CN112823177A - Resin composition - Google Patents

Resin composition Download PDF

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CN112823177A
CN112823177A CN201980066398.XA CN201980066398A CN112823177A CN 112823177 A CN112823177 A CN 112823177A CN 201980066398 A CN201980066398 A CN 201980066398A CN 112823177 A CN112823177 A CN 112823177A
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resin composition
component
general formula
composition according
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CN112823177B (en
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岩谷一希
新井史纪
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Namis Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

A resin composition, the resin composition comprising: (A) an epoxy resin; (B) at least one bifunctional thiol compound selected from the group consisting of: a bifunctional thiol compound having a molecular chain containing an aromatic ring structure or an alicyclic structure and a hetero atom-containing ester bond in the molecule, the molecular chain having a thiol group at an end, and having a molecular weight of 210 or more; a molecular chain containing an aromatic ring structure or a heterocyclic structure and optionally containing hetero atoms, no ester bond and having a thiol group at a terminal, and a bifunctional thiol compound having a molecular weight of 210 or more; (C) an amine compound; and (D) a filler having an average particle diameter of 0.1 to 10 μm.

Description

Resin composition
Technical Field
The present invention relates to a resin composition which can be used for applications requiring heat curing at a relatively low temperature, specifically, heat curing at about 80 ℃.
Background
In manufacturing an image sensor module used as a camera module of a mobile phone or a smartphone, an adhesive (a binder) or a sealing material that is thermally cured at a relatively low temperature, specifically, at a temperature of about 80 ℃. In the production of semiconductor devices including electronic parts such as semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors, adhesives and sealants containing resin compositions that are heat-cured at temperatures around 80 ℃ are also preferably used.
In addition, moisture resistance is also required for adhesives and sealing materials used in the production of image sensor modules and semiconductor devices. Further, for mobile devices such as mobile phones and smartphones, impact resistance against dropping and the like is required; on the other hand, a cured product such as an adhesive used in a semiconductor device is required to have stress absorbability.
For example, patent document 1 discloses a resin composition containing a thiol compound having 4 thiol groups in the molecule, as a one-component adhesive which can be heat-cured at a low temperature and is excellent in resistance even in a pressure cooker test (プレッシャークッカーテスト) (hereinafter, also referred to as "PCT") in which a test is performed at a high temperature and a high humidity of 100 ℃ or higher and 70% or higher.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015/141347
Disclosure of Invention
Technical problem to be solved by the invention
However, a resin composition mainly composed of a polythiol compound having 4 thiol groups in the molecule is large in the number of crosslinking points, and the resulting cured product may have poor stress absorption properties. Further, adhesives and sealing materials used for assembling image sensor modules and semiconductor devices are required to have moisture resistance after curing and to have small viscosity change with respect to temperature change during application.
Accordingly, an object of the present invention is to provide a resin composition which can be cured at a low temperature, can give a cured product excellent in moisture resistance and stress absorption, and has good workability in use.
Means for solving the problems
Means for solving the above technical problems are described below, and the present invention includes the following aspects.
[1] A resin composition, the resin composition comprising:
(A) an epoxy resin;
(B) at least one bifunctional thiol compound selected from the group consisting of: a bifunctional thiol compound having a molecular chain containing an aromatic ring structure or an alicyclic structure and a hetero atom-containing ester bond in the molecule, the molecular chain having a thiol group at an end, and having a molecular weight of 210 or more; a molecular chain containing an aromatic ring structure or a heterocyclic structure and optionally containing hetero atoms, no ester bond and having a thiol group at a terminal, and a bifunctional thiol compound having a molecular weight of 210 or more;
(C) an amine compound; and
(D) a filler having an average particle diameter of 0.1 to 10 μm.
[2] The resin composition according to the above [1], wherein the component (B) is a bifunctional thiol compound comprising an alicyclic structure and a molecular chain containing a thioether bond, not containing an ester bond, and having a thiol group at a terminal.
[3] The resin composition according to the above [1], wherein the component (B) is a bifunctional thiol compound having an aromatic ring structure and a molecular chain containing an ether bond, not containing an ester bond, and having a thiol group at an end.
[4] The resin composition according to the above [1], wherein the component (B) is a bifunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3):
[ solution 1]
Figure BDA0003011653750000021
In the general formula (B-1), n and m are each independently an integer of 1 to 3;
[ solution 2]
Figure BDA0003011653750000031
In the general formula (B-2), R1、R2、R3And R4Each independently a hydrogen atom or a group represented by the following general formula (b-1), however, R1And R2One is a group represented by the following general formula (b-1), R3And R4One is a group represented by the following general formula (b-1),
[ solution 3]
Figure BDA0003011653750000032
In the general formula (b-1), r is an integer of 1-3;
[ solution 4]
Figure BDA0003011653750000033
In the general formula (B-3), G1、G2Each independently is through-O-or-CH2-a bonded 2-valent group, p, q each independently being an integer from 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 general formula (B-4) or (B-5):
[ solution 5]
Figure BDA0003011653750000041
In the general formula (B-4), s and t are each independently an integer of 3 or 4;
[ solution 6]
Figure BDA0003011653750000042
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 the above [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 the above [1] to [6], wherein the amine compound of the component (C) is at least one amine compound selected from imidazole compounds, tertiary amine compounds and amine adducts.
[8] The resin composition according to any one of the above [1] to [7], wherein the total number of thiol groups of the bifunctional thiol compound of the component (B) is 20 to 100, assuming that the number of all thiol groups in the resin composition is 100.
