CN112752783A - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- CN112752783A CN112752783A CN201980004492.2A CN201980004492A CN112752783A CN 112752783 A CN112752783 A CN 112752783A CN 201980004492 A CN201980004492 A CN 201980004492A CN 112752783 A CN112752783 A CN 112752783A
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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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- 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
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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Abstract
The present invention relates to: curing in a short time even under low temperature conditions, providing a glass transition temperature (T)g) An epoxy resin composition which is a cured product having a low tensile strength; a sealing material comprising the epoxy resin composition; a cured product obtained by curing the epoxy resin composition; and an electronic component comprising the cured product. The epoxy resin composition of the present invention provides a cured TgA cured product having a low tensile strength and a high tensile strength is useful as an adhesive, a sealing material, a dam agent, or the like for a semiconductor device or an electronic component.
Description
Technical Field
The present invention relates to an epoxy resin composition, a sealing material containing the same, a cured product obtained by curing the same, and an electronic component containing the cured product.
Background
Conventionally, in the assembly and mounting of electronic components used in semiconductor devices, for example, semiconductor chips, adhesives, sealing materials, and the like containing curable resin compositions, particularly epoxy resin compositions, have been frequently used for the purpose of maintaining reliability and the like. In particular, in the case of a semiconductor device including a member which is deteriorated under high temperature conditions, the manufacturing process thereof needs to be performed under low temperature conditions. Therefore, adhesives and sealing materials used for manufacturing such devices are required to exhibit sufficient curability even under low temperature conditions. For them, curing in a short time is also required at the same time from the aspect of production cost.
The epoxy resin composition (hereinafter, sometimes simply referred to as "curable composition") used for an adhesive or a sealing material for electronic components generally contains an epoxy resin and a curing agent. The epoxy resin includes various polyfunctional epoxy resins (epoxy resins having 2 or more epoxy groups). The curing agent contains a compound having 2 or more functional groups that react with epoxy groups in the epoxy resin. It is known that the type of the curing agent using a thiol curing agent in such a curable composition can be cured in a short time even under a low temperature condition of 0 ℃ to-20 ℃. The thiol curing agent contains a polyfunctional thiol compound which is a compound having 2 or more thiol groups. As an example of such a curable composition, a curable composition disclosed in patent document 1 can be cited.
The epoxy resin composition provides a cured product having various characteristics depending on the composition thereof. In this connection, the glass transition temperature (T) depends on the purpose of use of the curable composition and the likeg) The higher is sometimes not preferred. For example, 2 members each made of a different material may be joined using the curable composition.
When the ambient temperature of an assembly in which 2 parts each made of a different material are bonded to each other by an adhesive is changed, the parts generate thermal stress according to the thermal expansion coefficients of the materials thereof, respectively. The thermal stress is not uniform due to the difference in thermal expansion coefficient and cannot be offset, resulting in deformation of the assembly. Stress caused by the deformation may act particularly on the joint of the members, that is, on the cured product of the adhesiveCracks and the like occur in the cured product. In particular, when the cured product is brittle and lacks flexibility, such cracks are likely to occur. Therefore, an adhesive for joining members made of different materials needs to have flexibility (low elastic modulus) to such an extent that it can follow deformation of an assembly due to thermal expansion of the members after curing. Therefore, T is required for a cured productgSuitably low.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2012/093510
Disclosure of Invention
[ problems to be solved by the invention ]
However, the present inventors found that: the epoxy resin composition described in the above patent document 1 is TgIt is sufficiently low and exhibits excellent low-temperature curability, but has a problem of low tensile strength (Japanese: プル strength). Electronic parts sometimes require drop impact resistance, and it is desirable to increase the tensile strength of the adhesive in order to improve the drop impact resistance.
The present invention has been made in view of the above problems, and an object of the present invention is to provide: curing in a short time even under low temperature conditions, providing a glass transition temperature (T)g) An epoxy resin composition which is a cured product having a low tensile strength; a sealing material comprising the epoxy resin composition. Another object of the present invention is to provide a cured product obtained by curing the epoxy resin composition or the sealing material. Still another object of the present invention is to provide an electronic component comprising the cured product.
