 or 4, and preferably 4.

[0058] The resin composition according to an embodiment of the present invention may further contain a thiol compound (monofunctional thiol compound, bifunctional thiol compound, trifunctional or higher thiol compound) other than the component (B). The number of thiol groups contained in the bifunctional thiol compound of the component (B) is preferably 20 to 100, more preferably 40 to 100, and even more preferably 50 to 100, when the number of all thiol groups in the resin composition is 100. The equivalent ratio (epoxy equivalent: thiol equivalent) of the thiol groups of all thiol compounds 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 equivalents or more than 1.5 equivalents relative to the epoxy equivalent of the epoxy resin contained in the resin composition, unreacted epoxy resin or thiol compound remains in the cured product, and the adhesive strength of the resin composition decreases.

[0059] Component (C): Amine compound In the resin composition according to one embodiment of the present invention, the amine compound of the component (C) is preferably at least one amine compound selected from imidazole compounds, tertiary amine compounds, and amine adducts. The amine compound of the component (C) is preferably one that functions as a curing accelerator for epoxy resins. For example, the amine compound of the component (C) is preferably a compound that is an insoluble solid at room temperature and is soluble by heating to function as a curing accelerator, and examples thereof include imidazole compounds, tertiary amine compounds, and solid dispersion-type amine adduct-type latent curing accelerators that are solid at room temperature, such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct-type latent curing accelerators), and reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct-type latent curing accelerators).

[0060] Examples of the imidazole compounds include 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-triazine, and 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine isoform. Examples of the imidazole include, but are not limited to, cyanuric 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)-adiboyldiamide, and the like.

[0061] Examples of the tertiary amine compounds include primary or secondary amines having a tertiary amino group in the molecule, such as amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, and imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 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, and 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazo 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-tris(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, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, etc. Examples of commercially available tertiary amine compounds include Fujicure FXR-1030 and Fujicure FXR-1020 (manufactured by T&K TOKA Corporation).

[0062] Examples of commercially available solid dispersion type amine adduct latent curing accelerators include Novacure HXA9322HP (manufactured by Asahi Kasei Corporation), Fujicure FXR-1121 (manufactured by T&K TOKA Corporation), Amicure PN-23, and Amicure PN-F (manufactured by Ajinomoto Fine-Techno Co., Ltd.) For more detailed examples of solid dispersion type amine adduct latent curing agents or latent curing accelerators, the description of JP2014-77024A is incorporated by reference.

[0063] The content of the amine compound of the component (C) contained in the resin composition varies depending on the type of the amine compound. From the viewpoint of extending the pot life, the amount of the amine compound (C) contained in the resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 35 parts by mass, and even more preferably 1.0 to 30 parts by mass, relative to 100 parts by mass of the epoxy resin contained in the resin composition. Some of the component (C) are provided in the form of a dispersion liquid in which the component (C) is dispersed in an epoxy resin. When such a form of the component (C) is used, the amount of the epoxy resin in which the component (C) is dispersed is also included in the amount of the component (A) in the resin composition of the present invention.

[0064] (D) Ingredient: Filler The filler of component (D) contained in the resin composition of one embodiment of the present invention has an average particle size of 0.1 μm or more and 10 μm or less, preferably 0.1 μm or more and 8 μm or less, more preferably 0.1 μm or more and 5 μm or less, and even more preferably 0.1 μm or more and 3 μm or less. When the average particle size of the filler of 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, the viscosity of the resin composition can be suppressed from decreasing, and the handling property can be improved. When the average particle size of the filler of component (D) is less than 0.1 μm, the viscosity increases and may adversely affect the workability. When the average particle size of the filler of component (D) exceeds 10 μm, the viscosity decreases significantly under heating. The average particle size of the filler refers to the particle size (median size) at which the volume cumulative frequency from the small diameter side in the volume-based particle size distribution measured by the laser diffraction scattering type particle size distribution measurement method reaches 50%. When a commercially available filler is used, the average particle size of the filler can be referred to the average particle size listed in the catalog.