[9] The resin composition according to any one of the above [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 the above [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 a liquid boric acid ester compound, an aluminum chelate compound and barbituric acid (バルビツール acid).
[12] An adhesive comprising the resin composition according to any one of the above [1] to [11 ].
[13] A sealing material comprising the resin composition according to any one of the above [1] to [11 ].
[14] An image sensor module manufactured using the adhesive as recited in the above item [12] or the sealing material as recited in the above item [13 ].
[15] A semiconductor device produced by using the adhesive according to item [12] above or the sealing material according to item [13] above.
Advantageous effects
The present invention provides a resin composition which can be cured at a low temperature of about 80 ℃ and can give a cured product excellent in moisture resistance and stress absorption and which is excellent in handling properties during use.
Detailed Description
The following description is based on embodiments of the resin composition, the adhesive, the sealing material, the image sensor module, and the semiconductor device according to the present disclosure. However, the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following resin composition, adhesive, sealing material, image sensor module, and semiconductor device.
The resin composition according to the first embodiment of the present invention includes:
(A) an epoxy resin;
(B) at least one bifunctional thiol compound selected from the group consisting of: a bifunctional thiol compound having a molecular chain containing an aromatic ring structure or an alicyclic structure and a hetero atom-containing ester bond in the molecule, the molecular chain having a thiol group at an end, and having a molecular weight of 210 or more; a molecular chain containing an aromatic ring structure or a heterocyclic structure and optionally containing hetero atoms, no ester bond and having a thiol group at a terminal, and a bifunctional thiol compound having a molecular weight of 210 or more;
(C) an amine compound; and
(D) a filler having an average particle diameter of 0.1 to 10 μm.
(A) The components: epoxy resin
The resin composition contains an epoxy resin as the component (A). Examples of the epoxy resin as the component (A) include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol; an epoxy resin having a naphthalene skeleton such as 1, 6-bis (2, 3-glycidoxy) naphthalene; epoxidized phenol novolac resin (エポキシ - フェノールノボラック resin), epoxidized cresol novolac resin (エポキシ - クレゾールノボラック resin), epoxidized polyolefin, cyclic aliphatic epoxy resin, urethane-modified epoxy resin, silicone-modified epoxy resin, and the like. And is not limited to these resins. In order to improve the moisture resistance of a cured product formed from the resin composition, the epoxy resin of the component (a) is preferably an epoxy resin having no ester bond. Examples of such epoxy resins include bisphenol a type epoxy resins and bisphenol F type epoxy resins.
(A) The epoxy resin of component (a) may be an epoxy resin containing no aromatic ring. Here, the aromatic ring is a structure satisfying the Huckel rule (ヒュッケル means), such as a benzene ring. Examples of the epoxy resin of the component (a) include epoxy resins containing no aromatic ring, such as hydrogenated bisphenol epoxy resins, alicyclic epoxy resins, alcohol ether epoxy resins, and aliphatic epoxy resins. And is not limited to these resins. Examples of such epoxy resins include hydrogenated bisphenol a epoxy resins, hydrogenated bisphenol F epoxy resins, epoxy-modified polybutadienes, and 1, 4-cyclohexanedimethanol diglycidyl ether. When an epoxy resin containing no aromatic ring is used as the component (a), the number of epoxy groups contained in the epoxy resin containing no aromatic ring is preferably 20 to 100, more preferably 40 to 100, and further preferably 50 to 100, from the viewpoint of viscosity and adhesiveness, when the number of all epoxy groups in the resin composition is 100.
Examples of the epoxy resin as the component (A) include epoxy resins represented by the following formula (A-1).
[ solution 7]
Figure BDA0003011653750000061
In the formula (A-1), R5Is a linear or branched alkylene group having 1 to 15 carbon atoms, and w is an integer of 1 to 20.
The epoxy resin represented by the formula (A-1) may be an epoxy resin represented by the following formula (A-1-1) and/or (A-1-2).
[ solution 8]
Figure BDA0003011653750000071
In the formula (A-1-1), x is an integer of 1 to 15.
[ solution 9]
Figure BDA0003011653750000072
In the formula (A-1-2), y is an integer of 1 to 20.
For example, the epoxy resin of the component (A) may be an epoxy resin represented by the following formula (A-2).
[ solution 10]
Figure BDA0003011653750000073
In the formula (A-2), R6～R9Each independently is a linear or branched alkyl group having 1 to 3 carbon atoms.
The weight average molecular weight of the epoxy resin of the component (a) is preferably 240 to 1,000 from the viewpoint of balance between viscosity and volatility. (A) The weight average molecular weight of the epoxy resin of component (A) is preferably 250 to 1,000, more preferably 260 to 1,000, and still more preferably 270 to 1,000. If the weight average molecular weight of the epoxy resin of component (a) is less than 240, the volatility tends to be high, and voids may be generated in the cured product. On the other hand, if the weight average molecular weight of the epoxy resin of the component (a) exceeds 1,000, the viscosity becomes high, and workability may be deteriorated. In the present specification, the weight average molecular weight refers to a value according to a calibration curve of Gel Permeation Chromatography (GPC) using standard polystyrene.
(B) The components: difunctional thiol compounds
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: a bifunctional thiol compound having a molecular chain containing an aromatic ring structure or an alicyclic structure and a hetero atom-containing ester bond in the molecule, the molecular chain having a thiol group at an end, and having a molecular weight of 210 or more; and a bifunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in a molecule, and optionally contains a heteroatom, does not contain an ester bond, and has a thiol group at an end. (B) The bifunctional thiol compound of component (a) can be obtained from four chemical industries, Ltd.