Means for solving the problems
Under such circumstances, the present inventors have developed a curing method for curing a curable resin composition in a short time even under low temperature conditions, and have provided a cured resin composition containing TgA curable composition of a cured product having a low tensile strength has been intensively studied. The results are unexpectedly found to be: as a component of the curable composition, a thiol curing agent and an epoxy resin are used, and a crosslinking density modifier containing an aromatic monofunctional epoxy resin is used to cure the curable compositionBy adjusting the physical property values of the compounds to predetermined ranges, the tensile strength of the resulting cured product is increased, i.e., the falling impact resistance is excellent. The present invention has been completed based on the above new findings.
That is, the present invention is not limited to the following, but includes the following inventions.
1. An epoxy resin composition comprising the following components (A) to (D):
component (A): a thiol-based curing agent comprising at least 1 multifunctional thiol compound having 3 or more thiol groups;
component (B): at least 1 multifunctional epoxy resin;
component (C): a crosslink density modifier comprising at least 1 aromatic monofunctional epoxy resin; and
component (D): a curing catalyst is used for curing the epoxy resin,
the epoxy resin composition provides: a cured product having a frequency of 10Hz, a temperature rise rate of 3 ℃/min, and a temperature at which the loss modulus (E') is maximum in a DMA measurement by a stretching method, which is in the range of 20 ℃ to 55 ℃.
2. The epoxy resin composition as described in the above item 1, wherein the molar ratio (B)/(A) of the component (B) to the component (A) is 1.15 or more and 1.45 or less.
3. The epoxy resin composition according to item 1 or 2 above, wherein the molar ratio (C)/(A) of the component (C) to the component (A) is 0.55 to 1.65.
4. The epoxy resin composition as described in any one of the preceding items 1 to 3, wherein the component (C) comprises an aromatic monofunctional epoxy resin.
5. A sealing material comprising the epoxy resin composition as described in any one of the above items 1 to 4.
6. A cured product obtained by curing the epoxy resin composition according to any one of the above items 1 to 4 or the sealing material according to the above item 5.
7. An electronic component comprising the cured product of item 6 above.
Drawings
Fig. 1 is a graph showing the relationship between the corrected tensile strength and the peak temperature (maximum value) of E ″.
Detailed Description
The present invention is described in detail below.
The epoxy resin composition (curable composition) of the present invention contains, as essential components, a thiol curing agent (component (a)), a polyfunctional epoxy resin (component (B)), a crosslinking density modifier (component (C)), and a curing catalyst (component (D)) as described above. These components (A) to (D) will be described below.
In the present specification, in accordance with the common practice in the field of epoxy resins, the name of the term "resin" which is generally used to refer to a polymer (particularly a synthetic polymer) is sometimes used for components constituting an epoxy resin composition before curing, even though the components are not polymers.
(1) Thiol curing agent (component (A))
The thiol curing agent (component (a)) used in the present invention contains at least 1 kind of polyfunctional thiol compound having 3 or more thiol groups that react with epoxy groups in the polyfunctional epoxy resin (component (B)) and the crosslinking density adjusting agent (component (C)) described later. Component (a) preferably comprises 3-functional and/or 4-functional thiol compounds. The mercaptan equivalent is preferably 90 to 150g/eq, more preferably 90 to 140g/eq, and still more preferably 90 to 130 g/eq. The 3-functional and 4-functional thiol compounds are thiol compounds having 3 thiol groups and 4 thiol groups, respectively.
In one embodiment of the present invention, the above-mentioned polyfunctional thiol compound is preferably used as the component (a) containing a non-hydrolyzable polyfunctional thiol compound having no hydrolyzable partial structure such as an ester bond, from the viewpoint of improving the moisture resistance of a cured product. The non-hydrolyzable polyfunctional thiol compound is not easily hydrolyzed even in a high-temperature and high-humidity environment.
In another embodiment of the present invention, the component (a) contains a thiol compound having an ester bond in a molecule and a thiol compound having no ester bond in a molecule. In addition, from low TgFrom the viewpoint of conversion, the component (a) preferably contains a thiol resin having no urea bond.
