CN112823177B - Resin composition - Google Patents
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- CN112823177B CN112823177B CN201980066398.XA CN201980066398A CN112823177B CN 112823177 B CN112823177 B CN 112823177B CN 201980066398 A CN201980066398 A CN 201980066398A CN 112823177 B CN112823177 B CN 112823177B
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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
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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
- C08G59/50—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
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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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Abstract
A resin composition, the resin composition comprising: (A) an epoxy resin; (B) At least one difunctional thiol compound selected from the group consisting of: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain optionally containing a heteroatom and not containing an ester bond and having a thiol group at the end; (C) an amine compound; and (D) a filler having an average particle diameter of 0.1 μm or more and 10 μm or less.
Description
Technical Field
The present invention relates to a resin composition useful 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 for a mobile phone or a smart phone, an adhesive or a sealing material thermally cured at a relatively low temperature, specifically, at a temperature of about 80 ℃ is used for assembling a structure. In the case of manufacturing a semiconductor device including electronic components such as a semiconductor element, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a capacitor, an adhesive or a sealing material containing a resin composition thermally cured at a temperature of about 80 ℃ is also preferably used.
In addition, moisture resistance is also required for adhesives or sealing materials used in manufacturing 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; in contrast, cured products such as adhesives used in semiconductor devices are 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 excellent in resistance even in a pressure cooker test (hereinafter also referred to as PCT) in which the resin composition can be thermally cured at a low temperature and the test can be performed at a high temperature and a high humidity of at least 100 ℃ and a humidity of at least 70%.
Prior art literature
Patent literature
Patent document 1: international publication No. 2015/141347
Disclosure of Invention
Technical problem to be solved by the invention
However, the resin composition mainly composed of a polythiol compound having 4 thiol groups in the molecule has many crosslinking points, and the resulting cured product may have poor stress absorbability. In addition, adhesives and sealing materials used for assembling image sensor modules and semiconductor devices are required to have moisture resistance after curing and also to have a small viscosity change at the time of coating with respect to a temperature change.
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 absorbability, and is excellent in handleability when used.
Technical means for solving the technical problems
Means for solving the above technical problems the present invention includes the following aspects.
[1] A resin composition, the resin composition comprising:
(A) An epoxy resin;
(B) At least one difunctional thiol compound selected from the group consisting of: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain optionally containing a heteroatom and not containing an ester bond and having a thiol group at the end;
(C) An amine compound; and
(D) A filler having an average particle diameter of 0.1 μm or more and 10 μm or less.
[2] The resin composition according to the above [1], wherein the component (B) is a difunctional thiol compound having an alicyclic structure and a molecular chain containing no ester bond and having a thiol group at the end thereof in the molecule.
[3] The resin composition according to the above [1], wherein the component (B) is a difunctional thiol compound having an aromatic ring structure in the molecule and a molecular chain having an ether bond and no ester bond and having a thiol group at the end.
[4] The resin composition according to the above [1], wherein the component (B) is a difunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3):
[ chemical 1]
In the general formula (B-1), n and m are each independently integers of 1 to 3;
[ chemical 2]
In the general formula (B-2), R 1 、R 2 、R 3 And R is 4 Each independently is a hydrogen atom or a group represented by the following formula (b-1), however, R 1 And R is 2 One of them is a group represented by the following general formula (b-1), R 3 And R is 4 One of them is a group represented by the following general formula (b-1),
[ chemical 3]
In the general formula (b-1), r is an integer of 1 to 3;
[ chemical 4]
In the general formula (B-3), G 1 、G 2 Each independently is through-O-or-CH 2 -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 difunctional thiol compound represented by the following general formula (B-4) or (B-5):
[ chemical 5]
In the general formula (B-4), s and t are each independently integers of 3 or 4;
[ chemical 6]
In the general formula (B-5), u and v are each independently an integer of 3 or 4.
[6] The resin composition according to any one of [1] to [5], wherein the weight average molecular weight of the component (A) is 240 to 1,000.
[7] The resin composition according to any one of the above [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 [1] to [7], wherein the total number of thiol groups of the difunctional thiol compound of the component (B) is 20 to 100, when 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 filler content of the component (D) is 5 to 70% by mass based on 100% by mass of the total resin composition.
[10] The resin composition according to any one of [1] to [9], wherein the resin composition further comprises (E) a stabilizer.
[11] The resin composition according to the above [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 [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 as described in the above [12] or the sealing material as described in the above [13 ].
[15] A semiconductor device manufactured by using the adhesive according to the above [12] or the sealing material according to the above [13 ].
Advantageous effects
According to the present invention, a resin composition which can be cured at a low temperature of about 80 ℃, can provide a cured product excellent in moisture resistance and stress absorbability, and has good handleability when used can be provided.
Detailed Description
Hereinafter, embodiments of the resin composition, the adhesive, the sealing material, the image sensor module, and the semiconductor device according to the present disclosure will be described. 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 difunctional thiol compound selected from the group consisting of: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, a molecular chain optionally containing a heteroatom and not containing an ester bond and having a thiol group at the end;
(C) An amine compound; and
(D) A filler having an average particle diameter of 0.1 μm or more and 10 μm or less.