(B) Since the molecular weight of the bifunctional thiol compound of component (a) is 210 or more and the volatility is low, when the resin composition is thermally cured at a low temperature of 80 ℃, for example, the bifunctional thiol compound does not volatilize, generation of voids is suppressed, and a cured product maintaining physical properties can be obtained. The molecular weight is more preferably 280 or more. The molecular weight of the difunctional thiol compound of component (B) is preferably 1,000 or less, more preferably 600 or less, from the viewpoint of curability.
(B) The bifunctional thiol compound of component (a) has a hetero atom, has good miscibility (compatibility) with the epoxy resin of component (a), and can be cured at a low temperature of, for example, 80 ℃ to obtain a uniform cured product. (B) The aromatic ring structure of the component (A) includes a monocyclic aromatic ring structure having 5 or more rings, for example, cyclopentadiene, benzene and the like. Examples of the alicyclic structure include monocyclic alicyclic structures having 5 or more rings, for example, 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 fused polycyclic structure having a heteroatom. Examples of the hetero atom contained in the molecular chain include a sulfur (S) atom and an oxygen (O) atom, and a thioether bond or an ether bond is preferably contained in the molecular chain. From the viewpoint of miscibility with an epoxy resin and low volatility, the bifunctional thiol compound of component (B) is preferably a sulfur atom as a heteroatom, that is, a molecular chain containing an alicyclic structure and a thioether bond in the molecule, not containing an ester bond, and having a thiol group at the end. In the difunctional thiol compound of the component (B), it is preferable that the hetero atom is an oxygen atom, that is, a molecular chain containing an aromatic ring structure and an ether bond in the molecule, not containing an ester bond, and having a thiol group at the end is preferable from the viewpoint of miscibility with an epoxy resin and low volatility. The bifunctional thiol compound of the component (B) preferably contains an alicyclic structure and a molecular chain containing a thioether bond, not containing an ester bond, and having a thiol group at a terminal in a molecule from the viewpoint of the adhesive strength to a metal.
Since the difunctional thiol compound of component (B) has 2 thiol groups, a cured product having excellent stress absorbability can be obtained when curing the resin composition, as compared with a cured product mainly composed of a trifunctional or higher thiol compound.
Further, the bifunctional thiol compound of the component (B) does not contain an ester bond in the molecule, and therefore, even under high temperature and high humidity conditions such as the environment in PCT, hydrolysis resistance is high, and the adhesive strength of the obtained cured product can be maintained.
For example, the component (B) is preferably a bifunctional thiol compound represented by the following general formula (B-1). The bifunctional thiol compound represented by (B-1) can be obtained from Kagaku Kogyo K.K.
[ solution 11]
Figure BDA0003011653750000091
In the general formula (B-1), n and m are each independently an integer of 1 to 3, preferably n and m are each 2.
The bifunctional thiol compound represented by the general formula (B-1) is preferably a bifunctional thiol compound represented by the following general formula (B-1-1).
[ solution 12]
Figure BDA0003011653750000092
For example, the component (B) is preferably a bifunctional thiol compound represented by the following general formula (B-2). The bifunctional thiol compound represented by (B-2) can be obtained from Kagaku Kogyo K.K.
[ solution 13]
Figure BDA0003011653750000093
In the general formula (B-2), R1、R2、R3And R4Each independently a hydrogen atom or a group represented by the following general formula (b-1), however, R1And R2One is a group represented by the following general formula (b-1), R3And R4One is a group represented by the following general formula (b-1).
[ solution 14]
Figure BDA0003011653750000101
In the general formula (b-1), r is an integer of 1 to 3, preferably 2.
The bifunctional thiol compound represented by the general formula (B-2) is preferably a bifunctional thiol compound represented by the following general formula (B-2-1).
[ solution 15]
Figure BDA0003011653750000102
For example, the component (B) is preferably a bifunctional thiol compound represented by the following general formula (B-3). The bifunctional thiol compound represented by (B-3) can be obtained from Kagaku Kogyo K.K.
[ solution 16]
Figure BDA0003011653750000103
In the general formula (B-3), G1、G2Each independently is through-O-or-CH2-a bonded 2-valent group, p, q each independently being an integer from 2 to 5. G1、G2Preferred are 2-valent groups bonded via-O-, and p and q are preferably 3 or 4, more preferably 4.
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).
[ solution 17]
Figure BDA0003011653750000111
For example, the component (B) is preferably a bifunctional thiol compound represented by the following general formula (B-4). The bifunctional thiol compound represented by (B-4) can be obtained from Kagaku Kogyo K.K.
[ solution 18]
Figure BDA0003011653750000112
In the general formula (B-4), s and t are each independently an integer of 3 or 4, preferably 4.
For example, the component (B) is preferably a bifunctional thiol compound represented by the following general formula (B-5). The bifunctional thiol compound represented by (B-5) can be obtained from Kagaku Kogyo K.K.
[ solution 19]
Figure BDA0003011653750000113
In the general formula (B-5), u and v are each independently an integer of 3 or 4, preferably 4.