[0065] The content of the filler in the (D) component is preferably 5 to 70% by mass, more preferably 8 to 60% by mass, and even more preferably 10 to 50% by mass, based on 100% by mass of the total amount of the resin composition. If the content of the filler in the (D) component is less than 5% by mass, based on 100% by mass of the total amount of the resin composition, the amount of filler is too small, making it difficult to suppress a decrease in the viscosity of the resin composition, for example, under high temperature (heating), while if it exceeds 70% by mass, the amount of filler is too large, making the viscosity of the resin composition high and making it difficult to handle.

[0066] The particle shape of the filler of component (D) is not particularly limited so long as the average particle size is from 0.1 μm to 10 μm, and for example, spherical or scale-shaped particles can be used.

[0067] The filler of component (D) is not particularly limited in material as long as it has an average particle size of 0.1 μm or more and 10 μm or less, and can be widely selected from fillers added for adhesives or sealants. Specific examples include fillers made of inorganic substances such as silica, alumina, titania, magnesia, and glass. Among these, fillers made of silica and alumina are preferably used from the viewpoint of low thermal expansion and low water absorption. The filler of component (D) may be used alone or in combination of two or more kinds. Examples of commercially available products include silica filler (product name: SOE2, manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm), silica filler (product name: SE1050, manufactured by Admatechs Co., Ltd., average particle size: 0.3 μm), silica filler (product name: MP-8FS, manufactured by Tatsumori Co., Ltd., average particle size: 0.7 μm), silica filler (product name: SOE5, manufactured by Admatechs Co., Ltd., average particle size: 1.5 μm), silica filler (product name: FB5SDX, manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size: 5 μm), silica filler (product name: BSP6, manufactured by Tatsumori Co., Ltd., average particle size: 5 μm), and silica filler (product name: FB7SDX, manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size: 7 μm).

[0068] (E) Ingredient: Stabilizer The resin composition according to one embodiment of the present invention may contain a stabilizer as component (E). By containing the stabilizer as component (E), the resin composition can improve the storage stability at room temperature (25°C) and extend the pot life. As the stabilizer as component (E), at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and barbituric acids is preferred because it is highly effective in improving the storage stability at room temperature (25°C).

[0069] Examples of the liquid boric acid ester compound that can be used include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate. The liquid borate ester compound contained as component (E) is preferred because it is liquid at room temperature (25° C.) and therefore the viscosity of the resin composition can be kept low. When a liquid boric acid ester compound is contained in the resin composition as the component (E), the amount is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the resin composition.

[0070] As the aluminum chelate, for example, aluminum trisacetylacetonate (for example, ALA: aluminum chelate A, manufactured by Kawaken Fine Chemical Co., Ltd.) can be used. When an aluminum chelate is contained as the component (E), the amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the resin composition.

[0071] When barbituric acid is contained as the component (E), the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the resin composition.

[0072] The resin composition according to one embodiment of the present invention may further contain, as other components (F), at least one additive 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 necessary, and may also contain a viscosity modifier, a flame retardant, a solvent, or the like.

[0073] Viscosity of the resin composition The resin composition according to one embodiment of the present invention is applied by a dispenser. Generally, the discharge part of the dispenser is heated. The discharge part of the dispenser may not be provided with a cooling system. In such a case, even if the resin composition is applied at 30°C initially, the temperature of the discharge part may become 40°C or higher over time. The resin composition according to one embodiment of the present invention preferably has a viscosity at 30°C of 0.05 to 100 Pa·s, more preferably 0.05 to 80 Pa·s, and even more preferably 0.1 to 70 Pa·s. When the viscosity of the resin composition at 30°C is in the range of 0.05 to 100 Pa·s, the resin composition has good handleability near room temperature and has a viscosity suitable for assembling an image sensor module or a semiconductor device. The viscosity at 30°C can be measured using a viscoelasticity measuring device (rheometer) (for example, model number: ARES-G2 manufactured by TA Instrument Japan Co., Ltd.) based on the evaluation method in the examples described below.