(A) The components are as follows: 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 a polyhydric phenol such as bisphenol a, bisphenol F, bisphenol AD, catechol, resorcinol, etc. with epichlorohydrin; epoxy resins having a naphthalene skeleton such as 1, 6-bis (2, 3-glycidoxy) naphthalene; epoxidized phenol novolac resin (d.p.d. jet resin), an epoxidized cresol novolac resin (a synthetic resin of the rakuk family), epoxidized polyolefin, cycloaliphatic epoxy resins, urethane-modified epoxy resins, silicone-modified epoxy resins, and the like. The resin is not limited to these resins. In order to improve moisture resistance of a cured product formed from the resin composition, the epoxy resin of the component (a) is preferably an epoxy resin containing 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 the component (a) may be an aromatic ring-free epoxy resin. Here, the aromatic ring is a structure satisfying the Siberian style, for example, a benzene ring. Examples of the epoxy resin of the component (a) include hydrogenated bisphenol epoxy resin, alicyclic epoxy resin, alcohol ether type epoxy resin, aliphatic epoxy resin, and the like. The resin is not limited to these resins. Examples of such epoxy resins include hydrogenated bisphenol a epoxy resins, hydrogenated bisphenol F epoxy resins, epoxy-modified polybutadiene, 1, 4-cyclohexanedimethanol diglycidyl ether, and the like. When an aromatic ring-free epoxy resin is used as the component (a), the number of epoxy groups contained in the aromatic ring-free epoxy resin 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 viewpoints of viscosity and adhesiveness.
Examples of the epoxy resin as the component (A) include epoxy resins represented by the following formula (A-1).
[ chemical 7]
In the formula (A-1), R 5 Is a linear or branched alkylene group having 1 to 15 carbon atoms, and w is an integer of 1 to 20.
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).
[ chemical 8]
In the formula (A-1-1), x is an integer of 1 to 15.
[ chemical 9]
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).
[ chemical 10]
In the formula (A-2), R 6 ～R 9 Each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms.
From the viewpoint of balance between viscosity and volatility, the weight average molecular weight of the epoxy resin of component (a) is preferably 240 to 1,000. (A) The weight average molecular weight of the epoxy resin of the component (a) is preferably 250 to 1,000, 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, the volatility tends to increase, 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 the workability may deteriorate. In the present specification, the weight average molecular weight refers to a value of a calibration curve using standard polystyrene according to Gel Permeation Chromatography (GPC).
(B) The components are as follows: difunctional thiol compounds
The (B) difunctional thiol compound contained in the resin composition according to one embodiment of the present invention is at least one difunctional thiol compound selected from the group consisting of the following difunctional thiol compounds: a difunctional thiol compound having a molecular weight of 210 or more, wherein the difunctional thiol compound has an aromatic ring structure or an alicyclic structure in the molecule, contains a hetero atom, does not contain an ester bond, and has a thiol group at the end; and a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or a heterocyclic structure in the molecule, optionally contains a heteroatom, does not contain an ester bond, and has a thiol group at the end. (B) The difunctional thiol compound of the component (A) is available from Kagaku Kogyo Co., ltd.
(B) The difunctional thiol compound of the component has a molecular weight of 210 or more, and thus has low volatility, and therefore, for example, when the resin composition is thermally cured at a low temperature of 80 ℃, the difunctional thiol compound does not volatilize, the generation of voids is suppressed, and a cured product maintaining physical properties can be obtained. More preferably, the molecular weight is 280 or more. From the viewpoint of curability, the molecular weight of the difunctional thiol compound of the component (B) is preferably 1,000 or less, more preferably 600 or less.
(B) The difunctional thiol compound of the component (a) has a heteroatom, and is excellent in miscibility (compatibility) with the epoxy resin of the component (a), and a uniform cured product can be obtained by curing at a low temperature of, for example, 80 ℃. (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, such as cyclopentane and cyclohexene. The heterocyclic structure may be a single ring or a multiple ring, 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. 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 in the molecular chain is preferable. From the viewpoints of miscibility with an epoxy resin and low volatility, the hetero atom in the difunctional thiol compound of the component (B) is preferably a sulfur atom, that is, a molecular chain containing an alicyclic structure and a thioether bond in the molecule and having no ester bond and a thiol group at the end is preferable. In addition, from the viewpoints of miscibility with an epoxy resin and low volatility, the hetero atom is preferably an oxygen atom, that is, a molecular chain containing an aromatic ring structure and an ether bond in the molecule, containing no ester bond, and having a thiol group at the terminal is preferable in the difunctional thiol compound of the component (B). From the viewpoint of adhesion strength to metal, the difunctional thiol compound of the component (B) is more preferably a molecular chain containing an alicyclic structure and a thioether bond in the molecule, containing no ester bond, and having a thiol group at the terminal.