The resin composition according to one embodiment of the present invention may further contain a thiol compound (a monofunctional thiol compound, a difunctional thiol compound, or a trifunctional or higher thiol compound) other than the component (B). The number of thiol groups contained in the difunctional thiol compound of component (B) is preferably 20 to 100, more preferably 40 to 100, and even more preferably 50 to 100, assuming that the number of all thiol groups in the resin composition is 100. The equivalent ratio of thiol groups of the entire thiol compound to epoxy groups of the epoxy resin contained in the resin composition (epoxy equivalent: thiol equivalent) is preferably 1:0.5 to 1: 1.5. In the resin composition, when the thiol equivalent is less than 0.5 equivalent or more than 1.5 equivalent relative to the epoxy equivalent of the epoxy resin contained in the resin composition, unreacted epoxy resin or thiol compound remains in the cured product, and thus the adhesive strength of the resin composition is reduced.
(C) The components: 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 the group consisting of imidazole compounds, tertiary amine compounds, and amine adducts. (C) The amine compound of component (a) is preferably an amine compound having a function as a curing accelerator for an epoxy resin. For example, the amine compound of component (C) is preferably a compound which is insoluble in solid at room temperature and functions as a curing accelerator by being solubilized by heating, and examples thereof include imidazole compounds, tertiary amine compounds, and solid-dispersed amine adduct type latent curing accelerators which are solid at room temperature, for example, a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct type latent curing accelerator), a reaction product of an amine compound and an isocyanate compound or a urea compound (urea type adduct type latent curing accelerator), and the like.
Examples of the imidazole-based compound 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, 2, 4-diamino-6- (2 '-methylimidazolyl- (1)') -ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and mixtures thereof, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate (トリメリテイト), 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, N '- (2-methylimidazolyl- (1) -ethyl) -adipamide (N, N' - (2- メチルイミダゾリル - (1) - エチル) - アジポイルジアミド), and the like, but is not limited thereto.
Examples of the tertiary amine compounds include primary amines or secondary amines having a tertiary amino group in the molecule, such as amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-N-propylamine, 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, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazole Oxazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, N-. beta. -hydroxyethylmorpholine, 2-dimethylaminoethylthiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as N-dimethylaminobenzoic acid, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N-dimethylglycine hydrazide, N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide. Examples of commercially available tertiary amine compounds include フジキュアー FXR-1030 and フジキュアー FXR-1020 (manufactured by T & K TOKA, Ltd.).
Examples of commercially available solid-dispersion amine-adduct type latent curing accelerators include ノバキュア HXA9322HP (manufactured by Asahi Kasei corporation), フジキュアー FXR-1121 (manufactured by T & K TOKA, K.K.), アミキュア PN-23 and アミキュア PN-F (manufactured by Meizhou Su ファインテクノ K.K.). More detailed examples of the solid dispersion type amine addition type latent curing agent or latent curing accelerator are described in japanese patent application laid-open No. 2014-77024.
The content of the amine compound of component (C) contained in the resin composition varies depending on the kind of the amine compound. From the viewpoint of extending the pot life (ポットライフ), 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. In addition, the component (C) may be provided in the form of a dispersion liquid dispersed in an epoxy resin. When the component (C) is used in this form, 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.
(D) The components: filler material
The average particle diameter of the filler of component (D) contained in the resin composition of one embodiment of the present invention is 0.1 to 10 μm, preferably 0.1 to 8 μm, more preferably 0.1 to 5 μm, and still more preferably 0.1 to 3 μm. When 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, the decrease in viscosity of the resin composition can be suppressed and the workability can be improved even when the resin composition is used in a high-temperature environment. (D) When the average particle diameter of the filler of component (a) is less than 0.1. mu.m, the viscosity increases, and workability may be adversely affected. (D) When the average particle diameter of the filler of the component (B) exceeds 10 μm, the viscosity under heating is remarkably reduced. The average particle diameter of the filler is a particle diameter (median diameter) at which the cumulative frequency of volume from the small diameter side reaches 50% in the volume-based particle size distribution obtained by the laser diffraction scattering particle size distribution measurement method. When a commercially available filler is used, the average particle diameter of the filler may be referred to the average particle diameter described in the catalog.
The content of the filler of component (D) is preferably 5 to 70% by mass, more preferably 8 to 60% by mass, and still more preferably 10 to 50% by mass, based on 100% by mass of the total amount of the resin composition. When the content of the filler of the component (D) is less than 5% by mass relative to 100% by mass of the total amount of the resin composition, the amount of the filler is too small, and it is difficult to suppress a decrease in viscosity of the resin composition at a high temperature (under heating), for example; if the amount is more than 70% by mass, the amount of the filler is too large, and the viscosity of the resin composition becomes high, which may result in poor workability.
(D) The particle shape of the filler of component (a) is not particularly limited as long as it is a filler having an average particle diameter of 0.1 μm or more and 10 μm or less, and for example, a spherical or flaky filler can be used.
(D) The filler of component (C) is not particularly limited as long as it has an average particle diameter of 0.1 to 10 μm, and the material is widely selected from fillers added in adhesive applications or sealing material applications. Specifically, the filler is formed of an inorganic substance such as silica, alumina, titania, magnesia, glass, or the like. Among these, a filler made of silica or alumina can be preferably used from the viewpoint of low thermal expansion and low water absorption. (D) The filler of the component (a) may be used alone or in combination of two or more. Examples of commercially available products include: silica filler (product name: SOE2, manufactured by アドマテックス, average particle diameter: 0.5 μm), silica filler (product name: SE1050, manufactured by アドマテックス, average particle diameter: 0.3 μm), silica filler (product name: MP-8FS, manufactured by Lorson, K.K.), silica filler (product name: SOE5, manufactured by アドマテックス, average particle diameter: 1.5 μm), silica filler (product name: FB5SDX, manufactured by Dendron, K.K., electric chemical industry Co., Ltd., average particle diameter: 5 μm), silica filler (product name: BSP6, manufactured by Lorson, average particle diameter: 5 μm), silica filler (product name: FB7SDX, manufactured by Dendron, electric chemical industry Co., Ltd., average particle diameter: 7 μm), and the like.