[0074] The resin composition of one embodiment of the present invention preferably has a viscosity of 0.05 to 100 Pa·s, more preferably 0.05 to 80 Pa·s, and even more preferably 0.1 to 70 Pa·s at 50°C, as measured with the above-mentioned rheometer. When the resin composition has a viscosity of 0.05 to 100 Pa·s at 50°C, the resin composition has good handleability even when used in a relatively high temperature environment, and has a viscosity suitable for assembling an image sensor module or a semiconductor device.

[0075] In the resin composition according to one embodiment of the present invention, the ratio of the viscosity of the resin composition at 50° C. to the viscosity at 30° C. (viscosity at 30° C. / viscosity at 50° C.) is preferably 1 to 4, more preferably 1 to 3.5, and even more preferably 1 to 3. When the ratio of the viscosity of the resin composition at 50° C. to the viscosity at 30° C. (viscosity at 30° C. / viscosity at 50° C.) is 1 to 4, even if there is some change in the temperature at which the resin composition is used, there is no need to change the handling conditions, such as the discharge conditions of a dispenser, and the handleability is good.

[0076] Stress absorption (difference in glass transition temperature (Tg) (ΔTg)) The stress absorption of the cured resin composition can be indexed by the difference (ΔTg) between the loss modulus (Tg1) (°C) and the loss tangent (Tg2) (°C). In this specification, the loss modulus (Tg1) is the peak temperature of the loss modulus (if there are multiple maximal values, the temperature of the maximum value among them), and the loss tangent (Tg2) is the peak temperature of the loss tangent (if there are multiple maximal values, the temperature of the maximum value among them). The loss modulus (Tg1) indicates the temperature at which the cured resin begins to change from the glass region to the glass transition region, whereas the loss tangent (Tg2) indicates the temperature at which the physical properties of the cured resin are intermediate between the glass region and the rubber region, and at which the cured resin has the highest ability to absorb stress applied from the outside by deforming. Therefore, it can be said that the larger the temperature difference between the loss modulus (Tg1) and the loss tangent (Tg2), the wider the glass transition region and the easier it is to absorb stress in a wide temperature range. The loss modulus (Tg1) and loss tangent (Tg2) can be mechanically calculated by measurement using a dynamic viscoelasticity measuring device (DMA) or a rheometer, etc. When measured by DMA, the loss modulus is expressed as E'' and the loss tangent is expressed as tan δ.

[0077] In a resin composition according to one embodiment of the present invention, the temperature difference between the loss modulus E'' (Tg1) and the loss tangent tan δ (Tg2) of a cured product measured by DMA is preferably 10°C or more, more preferably 12°C or more, and even more preferably 14°C or more. Furthermore, if the glass transition region is too wide, the stress absorption property relatively decreases, so the temperature difference is preferably 50°C or less, more preferably 40°C or less, and even 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 can be measured, for example, using a dynamic viscoelasticity measuring device (for example, SII NanoTechnology, product name: DMS6100). The temperature rise rate can be, for example, 1 to 5°C / min.

[0078] Method for producing resin composition The resin composition according to one embodiment of the present invention can be produced by adding and kneading the components (A) to (D) and, if necessary, the component (E). The method for producing the resin composition is not particularly limited. For example, the resin composition according to this embodiment can be produced by mixing raw materials including the components (A) to (D) and, if necessary, the component (E) using a mixer such as a mortar mixer, a pot mill, a triple roll mill, a hybrid mixer, a rotary mixer, or a twin-shaft mixer. These components may be mixed simultaneously, or some of them may be mixed first and the rest may be mixed later. The above devices may also be used in appropriate combination.