Further, since the difunctional thiol compound of the component (B) has 2 thiol groups, a cured product having excellent stress absorbability can be obtained when the resin composition is cured, as compared with a cured product mainly composed of a trifunctional or higher thiol compound.
Further, the difunctional thiol compound of the component (B) does not contain an ester bond in the molecule, and therefore, even under high temperature and high humidity such as the environment in PCT, the hydrolysis resistance is high, and the adhesive strength of the obtained cured product can be maintained.
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-1). The difunctional thiol compound shown in (B-1) is available from Kagaku Kogyo Co., ltd.
[ chemical 11]
In the general formula (B-1), n and m are each independently an integer of 1 to 3, and preferably n and m are each 2.
The difunctional thiol compound represented by the general formula (B-1) is preferably a difunctional thiol compound represented by the following general formula (B-1-1).
[ chemical 12]
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-2). The difunctional thiol compound shown in (B-2) is available from Kagaku Kogyo Co., ltd.
[ chemical 13]
In the general formula (B-2), R 1 、R 2 、R 3 And R is 4 Each independently is a hydrogen atom or a group represented by the following formula (b-1), however, R 1 And R is 2 One of them is a group represented by the following general formula (b-1), R 3 And R is 4 One of them is a group represented by the following general formula (b-1).
[ chemical 14]
In the general formula (b-1), r is an integer of 1 to 3, preferably 2.
The difunctional thiol compound represented by the general formula (B-2) is preferably a difunctional thiol compound represented by the following general formula (B-2-1).
[ 15]
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-3). The difunctional thiol compound shown in (B-3) is available from Kagaku Kogyo Co., ltd.
[ 16]
In the general formula (B-3), G 1 、G 2 Each independently is through-O-or-CH 2 -a bonded 2-valent group, p, q each independently being an integer from 2 to 5. G 1 、G 2 Preferably a 2-valent group bonded via-O-, p and q are preferably 3 or 4, more preferably 4.
The difunctional thiol compound represented by the above general formula (B-3) is preferably a difunctional thiol compound represented by the following general formula (B-3-1).
[ chemical 17]
For example, the component (B) is preferably a difunctional thiol compound represented by the following general formula (B-4). The difunctional thiol compound shown in (B-4) is available from Kagaku Kogyo Co., ltd.
[ chemical 18]
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 difunctional thiol compound represented by the following general formula (B-5). The difunctional thiol compound shown in (B-5) is available from Kagaku Kogyo Co., ltd.
[ chemical 19]
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 (monofunctional thiol compound, difunctional thiol compound, trifunctional or higher thiol compound) other than the component (B). When the number of all thiol groups in the resin composition is 100, the number of thiol groups contained in the difunctional thiol compound of the component (B) is preferably 20 to 100, more preferably 40 to 100, and even more preferably 50 to 100. The equivalent ratio of thiol groups (epoxy equivalent: thiol equivalent) to all thiol compounds of epoxy groups of the epoxy resin contained in the resin composition 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 therefore the adhesive strength of the resin composition is lowered.
(C) The components are as follows: amine compound
In the resin composition according to one embodiment of the present invention, the amine compound of 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 the 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 solid insoluble at room temperature and is soluble by heating to function as a curing accelerator, and examples thereof include imidazole compounds, tertiary amine compounds, solid dispersion type amine adduct type latent curing accelerators which are solid at room temperature, for example, reaction products of amine compounds and epoxy compounds (amine-epoxy adduct type latent curing accelerators), reaction products of amine compounds and isocyanate compounds or urea compounds (urea type adduct type latent curing accelerators), and the like.
Examples of the imidazole 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, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, N '- (2-methylimidazolyl- (1) -ethyl) -adipodiamide (N, N' - (2-methylethyl) -1-clamp), and the like, but are not limited thereto.
Examples of the tertiary amine compound include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-N-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, and primary or secondary amines having a tertiary amino group in the molecule such as 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-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, N-. Beta. -hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N-dimethylcarbamic acid, N-dimethylglycine, N-nicotinic acid, N-dimethylglycine, N-methylglycine, N-dimethylhydrazine, alcohols having a tertiary amino group in the molecule, such as N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide, phenols, thiols, carboxylic acids and hydrazides. Examples of the commercially available tertiary amine compound include a frame FXR-1030 and a frame FXR-1020 (manufactured by T & K TOKA, inc.).
Examples of commercially available solid dispersion type amine adduct type latent curing accelerators include HXA9322HP (manufactured by Asahi Kabushiki Kaisha), fair FXR-1121 (manufactured by T & K TOKA, co., ltd.), fair, uta PN-23, fair, PN-F (manufactured by Wei Fair, fu, co., ltd.), and the like. More detailed examples of solid dispersion type amine addition type latent curing agents or latent curing accelerators are incorporated in Japanese patent application laid-open No. 2014-77024.