(E) The components: stabilizer
The resin composition according to one embodiment of the present invention may contain a stabilizer of the component (E). The storage stability of the resin composition at normal temperature (25 ℃) can be improved and the storage life can be prolonged by the stabilizer containing the component (E). The stabilizer of component (E) is preferably at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and barbituric acid because of its high effect of improving storage stability at room temperature (25 ℃).
As the liquid borate ester compound, for example, 2 '-oxybis (5,5' -dimethyl-1, 3, 2-oxaborole-hexane) (2, 2'- オキシビス (5,5' - ジメチル -1,3,2- オキサボリナン)), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, trilaurylborate, tricetylborate, tristearylborate, 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-tolyl borate, tri-m-tolyl borate, triethanolamine borate.
Further, since the liquid boric acid ester compound is liquid at room temperature (25 ℃), the liquid boric acid ester compound contained as the component (E) is preferable because the viscosity of the resin composition can be suppressed to be low.
When the liquid boric acid ester compound is contained as the component (E) in the resin composition, it is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the resin composition.
As the aluminum chelate compound, for example, aluminum triacetylacetonate (for example, ALA: aluminum chelate compound A manufactured by Kagaku ファインケミカル Co., Ltd.) can be used.
When the aluminum chelate compound 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 still more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the resin composition.
When the barbituric acid is contained as the component (E), it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the resin composition.
The resin composition according to one embodiment of the present invention may further contain, as (F) other components, at least one additive selected from the group consisting of a silane coupling agent, an ion capturing agent, a leveling agent, an antioxidant, a defoaming agent, and a thixotropic agent ( variation), as required. In addition, a viscosity modifier, a flame retardant, a solvent, or the like may be contained.
Viscosity of resin composition
The resin composition of one embodiment of the present invention is applied by a dispenser (ディスペンサ). Generally, the discharge portion of the dispenser is heated. There are also cases where no cooling system is provided in the discharge portion of the dispenser. In this case, even if the coating is initially performed at 30 ℃, the discharge portion may reach 40 ℃ or more as time elapses. The viscosity of the resin composition according to one embodiment of the present invention at 30 ℃ is preferably 0.05 pas to 100 pas, more preferably 0.05 pas to 80 pas, and still more preferably 0.1 pas to 70 pas. When the viscosity of the resin composition is in the range of 0.05 pas to 100 pas at 30 ℃, the resin composition has good workability at around room temperature, and has a viscosity suitable for assembling an image sensor module or a semiconductor device. The viscosity at 30 ℃ can be measured by the evaluation method in the examples described below using a viscoelasticity measuring apparatus (rheometer) (for example, ティー, エイ, インスツルメント (TA Instrument) manufactured by Japan K.K., model: ARES-G2).
The viscosity at 50 ℃ of the resin composition according to one embodiment of the present invention measured by the aforementioned rheometer is preferably 0.05 pas to 100 pas, more preferably 0.05 pas to 80 pas, and still more preferably 0.1 pas to 70 pas. When the viscosity of the resin composition is in the range of 0.05 pas to 100 pas at 50 ℃, the resin composition has good workability even when the resin composition is used in a high-temperature environment, and has a viscosity suitable for assembling an image sensor module or a semiconductor device.
In the resin composition of one embodiment of the present invention, the ratio of the viscosity at 50 ℃ to the viscosity at 30 ℃ (viscosity at 30 ℃/viscosity at 50 ℃) of the resin composition is preferably 1 to 4, more preferably 1 to 3.5, and still more preferably 1 to 3. When the ratio of the viscosity of the resin composition at 50 ℃ to the viscosity at 30 ℃ (viscosity at 30 ℃/viscosity at 50 ℃) is 1 to 4, even if the temperature of the resin composition used is slightly changed, the operation conditions such as the discharge conditions of the dispenser do not need to be changed, and the operability is good.
Stress absorbability (difference in glass transition temperature (Tg) (. DELTA.Tg))
The stress absorbability of the cured product of the resin composition can be measured by the difference (. DELTA.Tg) between the loss elastic modulus (Tg1) (DEG C.) and the loss tangent (Tg2) (DEG C.). In the present specification, the loss elastic modulus (Tg1) is a peak temperature of the loss elastic modulus (a temperature at which the maximum value is the maximum value among a plurality of values), and the loss tangent (Tg2) is a peak temperature of the loss tangent (a temperature at which the maximum value is the maximum value among a plurality of values). The loss elastic modulus (Tg1) represents the temperature at which the resin cured product starts to change from the glass region to the glass transition region; in contrast, the loss tangent (Tg2) represents a temperature at which the physical properties of the cured resin product are between those of the glass region and the rubber region and at which the cured resin product is deformed to have the highest ability to absorb stress applied from the outside. Therefore, it can be said that the larger the temperature difference between the loss elastic modulus (Tg1) and the loss tangent (Tg2), the wider the glass transition region, and the more easily the stress is absorbed in the wide temperature region. The loss elastic modulus (Tg1) and the loss tangent (Tg2) can be mechanically calculated by measurement using a dynamic viscoelasticity measuring apparatus (DMA), a rheometer, or the like. In addition, in the case of measurement by DMA, the loss elastic modulus is represented by E ", and the loss tangent is represented by tan δ.