[0079] glue The adhesive of one embodiment of the present invention uses the above-mentioned resin composition. The adhesive of one embodiment of the present invention has good handling properties during use, can be cured at low temperatures, and can obtain a cured product with excellent stress absorption properties without impairing physical properties. Specific heat curing conditions are, for example, 60°C or higher and 120°C or lower.

[0080] Encapsulating materials The encapsulant of one embodiment of the present invention uses the above-mentioned resin composition. The encapsulant of one embodiment of the present invention has good handling properties during use, can be cured at low temperatures, and can obtain a cured product with excellent stress absorption properties without impairing physical properties. Specific heat curing conditions are, for example, 60°C or higher and 120°C or lower.

[0081] Image Sensor Module An image sensor module according to one embodiment of the present invention is formed using an adhesive or a sealant containing the above-mentioned resin composition. The image sensor module also includes a camera module for a mobile phone or a smartphone. The resin composition according to one embodiment of the present invention has good handleability during use, can be cured at low temperatures, and can give a cured product with excellent stress absorption properties without impairing physical properties. Therefore, the resin composition can be suitably used as a resin composition contained in an adhesive or a sealant used in assembling an image sensor module that requires curing at a low temperature of about 80°C.

[0082] Semiconductor Device A semiconductor device according to one embodiment of the present invention is formed using an adhesive or a sealant containing the resin composition described above. The semiconductor device generally refers to devices that can function by utilizing semiconductor properties, and includes electronic components, semiconductor circuits, modules incorporating these, and electronic devices. The resin composition according to one embodiment of the present invention has good handleability during use, can be cured at a low temperature of about 80°C, and can obtain a cured product with excellent stress absorption properties without impairing physical properties, and can therefore be suitably used as a resin composition contained in an adhesive or sealant used in the assembly of an image sensor module that requires curing at a low temperature. EXAMPLES

[0083] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0084] Examples and Comparative Examples Resin compositions were prepared by mixing the components according to the ratios shown in Tables 1 and 2 below. In the tables below, the figures showing the mixing ratios of components (A) to (F) all indicate parts by mass. The components in Tables 1 and 2 are as follows.

[0085] Component (A): Epoxy resin (A1) EPICLON EXA-850CRP: bisphenol A type epoxy resin, DIC Corporation, weight average molecular weight: 344, epoxy equivalent: 172g / eq. (A2) YDF8170: Bisphenol F type epoxy resin, Nippon Steel Chemical & Material Co., Ltd., weight average molecular weight: 316, epoxy equivalent: 158g / eq. (A3) YX8000: hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 410, epoxy equivalent: 205 g / eq. (A4) YX7400: epoxy resin represented by general formula (A-1-1), where x in general formula (A-1-1) is 10.3, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 870, epoxy equivalent: 435 g / eq. (A5) TSL9906: Represented by general formula (A-2), R in general formula (A-2) 6 ~R 9 Epoxy resin with methyl groups, manufactured by Momentive Performance Materials, weight average molecular weight 296, epoxy equivalent weight 181g / eq.

[0086] Thiol Compounds (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) DMDO: 3,6-dioxa-1,8-octanedithiol (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, manufactured by Tokyo Chemical Industry Co., Ltd., 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), manufactured by SC Organic Chemicals Co., Ltd., 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 Industry Co., Ltd., molecular weight 432, thiol equivalent 114 g / eq.

[0087] Component (C): 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 (microencapsulated imidazole adduct), manufactured by Asahi Kasei Corporation, 1 / 3 of the weight is microencapsulated imidazole adduct, 2 / 3 is a mixture of bisphenol 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.

[0088] (D) Ingredient: Filler (D1) SOE5: Silica filler, manufactured by Admatechs Co., Ltd., average particle size 1.5 μm. (D2) BSP6: Silica filler, manufactured by Tatsumori Co., Ltd., average particle size 5 μm. (D') Filler other than component (D) (D'3) MSV-25G: Silica filler, manufactured by Tatsumori Co., Ltd., average particle size 25 μm.