The content of the amine compound of the component (C) contained in the resin composition varies depending on the kind of the amine compound. From the viewpoint of extending the pot life, the (C) amine compound contained in the resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 35 parts by mass, 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 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 contained in the amount of the above-mentioned component (A) in the resin composition of the present invention.
(D) The components are as follows: packing material
The filler of component (D) contained in the resin composition according to one embodiment of the present invention has an average particle diameter 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, still more preferably 0.1 μm or more and 3 μm or less. When the filler of component (D) contained in the resin composition has an average particle diameter of 0.1 μm or more and 10 μm or less, the resin composition can be prevented from decreasing in viscosity and improved in handleability even when the resin composition is used in an environment of a relatively high temperature. (D) If the average particle diameter of the filler of the component (a) is smaller than 0.1. Mu.m, the viscosity may be increased, which may adversely affect the workability. (D) When the average particle diameter of the filler of the component exceeds 10. Mu.m, the viscosity under heating is remarkably reduced. The average particle diameter of the filler is a particle diameter (median particle diameter) at which the volume accumulation frequency 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 can be referred to as the average particle diameter described in the commercial catalogue.
The content of the filler of the component (D) is preferably 5 to 70% by mass, more preferably 8 to 60% by mass, and even more preferably 10 to 50% by mass, relative to 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 mass% relative to 100 mass% of the total amount of the resin composition, the amount of the filler is too small, for example, it is difficult to suppress the decrease in viscosity of the resin composition at high temperature (under heating); when the amount is more than 70 mass%, the amount of filler is too large, and the viscosity of the resin composition may be high, resulting in poor handleability.
(D) The particle shape of the filler of the 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 scaly filler may be used.
(D) The filler of the component (A) is not particularly limited as long as it has an average particle diameter of 0.1 μm or more and 10 μm or less, and may be selected from fillers added for adhesive applications and sealing materials. Specifically, a filler formed of an inorganic substance such as silica, alumina, titania, magnesia, or glass is mentioned. Among these, from the viewpoints of low thermal expansion and low water absorption, a filler formed of silica or alumina can be preferably used. (D) The filler of the component (A) may be used alone or in combination of two or more. Examples of commercial products include: silica filler (product name: SOE2, manufactured by Kyowa, co., ltd., average particle size: 0.5 μm), silica filler (product name: SE1050, manufactured by Kyowa, co., ltd., average particle size: 0.3 μm), silica filler (product name: MP-8FS, manufactured by Kyowa, co., ltd., average particle size: 0.7 μm), silica filler (product name: SOE5, manufactured by Kyowa, co., ltd., average particle size: 1.5 μm), silica filler (product name: FB5SDX, manufactured by electric chemical industry Co., ltd., average particle size: 5 μm), silica filler (product name: BSP6, manufactured by Kyowa, average particle size: 5 μm), silica filler (product name: FB7SDX, manufactured by electric chemical industry Co., ltd., average particle size: 7 μm), and the like.
(E) The components are as follows: stabilizing agent
The resin composition according to one embodiment of the present invention may contain a stabilizer of component (E). The storage stability of the resin composition at ordinary temperature (25 ℃) can be improved and the pot 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 normal temperature (25 ℃).
Examples of the liquid borate compound include 2,2' -oxybis (5, 5' -dimethyl-1, 3, 2-oxaborole) (2, 2' -macy-1, 3, 2-macy-1, 3-oxaborole), 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, trilauryl borate, tricetyl borate, tristearyl borate, tris (2-ethylhexyl oxy) borane, bis (1, 4,7, 10-tetraoxaundecyl) (1, 4,7,10, 13-pentaoxatetradecyl) (1, 4, 7-trioxaundecyl) borane, triphenyl borate, and trioctyl borate.
In addition, the liquid boric acid ester compound contained as the component (E) is preferably a liquid boric acid ester compound at room temperature (25 ℃) 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, the content 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, aluminum triacetylacetonate (for example, ALA: aluminum chelate compound a manufactured by chemical company of shimmy) can be used.
When the aluminum chelate compound is contained in the component (E), it 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 barbituric acid is contained in 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 the other component (F), at least one additive selected from the group consisting of a silane coupling agent, an ion capturing agent, a leveling agent, an antioxidant, an antifoaming agent, and a thixotropic agent ( agent), 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 according to one embodiment of the present invention is applied by a dispenser. In general, 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 higher as time passes. The viscosity of the resin composition according to one embodiment of the present invention is preferably 0.05pa·s to 100pa·s, more preferably 0.05pa·s to 80pa·s, and still more preferably 0.1pa·s to 70pa·s at 30 ℃. When the viscosity of the resin composition is in the range of 0.05pa·s to 100pa·s at 30 ℃, the resin composition in the vicinity of room temperature is excellent in handleability, and the viscosity is suitable for assembling an image sensor module or a semiconductor device. The viscosity at 30℃can be measured by using a viscoelastometer (for example, a viscoelastometer, model: ARES-G2, manufactured by TA instrument, japan Co., ltd.) based on the evaluation method in examples described below.