The resin composition according to one embodiment of the present invention has a temperature difference between the loss elastic modulus E ″ (Tg1) and the loss tangent tan δ (Tg2) of the cured product measured by DMA, of preferably 10 ℃ or more, more preferably 12 ℃ or more, and still more preferably 14 ℃ or more. Further, since the stress absorbability is relatively lowered when the glass transition region is too wide, the temperature difference is preferably 50 ℃ or less, more preferably 40 ℃ or less, and still more preferably 30 ℃ or less.
For example, the loss elastic modulus (Tg1) (DEG C.) and loss tangent (Tg2) (DEG C.) of a cured product obtained by curing the resin composition according to one embodiment of the present invention can be measured using a dynamic viscoelasticity measuring apparatus (for example, product name: DMS6100, manufactured by エスアイアイ & ナノテクノロジー Co.). For example, the temperature increase rate may be 1 ℃ to 5 ℃ per minute.
Method for producing resin composition
The resin composition according to one embodiment of the present invention can be produced by adding the components (a) to (D) and, if necessary, (E) and kneading (mixing ). The method for producing the resin composition is not particularly limited. For example, the resin composition according to the present embodiment can be produced by mixing a raw material containing the components (A) to (D) and, if necessary, the component (E) with a mixer such as a kneader (ライカイ), a can mill, a three-roll mill, a hybrid mixer (ハイブリッドミキサー), a rotary mixer, or a two-shaft mixer. The ingredients may be mixed simultaneously or one part may be mixed first and the remaining part mixed later. Further, the above-described devices may be used in combination as appropriate.
Adhesive agent
An adhesive according to an embodiment of the present invention uses the above resin composition. The adhesive according to one embodiment of the present invention has good workability when used, can be cured at low temperature, and can give a cured product having excellent stress absorption properties without impairing physical properties. Specific heat curing conditions are, for example, 60 ℃ to 120 ℃.
Sealing material
The sealing material according to an embodiment of the present invention uses the resin composition. The sealing material according to one embodiment of the present invention has good workability during use, can be cured at low temperature, and can give a cured product having excellent stress absorption properties without impairing physical properties. Specific heat curing conditions are, for example, 60 ℃ to 120 ℃.
Image sensor module
An image sensor module according to an embodiment of the present invention is formed using an adhesive or a sealing material containing the resin composition. The image sensor module also includes camera modules for mobile phones and smart phones. The resin composition according to one embodiment of the present invention is excellent in handling properties during use, can be cured at low temperatures, and can give a cured product excellent in stress absorption without impairing physical properties, and therefore, can be suitably used as a resin composition contained in an adhesive or a sealing material used for assembling an image sensor module which is required to be cured at low temperatures of about 80 ℃.
Semiconductor device with a plurality of semiconductor chips
A semiconductor device according to an embodiment of the present invention is formed using an adhesive or a sealing material containing the resin composition. The semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, and modules, electronic devices, and the like in which these are assembled. The resin composition according to one embodiment of the present invention is excellent in handling properties during use, can be cured at a low temperature of about 80 ℃, and can give a cured product excellent in stress absorption without impairing physical properties, and therefore can be suitably used as a resin composition contained in an adhesive or a sealing material used for assembling an image sensor module which is required to be cured at a low temperature.
Examples
The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples.
Examples and comparative examples
Resin compositions were prepared by mixing the respective components in the proportions shown in table 1 or table 2 below. In the following tables, the numbers indicating the blending ratios of the components (a) to (F) each represent parts by mass. The ingredients in table 1 or table 2 are as follows.
(A) The components: epoxy resin
(A1) EPICLON EXA-850 CRP: bisphenol a epoxy resin, DIC corporation, weight average molecular weight: 344, epoxy equivalent: 172 g/eq.
(A2) YDF 8170: bisphenol F type epoxy resin, japanese ferrite ケミカル & マテリアル, weight average molecular weight: 316, epoxy equivalent: 158 g/eq.
(A3) YX 8000: hydrogenated bisphenol a epoxy resin, manufactured by mitsubishi ケミカル corporation, weight average molecular weight 410, epoxy equivalent: 205 g/eq.
(A4) YX 7400: an epoxy resin represented by the general formula (A-1-1) (wherein x in the general formula (A-1-1) is 10.3), produced by Mitsubishi ケミカル, having a weight average molecular weight of 870, an epoxy equivalent: 435 g/eq.
(A5) TSL 9906: r in (general formula (A-2)) represented by general formula (A-2)6～R9Methyl group) manufactured by モメンティブ · パフォーマンス · マテリアル ズ, a weight average molecular weight 296, an epoxy equivalent 181 g/eq.
Thiol compounds
(B) The components: difunctional thiol compounds
(B1) Thiol compound 1: a bifunctional thiol compound represented by the general formula (B-1-1), having a molecular weight of 389, thiol equivalent weight, manufactured by Sizhou Kasei Kogyo Co., Ltd: 211 g/eq.
(B2) Thiol compound 2: a bifunctional thiol compound represented by the general formula (B-2-1), having a molecular weight of 445 and a thiol equivalent, manufactured by Sizhou Kasei Kogyo Co., Ltd: 243 g/eq.
(B3) Thiol compound 3: a bifunctional thiol compound represented by the general formula (B-3-1), having a molecular weight of 286, thiol equivalent weight, manufactured by Sizhou Kasei Kogyo Co., Ltd: 159 g/eq.
Thiol compound other than component (B') (B)
(B'4) DMDO: 3, 6-dioxa-1, 8-octanedithiol (1, 8-dimercapto-3, 6-dioxaoctane), manufactured by Tokyo chemical industries, molecular weight 182, thiol equivalent 91 g/eq.