[0089] (E) Ingredient: Stabilizer (E1) TIPB: triisopropyl borate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0090] (F) Other ingredients (F1) KBM403: 3-glycidoxypropyltrimethoxysilane (silane coupling agent), manufactured by Shin-Etsu Chemical Co., Ltd.

[0091] Evaluation method Volatility The weight of a metal container with a diameter of 5 cm and a depth of 0.5 cm was measured. Approximately 1.0 g of a thiol compound was added to it, and it was left in an oven at 80°C for 1 hour without covering it. After cooling, the weight of the metal container was measured, and the volatile content from the thiol resin was measured. As a result, the volatile content of 1,10-decanedithiol was 11%, the volatile content of 3,6-dioxa-1,8-octanedithiol was 27%, while the volatile content of all other thiol resins, including thiol compounds 1, 2, and 3, was less than 1%.

[0092] Viscosity measurement The viscosity of the resin compositions in the examples and comparative examples was measured by increasing the temperature from 25°C, and measuring the viscosity (Pa·s) at 30°C and the viscosity (Pa·s) at 50°C. A viscoelasticity measuring device (rheometer) (manufactured by Thermo Fisher Scientific K.K., model number: MARS60) was used for the measurement. The measurement conditions are shown below. In addition, the ratio of the viscosity of the resin composition at 30°C to the viscosity at 50°C (viscosity at 30°C / viscosity at 50°C) was determined. This viscosity ratio is preferably 1 to 4, more preferably 1 to 3.8, even more preferably 1 to 3.5, and even more preferably 1 to 3. Plate diameter: 35mmφ (parallel type) Frequency: 1Hz Distortion: 0.5 Heating rate: 3℃ / min Gap: 500μm

[0093] Calculation of glass transition temperature (Tg) difference (ΔTg) Using a dynamic viscoelasticity measuring device (DMA) (manufactured by SII NanoTechnology, product name: DMS6100), the loss modulus E'' (Tg1) (℃) and loss tangent tanδ (Tg2) (℃) of the cured products obtained by curing the resin compositions of the examples and comparative examples were measured. Two glass plates with Teflon (registered trademark) tape attached were prepared, and a 125 μm spacer film and resin composition were placed on the Teflon (registered trademark) tape surface of one glass plate, and another glass plate was placed so that the Teflon (registered trademark) tape surfaces faced each other, and the two were heated and cured at 80 °C for 180 min in a blower dryer to obtain a cured product with a thickness of about 130 μm. In addition, if the resulting cured product was brittle, the thickness of the spacer film was appropriately changed to prepare a cured product. After peeling the cured product from the glass plate, a test piece (10 ± 0.5 mm × 40 ± 1 mm) was cut out from the cured product, and the width and thickness of the test piece were measured. Thereafter, measurements were performed using the dynamic viscoelasticity measuring device described above (heating rate: 3°C / min, frequency: 10Hz, measurement range: -40 to 150°C, strain amplitude 5.0μm, tensile method). The peak temperature of tanδ (loss tangent) (if there are multiple maximum values, the maximum temperature among them) was read and determined as the glass transition temperature (Tg2). In addition, the peak temperature of loss modulus E'' (if there are multiple maximum values, the maximum temperature among them) was read and determined 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.

[0094] Hydrolysis resistance A cured product with a thickness of about 130 μm was prepared under the same conditions as the above DMA measurement. When the resin composition contained a compound containing an ester bond, hydrolysis was performed under high temperature and high humidity, and the cured resin products of the compositions of Comparative Examples 5 and 6 were placed under PCT conditions (121° C., 2 atm) for 10 hours. The cured resin products liquefied and had poor hydrolysis resistance. On the other hand, the compositions of Examples 15 and 16, which contained a thiol compound containing an ester bond in the resin composition but used a bifunctional thiol compound according to the present invention in combination, showed no abnormalities in the appearance of the cured resin products.