The viscosity of the resin composition according to one embodiment of the present invention at 50℃measured by the rheometer is preferably 0.05 to 100 Pa.s, more preferably 0.05 to 80 Pa.s, and still more preferably 0.1 to 70 Pa.s. When the viscosity of the resin composition is in the range of 0.05pa·s to 100pa·s at 50 ℃, the operability of the resin composition is good even when the resin composition is used in an environment of a relatively high temperature, and the viscosity is suitable for assembling an image sensor module and a semiconductor device.
The ratio of the viscosity at 30℃to the viscosity at 50℃of the resin composition according to one embodiment of the present invention (viscosity at 30℃/viscosity at 50 ℃) is preferably 1 to 4, more preferably 1 to 3.5, and even more preferably 1 to 3. When the ratio of the viscosity at 30℃to the viscosity at 50℃ (viscosity at 30℃/viscosity at 50 ℃) of the resin composition is 1 to 4, even if the temperature at which the resin composition is used varies slightly, the operation conditions such as the discharge condition of the dispenser need not 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 indicated by the difference (ΔTg) between the loss elastic modulus (Tg 1) (DEG C) and the loss tangent (Tg 2) (DEG C). In the present specification, the loss elastic modulus (Tg 1) is the peak temperature of the loss elastic modulus (the temperature at which the maximum value is the maximum value among the values), and the loss tangent (Tg 2) is the peak temperature of the loss tangent (the temperature at which the maximum value is the maximum value among the values). The loss elastic modulus (Tg 1) 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 (Tg 2) represents a temperature at which the physical properties of the cured resin product are between the glass region and the rubber region and the ability of the cured resin product to absorb externally applied stress by deformation thereof is highest. Therefore, it can be said that the larger the temperature difference between the loss elastic modulus (Tg 1) and the loss tangent (Tg 2), the wider the glass transition region, and the easier the stress is absorbed in a wide temperature region. The loss elastic modulus (Tg 1) and the loss tangent (Tg 2) can be calculated mechanically by measurement using a dynamic viscoelasticity measuring Device (DMA), a rheometer, or the like. In addition, when the measurement is performed by DMA, the loss elastic modulus is represented by E ", and the loss tangent is represented by tan δ.
The temperature difference between the loss elastic modulus E "(Tg 1) and the loss tangent tan δ (Tg 2) of the cured product of the resin composition according to one embodiment of the present invention measured by DMA is preferably 10 ℃ or higher, more preferably 12 ℃ or higher, and still more preferably 14 ℃ or higher. In addition, when the glass transition region is too wide, the stress absorbability is relatively lowered, and therefore 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 (Tg 1) (. Degree. C.) and loss tangent (Tg 2) (. Degree. 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 device (for example, manufactured by Fata-Di Tek, product name: DMS 6100). For example, the temperature increase rate may be 1℃per minute 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 above-described 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 raw materials containing the above-described components (a) to (D) and, if necessary, component (E) with a mixer such as a kneader, a pot mill, a three-roll mill, a hybrid mixer, a rotary mixer, or a twin-shaft mixer. These components may be mixed at the same time, or a part may be mixed first and then the remaining part may be mixed. In addition, the above devices may be used in combination as appropriate.
Adhesive agent
The adhesive according to one embodiment of the present invention uses the above-described resin composition. The adhesive according to one embodiment of the present invention has good handleability when used, can be cured at a low temperature, and can give a cured product excellent in stress absorbability without impairing physical properties. Specific heat curing conditions are, for example, 60℃to 120 ℃.
Sealing material
The sealing material according to one embodiment of the present invention uses the above resin composition. The sealing material according to one embodiment of the present invention has good handleability when used, can be cured at a low temperature, and can give a cured product excellent in stress absorbability 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 above resin composition. The image sensor module also includes camera modules for mobile phones and smartphones. Since the resin composition according to one embodiment of the present invention has good handleability when used, can be cured at a low temperature, and can give a cured product excellent in stress absorbability without impairing physical properties, it can be suitably used as a resin composition contained in an adhesive or a sealant for use in the assembly of an image sensor module requiring curing at a low temperature of about 80 ℃.
Semiconductor device with a semiconductor device having a plurality of semiconductor chips
The semiconductor device according to one embodiment of the present invention is formed using an adhesive or a sealing material containing the above resin composition. The semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules, electronic devices, and the like in which they are assembled. Since the resin composition according to one embodiment of the present invention has good handleability in use and can be cured at a low temperature of about 80 ℃ and can give a cured product excellent in stress absorbability without impairing physical properties, the resin composition can be suitably used as a resin composition contained in an adhesive or a sealant for use in the assembly of a semiconductor device requiring curing at a low temperature.
Examples
The present invention will be specifically described below by way of examples. The present invention is not limited to these examples.
Examples and comparative examples
The components were mixed in the proportions shown in table 1 or table 2 below to prepare resin compositions. In the following table, numerals indicating the blending ratio of the components (a) to (F) each represent parts by mass. The components in table 1 or table 2 are as follows.