(B'5)1, 10-decanedithiol, molecular weight 206, thiol equivalent 103g/eq, manufactured by Tokyo chemical industries, Ltd.
(B'6) EPMG-4: tetraethylene glycol bis (3-mercaptopropionate) having a molecular weight of 372 and a thiol equivalent of 186g/eq, manufactured by SC organic chemical Co.
(B'7) PEMP: pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), available from SC organic chemical Co., Ltd., molecular weight was 489, and thiol equivalent was 122 g/eq.
(B'8) C3 TS-G: 1,3,4, 6-tetrakis (3-mercaptopropyl) glycoluril, manufactured by Sizhou chemical industry Co., Ltd., molecular weight 432, thiol equivalent 114 g/eq.
(C) The components: amine compound
(C1) フジキュアー FXR-1121: a solid dispersion type amine adduct is manufactured by T & KTOKA, K.K..
(C2) HXA9322 HP: a solid dispersion type latent curing catalyst of amine adduct type (microcapsule type imidazole adduct) manufactured by Asahi chemical Co., Ltd, 1/3 in weight is a microcapsule type imidazole adduct and 2/3 is a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, and the epoxy equivalent is 180 g/eq.
(C3) フジキュアー FXR-1020, Tertiary amine Compound, manufactured by T & K TOKA.
(D) The components: filler material
(D1) SOE 5: the silica filler was manufactured by アドマテックス K.K., and had an average particle diameter of 1.5. mu.m.
(D2) BSP 6: the silica filler was produced by Lorson corporation and had an average particle diameter of 5 μm.
(D') a filler other than the component (D)
(D'3) MSV-25G: the silica filler was produced by Lorson corporation and had an average particle diameter of 25 μm.
(E) The components: stabilizer
(E1) TIPB: triisopropyl borate ester, manufactured by Tokyo Kasei Kogyo Co.
(F) Other ingredients
(F1) KBM 403: 3-glycidoxypropyltrimethoxysilane (silane coupling agent), manufactured by shin-Etsu chemical Co., Ltd.
Evaluation method
Volatility
The weight of a metal container having a diameter of 5cm and a depth of 0.5cm was measured. 1.0g of a thiol compound was added thereto as a target, and the mixture was left in an oven at 80 ℃ for 1 hour without covering the lid. After cooling, the weight of the metal container was measured, and the volatile content derived from the thiol resin was measured. As a result, the volatile matter of 1, 10-decanedithiol was 11%, and the volatile matter of 3, 6-dioxa-1, 8-octanedithiol was 27%; on the other hand, the volatile contents of all the other thiol resins containing the thiol compounds 1, 2, and 3 are 1% or less.
Measurement of viscosity
For the viscosities of the resin compositions of examples and comparative examples, the temperature was raised from 25 ℃ and the viscosity at 30 ℃ (Pa · s) and the viscosity at 50 ℃ (Pa · s) were measured. The measurement was carried out using a viscoelastometer measuring apparatus (rheometer) (model: MARS60, manufactured by サーモフィッシャーサイエンティフィック K.K.). The measurement conditions are as follows. Further, the ratio of the viscosity at 30 ℃ to the viscosity at 50 ℃ of the resin composition (viscosity at 30 ℃ C./viscosity at 50 ℃ C.) was determined. The ratio of the viscosities 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: 35mm phi (parallel type)
Frequency: 1Hz
Distortion degree: 0.5
Temperature rise rate: 3 ℃ per minute
Clearance: 500 μm
Calculation of the difference in glass transition temperature (Tg) (. DELTA.Tg)
The loss modulus of elasticity E "(Tg 1) (DEG C) and loss tangent tan delta (Tg2) (DEG C) of cured products obtained by curing the resin compositions of examples and comparative examples were measured using a dynamic viscoelasticity measuring apparatus (DMA) (manufactured by エスアイアイ & ナノテクノロジー, product name: DMS 6100). 2 glass plates to which Teflon (registered trademark) tapes were attached were prepared, a 125 μm separator and a resin composition were placed on the Teflon (registered trademark) tape surface of one glass plate, the other glass plate was placed so that the Teflon (registered trademark) tape surfaces were opposed to each other, and the resulting plate was heated and cured at 80 ℃ for 180 minutes by an air dryer, whereby a cured product having a thickness of about 130 μm was obtained. When the obtained cured product is brittle, the thickness of the separator is appropriately changed to produce a cured product. After the cured product was peeled off from the glass plate, a test piece (10. + -. 0.5 mm. times.40. + -. 1mm) was cut out from the cured product, and the width and thickness of the test piece were measured. Then, the measurement was carried out using the dynamic viscoelasticity measuring apparatus (temperature rising rate: 3 ℃/min, frequency: 10Hz, measurement range: 40 ℃ C. -150 ℃ C., strain amplitude: 5.0. mu.m, tensile method). The peak temperature (temperature at which the maximum value is the maximum among a plurality of maximum values) of tan δ (loss tangent) was read as the glass transition temperature (Tg 2). Further, the peak temperature (the temperature at which the maximum value is the maximum value among a plurality of values) of the loss elastic modulus E ″ is read as the glass transition temperature (Tg 1). The difference Δ Tg (. degree.C.) between the glass transition temperature (Tg1) (degree.C.) and the glass transition temperature (Tg2) (degree.C.) was calculated. The Δ Tg is preferably 12 ℃ or higher.