Examples of the hydrolyzable polyfunctional thiol compound include: trimethylolpropane tris (3-mercaptopropionate) (manufactured by SC organic Chemicals: TMMP), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate (manufactured by SC organic Chemicals: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC organic Chemicals: PEMP), tetraethyleneglycol bis (3-mercaptopropionate) (manufactured by SC organic Chemicals: EGMP-4), dipentaerythritol hexa (3-mercaptopropionate) (manufactured by SC organic Chemicals: DPMP), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) PE1), 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1, 3, 5-triazine-2, 4,6(1H,3H,5H) -trione (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) NR1), and the like.
Preferred non-hydrolyzable polyfunctional thiol compounds usable in the present invention are compounds represented by the following formula (1):
[ solution 1]
(in the formula, wherein,
R1and R2Independently selected from hydrogen atom, C1-C12 alkyl or phenyl,
R3、R4、R5and R6Each independently selected from mercaptomethyl, mercaptoethyl, and mercaptopropyl).
Examples of the compound represented by the formula (1) include: 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Sizhou chemical industry Co., Ltd.), (1,3,4, 6-tetrakis (3-mercaptopropyl) glycoluril (trade name: C3 TS-G, manufactured by Sizhou chemical industry Co., Ltd.), 1,3,4, 6-tetrakis (mercaptomethyl) glycoluril, 1,3,4, 6-tetrakis (mercaptomethyl) -3 a-methylglycoluril, 1,3,4, 6-tetrakis (2-mercaptoethyl) -3 a-methylglycoluril, 1,3,4, 6-tetrakis (3-mercaptopropyl) -3 a-methylglycoluril, 1,3,4, 6-tetrakis (mercaptomethyl) -3 a,6 a-dimethylglycoluril, 1,3,4, 6-tetrakis (2-mercaptoethyl) -3 a,6 a-dimethylglycoluril, 1,3,4, 6-tetrakis (3-mercaptopropyl) -3 a,6 a-dimethylglycoluril, 1,3,4, 6-tetrakis (mercaptomethyl) -3 a,6 a-diphenylglycoluril, 1,3,4, 6-tetrakis (2-mercaptoethyl) -3 a,6 a-diphenylglycoluril, 1,3,4, 6-tetrakis (3-mercaptopropyl) -3 a,6 a-diphenylglycoluril, and the like. These may be used alone or in combination of two or more. Of these, 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril and 1,3,4, 6-tetrakis (3-mercaptopropyl) glycoluril are particularly preferable
Other preferred non-hydrolyzable polyfunctional thiol compounds that can be used in the present invention are compounds represented by the following formula (2):
(R8)m－A－(R7－SH)n (2)
(in the formula, wherein,
a is a residue of a polyhydric alcohol having n + m hydroxyl groups, containing n + m oxygen atoms derived from the above hydroxyl groups,
each R is7Independently an alkylene group having 1 to 10 carbon atoms,
each R is8Independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
m is an integer of 0 or more,
n is an integer of 3 or more,
r is as defined above7And R8Bonded to the above A via the above oxygen atom, respectively).
Two or more compounds represented by formula (2) may be used in combination. Examples of the compound represented by the formula (2) include pentaerythritol tripropylmercaptan (trade name: PEPT, manufactured by SC organic Chemicals) and pentaerythritol tetrapropylmercaptan. Among these, pentaerythritol tripropylmercaptan is particularly preferable.