(A) The components are as follows: 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, red iron chemical, weight average molecular weight: 316 epoxy equivalent: 158g/eq.
(A3) YX8000: hydrogenated bisphenol A type epoxy resin, mitsubishi chemical corporation, weight average molecular weight 410, epoxy equivalent: 205g/eq.
(A4) YX7400: an epoxy resin represented by the general formula (A-1-1) (wherein x in the general formula (A-1-1) is 10.3), mitsubishi chemical corporation, weight average molecular weight 870, epoxy equivalent: 435g/eq.
(A5) TSL9906: represented by the general formula (A-2) (R in the general formula (A-2) 6 ～R 9 Is a methyl group) of the epoxy resin, to sense and case sense. The subscriber company, weight average molecular weight 296, epoxy equivalent 181g/eq.
Thiol compound
(B) The components are as follows: difunctional thiol compounds
(B1) Thiol compound 1: difunctional thiol compound represented by the general formula (B-1-1), molecular weight 389, thiol equivalent: 211g/eq.
(B2) Thiol compound 2: difunctional thiol compound represented by the general formula (B-2-1), molecular weight 445, thiol equivalent: 243g/eq.
(B3) Thiol compound 3: difunctional thiol compound represented by the general formula (B-3-1), molecular weight 286, thiol equivalent: 159g/eq.
Thiol compounds other than component (B') (B)
(B' 4) DMDO:3, 6-dioxa-1, 8-octanediol (1, 8-dimercapto-3, 6-dioxaoctane), manufactured by tokyo chemical industry Co., ltd., molecular weight 182, thiol equivalent weight 91g/eq.
(B' 5) 1, 10-decanedithiol, manufactured by Tokyo chemical industry Co., ltd., molecular weight 206, thiol equivalent weight 103g/eq.
(B' 6) EPMG-4: tetraethyleneglycol bis (3-mercaptopropionate), manufactured by SC organic chemical Co., ltd., molecular weight 372, thiol equivalent 186g/eq.
(B' 7) PEMP: pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), manufactured by SC organic chemical Co., ltd., molecular weight 489, thiol equivalent 122g/eq.
(B' 8) C3 TS-G:1,3,4, 6-tetra (3-mercaptopropyl) glycoluril, manufactured by Kabushiki Kaisha, molecular weight 432, thiol equivalent 114g/eq.
(C) The components are as follows: amine compound
(C1) The first FXR-1121: solid dispersion type amine adduct, manufactured by T & K TOKA, inc.
(C2) HXA9322HP: a solid dispersion type latent curing catalyst (microcapsule imidazole adduct) was produced by Asahi Kabushiki Kaisha, 1/3 of the weight of which was a microcapsule imidazole adduct and 2/3 of which was a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, and the epoxy equivalent was 180g/eq.
(C3) Fujia-FXR-1020, tertiary amine compound, manufactured by T & K TOKA, inc.
(D) The components are as follows: packing material
(D1) SOE5: silica filler, manufactured by k corporation, having an average particle diameter of 1.5 μm.
(D2) BSP6: silica filler, manufactured by Lonsen, inc., having an average particle size of 5. Mu.m.
Fillers other than component (D') (D)
(D' 3) MSV-25G: silica filler, manufactured by Lonsen, inc., having an average particle size of 25. Mu.m.
(E) The components are as follows: stabilizing agent
(E1) TIPB: triisopropyl borate, manufactured by tokyo chemical industry co.
(F) Other ingredients
(F1) KBM403: 3-glycidoxypropyl trimethoxysilane (silane coupling agent), manufactured by Xinyue chemical Co., ltd.
Evaluation method
Volatility of
The weight of a metal container having a diameter of 5cm and a depth of 0.5cm was measured. To this was added as a target 1.0g of a thiol compound and left in an oven at 80℃for 1 hour without covering the cover. After cooling, the weight of the metal container was measured, and the volatile component derived from the thiol resin was measured. As a result, the volatile content of 1, 10-decanedithiol was 11%, and the volatile content of 3, 6-dioxa-1, 8-octanedithiol was 27%; in contrast, the volatile components of the other thiol resins containing thiol compounds 1, 2, and 3 are all 1% or less.
Determination 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℃and the viscosity at 50℃were measured (Pa.s). The measurement was performed using a viscoelastometer measuring device (model: MARS60, model number: MARS60, from Fu's company). The measurement conditions are as follows. Further, the ratio of the viscosity of the resin composition at 30℃to the viscosity at 50℃was determined (viscosity at 30℃/viscosity at 50 ℃). The viscosity ratio is preferably 1 to 4, more preferably 1 to 3.8, still more preferably 1 to 3.5, still more preferably 1 to 3.