[0095] [Table 1]

[0096] [Table 2]

[0097] 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. In addition, the ratio of the viscosity at 30°C to the viscosity at 50°C (viscosity at 30°C / viscosity at 50°C) of the resin compositions of Examples 1 to 20 was 1 to 4, so it was confirmed that the resin compositions had good handleability regardless of the environmental atmosphere in which they were used. In addition, the ΔTg of the cured products obtained by curing the resin compositions of Examples 1 to 20 was 12°C or higher, and it was confirmed that they had a wide glass transition region and excellent stress absorption properties.

[0098] The cured products obtained from the resin compositions of Comparative Examples 5 and 6 were easily hydrolyzed and did not have improved moisture resistance because the resin compositions contained a compound containing an ester bond. In addition, voids were mixed into the cured products obtained by curing the resin compositions of Comparative Examples 3 and 4. The ratio of the viscosity at 30°C to the viscosity at 50°C (viscosity at 30°C / viscosity at 50°C) of the resin compositions of Comparative Examples 1 to 6 was 4 or more, so they were sometimes difficult to handle depending on the environmental temperature. In addition, the cured product obtained by curing the resin composition of Comparative Example 6 had a ΔTg of about 10°C, and it was confirmed that the glass transition region was narrower and the stress absorption was inferior compared to other compositions.

Claims

1. (A) an epoxy resin; (B) at least one bifunctional thiol compound selected from the group consisting of bifunctional thiol compounds having a molecular weight of 210 or more and 600 or less, ... (C) an amine compound; (D) a filler having an average particle size of 0.1 μm or more and 10 μm or less.

2. (A) an epoxy resin; (B) at least one bifunctional thiol compound selected from the group consisting of a bifunctional thiol compound represented by the following general formula (B-4) having a molecular weight of 210 or more, and a bifunctional thiol compound represented by the following general formula (B-5) having a molecular weight of 210 or more, (C) an amine compound; (D) a filler having an average particle size of 0.1 μm or more and 10 μm or less. 【Chemistry 24】 (In general formula (B-4), s and t each independently represent an integer of 3 or 4.) 【Chemistry 25】 (In general formula (B-5), u and v each independently represent an integer of 3 or 4.)

3. The resin composition according to claim 1, wherein the component (B) is a bifunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3). 【Chemistry 20】 (In general formula (B-1), n ​​and m each independently represent an integer of 1 to 3.) 【Chemistry 21】 (In 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): １ and R ２ is a group represented by the following general formula (b-1), ３ and R ４ is a group represented by the following general formula (b-1): 【Chemical 22】 (In general formula (b-1), r is an integer of 1 to 3.) 【Chemistry 23】 (In general formula (B-3), G １ , G ２ each independently represents -O- or -CH ２ -, with the proviso that at least one of G 1 and G 2 is -O-, and p and q each independently represent an integer of 2 to 5.

4. The resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the component (A) is 240 to 1,000.

5. The resin composition according to any one of claims 1 to 4, 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.

6. The total number of thiol groups of the bifunctional thiol compound of the component (B) is 20 to 100 when the number of all thiol groups in the resin composition is 100. The resin composition according to any one of claims 1 to 5.

7. The resin composition according to any one of claims 1 to 6, wherein the content of the filler of the component (D) is 5 to 70 mass% relative to 100 mass% of the total amount of the resin composition.

8. The resin composition according to any one of claims 1 to 7, further comprising (E) a stabilizer.

9. 9. The resin composition according to claim 8, 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.

10. An adhesive comprising the resin composition according to any one of claims 1 to 9.

11. An encapsulant comprising the resin composition according to claim 1 .

12. An image sensor module manufactured using the adhesive according to claim 10 or the sealing material according to claim 11.

13. A semiconductor device manufactured by using the adhesive according to claim 10 or the sealing material according to claim 11.

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