As the non-hydrolyzable polyfunctional thiol compound, a 3-or more-functional polythiol compound having 2 or more thioether bonds in the molecule may also be used. Examples of such thiol compounds include: 1,2, 3-tris (mercaptomethylthio) propane, 1,2, 3-tris (2-mercaptoethylthio) propane, 1,2, 3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dimercaptoThio groupOctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, a salt thereof, a stabilizer,4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, 1,3, 3-tetrakis (mercaptomethylthio) propane, 1,2, 2-tetrakis (mercaptomethylthio) ethane, 1,5, 5-tetrakis (mercaptomethylthio) -3-thiopentane, 1,6, 6-tetrakis (mercaptomethylthio) -3, 4-dithiohexane, 2, 2-bis (mercaptomethylthio) ethanethiol, 3-mercaptomethylthio-1, 7-dimercapto-2, 6-dithioheptane, 3, 6-bis (mercaptomethylthio) -1, 9-dimercapto-2, 5, 8-trithiononane, 3-mercaptomethylthio-1, 6-dimercapto-2, 5-dithiohexane, 1,1,9, 9-tetrakis (mercaptomethylthio) -5- (3, 3-bis (mercaptomethylthio) -1-thiopropyl) 3, 7-dithiononane, tris (2, 2-bis (mercaptomethylthio) ethyl) methane, tris (4, 4-bis (mercaptomethylthio) -2-thiobutyl) methane, tetrakis (2, 2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4, 4-bis (mercaptomethylthio) -2-thiobutyl) methane, 3,5,9, 11-tetrakis (mercaptomethylthio) -1, 13-dimercapto-2, 6,8, 12-tetrathiotridecane, 3,5,9,11,15, 17-hexakis (mercaptomethylthio) -1, 19-dimercapto-2, 6,8,12,14, 18-hexathiononadecane, 9- (2, 2-bis (mercaptomethylthio) ethyl) -3, 5,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 6,8,10,12, 16-hexathioheptadecane, 3,4,8, 9-tetrakis (mercaptomethylthio) -1, 11-dimercapto-2, 5,7, 10-tetrathioundecane, 3,4,8,9,13, 14-hexakis (mercaptomethylthio) -1, 16-dimercapto-2, 5,7,10,12, 15-hexathiohexadecane, 8- [ bis (mercaptomethylthio) methyl group]-3, 4,12, 13-tetrakis (mercaptomethylthio) -1, 15-dimercapto-2, 5,7,9,11, 14-hexathiopentadecane, 4, 6-bis [3, 5-bis (mercaptomethylthio) -7-mercapto-2, 6-dithioheptylthio]-1, 3-dithiane, 4- [3, 5-bis (mercaptomethylthio) -7-mercapto-2, 6-dithioheptylthio]-6-mercaptomethylthio-1, 3-dithiane, 1-bis [ 4- (6-mercaptomethylthio) -1, 3-dithianylthio]-1, 3-bis (mercaptomethylthio) propane, 1- [ 4- (6-mercaptomethylthio) -1, 3-dithianylthio]-3- [2, 2-bis (mercaptomethylthio) ethyl]-7, 9-bis (mercaptomethylthio) -2, 4,6, 10-tetrathiaundecane, 3- [ 2- (1, 3-dithio-)Heterocyclic butyl radical)]Methyl-7, 9-bis (mercaptomethylthio) -1, 11-dimercapto-2, 4,6, 10-tetrathiaundecane, 9- [ 2- (1, 3-dithiocyclobutyl)]Methyl-3, 5,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 6,8,10,12, 16-hexathiaheptadecane, 3- [ 2- (1, 3-dithiocyclobutyl)]Aliphatic polythiol compounds such as methyl-7, 9,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 4,6,10,12, 16-hexathiaheptadecane; 4, 6-bis [ 4- (6-mercaptomethylthio) -1, 3-dithianylthio]-6- [ 4- (6-mercaptomethylthio) -1, 3-dithianylthio]-1, 3-dithiane, 4- [3,4,8, 9-tetrakis (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecanyl]-5-mercaptomethylthio-1, 3-dithiolane, 4, 5-bis [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio]-1, 3-dithiolane, 4- [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio]-5-mercaptomethylthio-1, 3-dithiolane, 4- [ 3-bis (mercaptomethylthio) methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithiooctyl]-5-mercaptomethylthio-1, 3-dithiolane, 2- { bis [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio]Methyl } -1, 3-dithiolane butane, 2- [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio]Mercaptomethylthiomethyl-1, 3-dithiocyclobutane, 2- [3,4,8, 9-tetrakis (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecylthio]Mercaptomethylthiomethyl-1, 3-dithiocyclobutane, 2- [ 3-bis (mercaptomethylthio) methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithiooctyl]Mercaptomethylthiomethyl-1, 3-dithiolane, 4- { 1- [ 2- (1, 3-dithiolane butyl)]-3-mercapto-2-thiopropylthio } -5- [1, 2-bis (mercaptomethylthio) -4-mercapto-3-thiobutylthio]Polythiol compounds having a cyclic structure such as 1, 3-dithiolane.