Plate diameter: 35mm phi (parallel type)
Frequency: 1Hz
Distortion degree: 0.5
Heating rate: 3 ℃/min
Gap: 500 μm
Calculation of the difference in glass transition temperature (Tg) (ΔTg)
The loss elastic modulus E "(Tg 1) (. Degree. C.) and the loss tangent tan delta (Tg 2) (. Degree. C.) of the cured products obtained by curing the resin compositions of examples and comparative examples were measured using a dynamic viscoelasticity measuring Device (DMA) (product name: DMS6100, manufactured by Easter, tech.) of the dead-end. 2 glass plates to which Teflon (registered trademark) tape was attached were prepared, a 125 μm release film and a resin composition were placed on the Teflon (registered trademark) tape face of one glass plate, and the other glass plate was placed with the Teflon (registered trademark) tape faces opposed to each other, and heat-cured at 80℃for 180 minutes by a blast dryer, whereby a cured product having a thickness of about 130 μm was obtained. In addition, when the obtained cured product is fragile, the thickness of the separator is appropriately changed to produce the cured product. After the cured product was peeled off from the glass plate, a test piece (10.+ -. 0.5 mm. Times.40.+ -. 1 mm) was cut out from the cured product, and the width and thickness of the test piece were measured. Then, the dynamic viscoelasticity was measured by the above-mentioned dynamic viscoelasticity measuring apparatus (heating rate: 3 ℃ C./min, frequency: 10Hz, measuring range: 40 ℃ C. -150 ℃ C., strain amplitude: 5.0 μm, stretching method). The peak temperature (temperature at which the maximum value is the maximum value among a plurality of values) of tan δ (loss tangent) is read as the glass transition temperature (Tg 2). Further, the peak temperature of the loss elastic modulus E "(the temperature at which the maximum value is the maximum value among them) was read as the glass transition temperature (Tg 1). The difference ΔTg (. Degree. C.) between the glass transition temperature (Tg 1 (. Degree. C.) and the glass transition temperature (Tg 2 (. Degree. C.) was calculated. The ΔTg is preferably 12℃or higher.
Hydrolysis resistance
A cured product having a thickness of about 130 μm was produced under the same conditions as in the DMA measurement. When the resin composition contains an ester bond-containing compound, hydrolysis is performed at high temperature and high humidity, and the resin cured products of the compositions of comparative examples 5 and 6 are continuously subjected to PCT conditions (121 ℃ and 2 atmospheres) for 10 hours, the resin cured products liquefy, and the hydrolysis resistance is poor. On the other hand, the compositions of examples 15 and 16, in which the difunctional thiol compound of the present invention was used in combination, did not show any abnormality in the appearance of the cured resin product, although the thiol compound containing an ester bond was contained in the resin composition.
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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, the ratio of the viscosity at 30℃to the viscosity at 50℃of the resin compositions of examples 1 to 20 (viscosity at 30℃/viscosity at 50 ℃) was 1 to 4, and it was confirmed that the resin compositions were excellent in handleability regardless of the atmosphere in which the resin compositions were used. Further, it was confirmed that the cured products obtained by curing the resin compositions of examples 1 to 20 had a Δtg of 12 ℃ or higher, a broad glass transition region, and excellent stress absorbability.
The cured products obtained from the resin compositions of comparative examples 5 and 6 contained an ester bond-containing compound, and therefore were easily hydrolyzed, 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 have a ratio of viscosity at 30℃to viscosity at 50℃ (viscosity at 30℃/viscosity at 50 ℃) of 4 or more, and thus are difficult to handle due to ambient temperature. Further, it was confirmed that the Δtg of the cured product obtained by curing the resin composition of comparative example 6 was about 10 ℃, and the glass transition region was narrower than that of other compositions, and the stress absorbability was poor.
Claims (13)
1. A resin composition, the resin composition comprising:
(A) An epoxy resin;
(B) At least one difunctional thiol compound selected from the group consisting of: a difunctional thiol compound having a molecular weight of 210 or more, which contains an aromatic ring structure or an alicyclic structure, contains no ester bond and has a thiol group at the end, and contains a thioether bond or an ether bond in the molecule; and a difunctional thiol compound represented by the following general formula (B-4) or (B-5);
(C) An amine compound; and
(D) A filler having an average particle diameter of 0.1 μm or more and 10 μm or less,
wherein the total number of thiol groups of the difunctional thiol compound of the component (B) is 20 to 100 when the number of all thiol groups in the resin composition is 100,
wherein the equivalent ratio of thiol groups of all thiol compounds with respect to epoxy groups of the epoxy resin contained in the resin composition, that is, the epoxy equivalent: thiol equivalent, is 1:0.5 to 1:1.5,
[ chemical 24]
In the general formula (B-4), s and t are each independently integers of 3 or 4;
[ chemical 25]
In the general formula (B-5), u and v are each independently an integer of 3 or 4.
2. The resin composition according to claim 1, wherein the component (B) is a difunctional thiol compound having an alicyclic structure and a molecular chain containing no ester bond and having a thiol group at the end thereof in the molecule.
3. The resin composition according to claim 1, wherein the component (B) is a difunctional thiol compound having an aromatic ring structure in the molecule and a molecular chain having an ether bond and no ester bond and having a thiol group at the end.