Resistance to hydrolysis
A cured product having a thickness of about 130 μm was prepared under the same conditions as in the above DMA measurement. When the resin composition contains a compound having an ester bond, hydrolysis is carried out at high temperature and high humidity, and when the resin cured products of the compositions of comparative examples 5 and 6 are continuously subjected to PCT conditions (121 ℃ C., 2 atm) for 10 hours, the resin cured products liquefy, and hydrolysis resistance is poor. On the other hand, although the resin compositions contained ester bond-containing thiol compounds, the compositions of examples 15 and 16 using the bifunctional thiol compound of the present invention in combination were not abnormal in appearance of the cured resin products.
Figure BDA0003011653750000231
Figure BDA0003011653750000241
The cured products obtained from the resin compositions of examples 1 to 20 were excellent in hydrolysis resistance and low volatility, and no voids were mixed in the cured products after curing. Further, since the ratio of the viscosity at 30 ℃ to the viscosity at 50 ℃ (viscosity at 30 ℃/viscosity at 50 ℃) of the resin compositions of examples 1 to 20 is 1 to 4, it can be confirmed that the handling property of the resin compositions is good regardless of the atmosphere in which the resin compositions are used. In addition, it was confirmed that the cured products obtained by curing the resin compositions of examples 1 to 20 had a Δ Tg of 12 ℃ or higher, a wide glass transition region, and excellent stress absorbability.
The cured products obtained from the resin compositions of comparative examples 5 and 6 were easily hydrolyzed because the resin compositions contained ester bond-containing compounds, and the moisture resistance was not improved. In addition, voids were mixed in the cured products obtained by curing the resin compositions of comparative examples 3 and 4. The resin compositions of comparative examples 1 to 6 each had a ratio of viscosity at 30 ℃ to viscosity at 50 ℃ (viscosity at 30 ℃/viscosity at 50 ℃) of 4 or more, and therefore were sometimes difficult to handle at ambient temperature. Further, it was confirmed that the cured product obtained by curing the resin composition of comparative example 6 had a Δ Tg of about 10 ℃, and the glass transition region was narrower and the stress absorption was inferior to those of other compositions.

Claims (15)

1. A resin composition, the resin composition comprising:
(A) an epoxy resin;
(B) at least one bifunctional thiol compound selected from the group consisting of: a bifunctional thiol compound having a molecular chain containing an aromatic ring structure or an alicyclic structure and a hetero atom-containing ester bond in the molecule, the molecular chain having a thiol group at an end, and having a molecular weight of 210 or more; a molecular chain containing an aromatic ring structure or a heterocyclic structure and optionally containing hetero atoms, no ester bond and having a thiol group at a terminal, and a bifunctional thiol compound having a molecular weight of 210 or more;
(C) an amine compound; and
(D) a filler having an average particle diameter of 0.1 to 10 μm.
2. The resin composition according to claim 1, wherein the component (B) is a bifunctional thiol compound comprising an alicyclic structure and a molecular chain containing a thioether bond, not containing an ester bond, and having a thiol group at a terminal.
3. The resin composition according to claim 1, wherein the component (B) is a bifunctional thiol compound having an aromatic ring structure and a molecular chain containing an ether bond, not containing an ester bond, and having a thiol group at a terminal.
4. 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):
[ solution 20]
Figure FDA0003011653740000011
In the general formula (B-1), n and m are each independently an integer of 1 to 3;
[ solution 21]
Figure FDA0003011653740000021
In the general formula (B-2), R1、R2、R3And R4Each independently a hydrogen atom or a group represented by the following general formula (b-1), however, R1And R2One is a group represented by the following general formula (b-1), R3And R4One is a group represented by the following general formula (b-1),
[ solution 22]
Figure FDA0003011653740000022
In the general formula (b-1), r is an integer of 1-3;
[ solution 23]
Figure FDA0003011653740000023
In the general formula (B-3), G1、G2Each independently is through-O-or-CH2-a bonded 2-valent group, p, q each independently being an integer from 2 to 5.
5. The resin composition according to claim 1, wherein the component (B) is a bifunctional thiol compound represented by the following general formula (B-4) or (B-5):
[ solution 24]
Figure FDA0003011653740000031
In the general formula (B-4), s and t are each independently an integer of 3 or 4;
[ solution 25]
Figure FDA0003011653740000032
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 claims 1 to 5, wherein the weight average molecular weight of the component (A) is 240 to 1,000.
7. The resin composition according to any one of claims 1 to 6, wherein the amine compound of the component (C) is at least one amine compound selected from the group consisting of imidazole compounds, tertiary amine compounds and amine adducts.
8. The resin composition according to any one of claims 1 to 7, wherein the total number of thiol groups of the bifunctional thiol compound of the component (B) is 20 to 100, where 100 is the number of all thiol groups in the resin composition.
9. The resin composition according to any one of claims 1 to 8, wherein the filler content of the component (D) is 5 to 70% by mass relative to 100% by mass of the total amount of the resin composition.
10. The resin composition according to any one of claims 1 to 9, further comprising (E) a stabilizer.
11. The resin composition according to claim 10, wherein the stabilizer of the component (E) is at least one selected from the group consisting of a liquid borate compound, an aluminum chelate compound and barbituric acid.
12. An adhesive comprising the resin composition according to any one of claims 1 to 11.
13. A sealing material comprising the resin composition according to any one of claims 1 to 11.
14. An image sensor module manufactured using the adhesive according to claim 12 or the sealing material according to claim 13.
15. A semiconductor device manufactured using the adhesive according to claim 12 or the sealing material according to claim 13.
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