(2) Epoxy resin (component (B))
The epoxy resin (component (B)) used in the present invention is not particularly limited as long as it contains at least 1 kind of polyfunctional epoxy resin. Therefore, conventionally used epoxy resins can be used as the component (B). As described above, the multifunctional epoxy resin means an epoxy resin having 2 or more epoxy groups. In one embodiment of the present invention, the component (B) contains a 2-functional epoxy resin.
The polyfunctional epoxy resin is roughly classified into an aliphatic polyfunctional epoxy resin and an aromatic polyfunctional epoxy resin.
Examples of the aliphatic polyfunctional epoxy resin include:
a diepoxy resin such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, and dicyclopentadiene type diglycidyl ether;
-a triglycidyl resin such as trimethylolpropane triglycidyl ether, glycerol triglycidyl ether;
alicyclic epoxy resins such as vinyl (3, 4-cyclohexene) dioxide, 2- (3, 4-epoxycyclohexyl) -5, 1-spiro- (3, 4-epoxycyclohexyl) m-dioxane;
glycidyl amine type epoxy resins such as tetraglycidyl bis (aminomethyl) cyclohexane;
hydantoin type epoxy resins such as 1, 3-diglycidyl-5-methyl-5-ethylhydantoin; and
epoxy resins having a siloxane skeleton such as 1, 3-bis (3-glycidoxypropyl) -1, 1,3, 3-tetramethyldisiloxane, and the like, but are not limited thereto.
In the above examples, "cyclohexane type diglycidyl ether" refers to a compound having the following structure: 2 glycidyl groups are bonded to a 2-valent saturated hydrocarbon group having 1 cyclohexane ring as a parent structure via an ether bond. "Dicyclopentadiene-type diglycidyl ether" refers to a compound having the following structure: 2 glycidyl groups are bonded to a 2-valent saturated hydrocarbon group having a dicyclopentadiene skeleton as a parent structure via an ether bond. The aliphatic polyfunctional epoxy resin preferably has an epoxy equivalent of 90 to 450 g/eq. Further, as the cyclohexane type diglycidyl ether, cyclohexanedimethanol diglycidyl ether is particularly preferable.
In one embodiment of the present invention, the component (B) contains an aliphatic multifunctional epoxy resin. When an aliphatic polyfunctional epoxy resin is used as the component (B), the component (a) to be combined preferably contains a 3-functional thiol compound or a 4-functional thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton. The ratio of the epoxy functional group equivalent of the aliphatic polyfunctional epoxy resin to the thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton ([ epoxy functional group equivalent ]/[ thiol functional group equivalent ]) is preferably 0.40 to 0.85.
In a certain embodiment of the present invention, the component (a) contains a 3-functional thiol compound or a 4-functional thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton. When a 3-functional thiol compound or a 4-functional thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton is used as the component (a), a cyclohexane-type diglycidyl ether or an epoxy resin having a silicone skeleton is preferably used as the component (B). Particular preference is given to using 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 3-bis (3-glycidoxypropyl) -1, 1,3, 3-tetramethyldisiloxane.
In addition, in a certain embodiment of the present invention, the component (a) contains a 3-functional thiol compound or a 4-functional thiol compound having no glycoluril skeleton or isocyanuric acid skeleton (specifically, a 3-functional thiol compound or a 4-functional thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton). In order to set the temperature at which E ″ becomes maximum to a desired range, the total amount of the aliphatic polyfunctional epoxy resin and the 3-functional thiol compound or the 4-functional thiol compound having no glycoluril skeleton or isocyanuric acid skeleton in the epoxy resin composition is preferably 10% by mass or more and 55% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and still more preferably 25% by mass or more and 50% by mass or less.
The aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin having a structure containing an aromatic ring such as a benzene ring. The epoxy resins are frequently used in the past, such as bisphenol a type epoxy resins. Examples of the aromatic polyfunctional epoxy resin include:
-bisphenol a type epoxy resins;
a branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether;
-bisphenol F type epoxy resins;
-epoxy resins of the novolac type;
-tetrabromobisphenol a type epoxy resin;
-epoxy resins of the fluorene type;
-biphenyl aralkyl epoxy resins;
diepoxy resins such as 1, 4-phenyl dimethanol diglycidyl ether;
biphenyl type epoxy resins such as 3,3',5,5' -tetramethyl-4, 4' -diglycidyloxybiphenyl;
glycidyl amine type epoxy resins such as diglycidyl aniline, diglycidyl toluidine, triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine; and
naphthalene ring-containing epoxy resins and the like, but are not limited thereto.
From the viewpoint of compatibility with the thiol compound, the component (B) preferably further contains an aromatic polyfunctional epoxy resin, as compared with the aliphatic polyfunctional epoxy resin. The aromatic polyfunctional epoxy resin is preferably a bisphenol F type epoxy resin, a bisphenol A type epoxy resin or a glycidylamine type epoxy resin, and among these, an epoxy resin having an epoxy equivalent of 90 to 200g/eq is particularly preferable, and an epoxy resin having an epoxy equivalent of 110 to 190g/eq is most preferable.
When an aromatic polyfunctional epoxy resin is used as the component (B), the component (a) to be combined is preferably a 3-functional thiol compound or a 4-functional thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton. The ratio of epoxy functional group equivalent of the aromatic polyfunctional epoxy resin to a thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton ([ epoxy functional group equivalent ]/[ thiol functional group equivalent ]) is preferably 0.30 to 1.10. When a 3-functional thiol compound or a 4-functional thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton is used as the component (a), it is preferable to use at least one of a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin and a naphthalene ring-containing epoxy resin as the component (B).
In order to set the temperature at which E ″ becomes maximum within a desired range, the total amount of the aromatic epoxy resin (monofunctional or polyfunctional aromatic epoxy resin) and the 3-functional thiol compound or 4-functional thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton in the epoxy resin composition is preferably 45% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 80% by mass or less, and still more preferably 50% by mass or more and 75% by mass or less.
(3) Crosslinking Density modifier (component (C))
The crosslinking density modifier (component (C)) used in the present invention is not particularly limited as long as it contains at least 1 aromatic monofunctional epoxy resin. Monofunctional epoxy resins are epoxy resins having 1 epoxy group, and have been conventionally used as reactive diluents for adjusting the viscosity of epoxy resin compositions. Monofunctional epoxy resins are roughly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the epoxy equivalent of the component (C) is preferably 180 to 400 g/eq. In the present invention, the component (C) preferably contains an aromatic monofunctional epoxy resin from the viewpoint of viscosity and low volatility. Further, the component (C) is more preferably substantially an aromatic monofunctional epoxy resin.
Examples of the aromatic monofunctional epoxy resin contained in the component (C) include: phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidylphthalimide, etc., but are not limited thereto. Among these, p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tert-butylphenyl glycidyl ether is particularly preferred. Examples of aliphatic monofunctional epoxy resins include: n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α -pinene oxide, allyl glycidyl ether, 1-vinyl-3, 4-epoxycyclohexane, 1, 2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane, 1, 3-bis (3-glycidoxypropyl) -1, 1,3, 3-tetramethyldisiloxane, glycidyl neodecanoate, and the like, but are not limited thereto.
(4) Curing catalyst (component (D))
The curing catalyst (component (D)) used in the present invention is not particularly limited as long as it is a curing catalyst for an epoxy resin (component (B)) and a known one can be used. Component (D) is preferably a latent curing catalyst. Latent cure catalysts refer to: the compound which is in an inactive state at room temperature, is activated by heating, and functions as a curing catalyst includes, for example: an imidazole compound which is solid at normal temperature; solid dispersion type amine adduct-based latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct-based); a reaction product of an amine compound with an isocyanate compound or a urea compound (urea-type adduct system), and the like. By using the above-mentioned component (D), the epoxy resin composition of the present invention can be cured in a short time even under low temperature conditions.