4. The resin composition according to claim 1, wherein the component (B) is a difunctional thiol compound represented by the following general formula (B-1), (B-2) or (B-3):
[ chemical 20]
In the general formula (B-1), n and m are each independently integers of 1 to 3;
[ chemical 21]
In the general formula (B-2), R 1 、R 2 、R 3 And R is 4 Each independently is a hydrogen atom or a group represented by the following formula (b-1), however, R 1 And R is 2 One of them is a group represented by the following general formula (b-1), R 3 And R is 4 One of them is a group represented by the following general formula (b-1),
[ chemical 22]
In the general formula (b-1), r is an integer of 1 to 3;
[ chemical 23]
In the general formula (B-3), G 1 、G 2 Each independently is through-O-or-CH 2 -a bonded 2-valent group, p, q each independently being an integer from 2 to 5.
5. The resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the component (A) is 240 to 1,000.
6. The resin composition according to any one of claims 1 to 4, wherein the amine compound of component (C) is at least one amine compound selected from the group consisting of imidazole compounds, tertiary amine compounds and amine adducts.
7. The resin composition according to claim 1 to 4, wherein the filler of the component (D) is contained in an amount of 5 to 70% by mass relative to 100% by mass of the total resin composition.
8. The resin composition according to any one of claims 1 to 4, wherein the resin composition further comprises (E) a stabilizer.
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 borate compound, an aluminum chelate compound and barbituric acid.
10. An adhesive comprising the resin composition according to any one of claims 1 to 9.
11. A sealing material comprising the resin composition according to any one of claims 1 to 9.
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 using the adhesive according to claim 10 or the sealing material according to claim 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018196086 | 2018-10-17 | ||
| JP2018-196086 | 2018-10-17 | ||
| PCT/JP2019/040617 WO2020080390A1 (en) | 2018-10-17 | 2019-10-16 | Resin composition |
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| KR (1) | KR20210080363A (en) |
| CN (1) | CN112823177B (en) |
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| WO2022254906A1 (en) * | 2021-06-02 | 2022-12-08 | 旭化学工業株式会社 | Thermoplastic epoxy resin, adhesive, modifier, and method for producing thermoplastic epoxy resin |
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| CN1232849A (en) * | 1998-04-22 | 1999-10-27 | 奥依列斯工业株式会社 | Lubricating coating, sliding structure and sliding bearing device using the same structure |
| CN101309992A (en) * | 2005-08-16 | 2008-11-19 | 切弗朗菲利浦化学公司 | Mercaptan-hardened epoxy polymer compositions and processes for making and using same |
| CN103189412A (en) * | 2010-11-05 | 2013-07-03 | 汉高爱尔兰有限公司 | Epoxy-thiol compositions with improved stability |
| CN103184022A (en) * | 2011-12-30 | 2013-07-03 | 汉高股份有限公司 | Adhesive composition used for temporary adhesion in wafer preparation |
| JP2016079313A (en) * | 2014-10-20 | 2016-05-16 | 京セラケミカル株式会社 | Repairable adhesive composition and electric and electronic component |
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| WO2013108629A1 (en) * | 2012-01-18 | 2013-07-25 | 三井化学株式会社 | Composition, composition for display device end-face sealing agent comprising composition, and display device and method for manufacturing same |
| JP6534189B2 (en) | 2014-03-17 | 2019-06-26 | ナミックス株式会社 | Resin composition |
| EP3702348A4 (en) * | 2017-10-26 | 2021-07-21 | Shikoku Chemicals Corporation | Thiol compounds, synthesis method therefor, and utilization of said thiol compounds |
| JP6983380B2 (en) * | 2018-01-18 | 2021-12-17 | 味の素株式会社 | One-component resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232849A (en) * | 1998-04-22 | 1999-10-27 | 奥依列斯工业株式会社 | Lubricating coating, sliding structure and sliding bearing device using the same structure |
| CN101309992A (en) * | 2005-08-16 | 2008-11-19 | 切弗朗菲利浦化学公司 | Mercaptan-hardened epoxy polymer compositions and processes for making and using same |
| CN103189412A (en) * | 2010-11-05 | 2013-07-03 | 汉高爱尔兰有限公司 | Epoxy-thiol compositions with improved stability |
| CN103184022A (en) * | 2011-12-30 | 2013-07-03 | 汉高股份有限公司 | Adhesive composition used for temporary adhesion in wafer preparation |
| JP2016079313A (en) * | 2014-10-20 | 2016-05-16 | 京セラケミカル株式会社 | Repairable adhesive composition and electric and electronic component |
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| Publication number | Publication date |
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| CN112823177A (en) | 2021-05-18 |
| KR20210080363A (en) | 2021-06-30 |
| WO2020080390A1 (en) | 2020-04-23 |
| JPWO2020080390A1 (en) | 2021-09-16 |
| TW202028286A (en) | 2020-08-01 |
| TWI814922B (en) | 2023-09-11 |
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