As typical examples of commercially available products of latent curing catalysts, amine-epoxy adduct systems (amine adduct systems) include: "AMICURE PN-23" (Ajinomoto Fine-Techni Co., trade name), "AMICURE PN-40" (Ajinomoto Fine-Techni Co., trade name), "AMICURE PN-50" (Ajinomoto Fine-Techni Co., trade name), "Harden X-3661S" (ACR Co., trade name), "Harden X-3670S" (ACR Co., trade name), "NOVACURE HXE-3742" (Asahi Kasei Co., trade name), "NOVACURE HXE-3721" (Asahi Kasei Co., trade name), "NOVARE A9322 HP" (Asahi Kasei Co., trade name), "NOVACURE 3922 HP" (Asahi Ka, Su Ka) (Asahi Ka) (Asahi Ka) (Asahi Ka 6745, Ka) (Fuji Ko Ka) 6782 (Fuji), and Ka, Trade name), "Fuji Cure FXR-1030" (T & K TOKA, trade name), and the like, but are not limited thereto. The component (D) may be used alone or in combination of two or more. The component (D) is preferably a solid dispersion type amine adduct type latent curing catalyst from the viewpoint of pot life and curability.
The component (D) includes a type provided in the form of a dispersion liquid dispersed in the polyfunctional epoxy resin. It is to be noted that, when the component (D) in this form is used, the amount of the polyfunctional epoxy resin in which the component (D) is dispersed is also included in the amount of the above-mentioned component (B) in the epoxy resin composition of the present invention.
Thiol functional group equivalents refer to: the total number of thiol groups of the thiol compound contained in the component or composition of interest is a quotient obtained by dividing the mass (g) of the thiol compound contained in the component or composition of interest by the thiol equivalent weight of the thiol compound (when a plurality of thiol compounds are contained, the total of the quotient of each thiol compound). The mercaptan equivalent weight can be determined by iodometric titration. This method is well known and is disclosed, for example, in paragraph 0079 of Japanese patent laid-open No. 2012-153794. When the thiol equivalent weight cannot be obtained by this method, it can be calculated as a quotient obtained by dividing the molecular weight of the thiol compound by the number of thiol groups in 1 molecule of the thiol compound.
On the other hand, the epoxy functional group equivalent means: the total number of epoxy groups in the epoxy resins (the above-mentioned components (B) and (C)) contained in the same component or composition is a quotient obtained by dividing the mass (g) of the epoxy resin contained in the component or composition of interest by the epoxy equivalent weight of the epoxy resin (when a plurality of epoxy resins are contained, the total of the quotient of the respective epoxy resins). The epoxy equivalent can be determined by the method described in JIS K7236. When the epoxy equivalent cannot be obtained by this method, the epoxy equivalent can be calculated as a quotient obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in 1 molecule of the epoxy resin.
The epoxy resin composition having an excess of thiol-based curing agent relative to the epoxy resin provides an initial Tg(T immediately after curingg) Low content of cured product. However, when the thiol curing agent is excessive in amount relative to the epoxy resin, many thiol groups remain in the cured product in an unreacted state without reacting with the epoxy group. The inventors of the present invention found that: although patent document 1 discloses T after the heat resistance testgHowever, such a composition may be newly crosslinked by excessive thiol groups after a moisture resistance reliability test (particularly, 100 hours in an environment of 85 ℃ and 85%) is performed. This crosslinking proceeds more slowly than when the epoxy resin is in excess relative to the thiol-based curing agent, but brings about TgIs increased. In one embodiment of the present invention, therefore, the ratio of the sum of the epoxy functional group equivalents of the components (B) and (C) to the thiol functional group equivalent of the component (a) [ epoxy functional group equivalent ]/[ thiol functional group equivalent ]) is preferably 0.70 or more and 1.10 or less, more preferably 0.75 or more and 1.10 or less, and particularly preferably 0.80 or more and 1.05 or less. In such a curable composition, since the epoxy group contained in the component (C) is present to reduce the unreacted thiol group, the unreacted thiol group is mostly eliminated as a result of the reaction between the epoxy group and the epoxy group. The polyfunctional epoxy resin contained in the component (B) has a function of extending polymer chains or forming crosslinks between polymer chains by linking 2 molecules of the polyfunctional thiol compound contained in the component (a). However, since the monofunctional epoxy resin contained in the component (C) does not have such a function, T which causes a cured product to be T can be suppressed by the reaction between the components (A) and (C)gIncreased new cross-linking occurs. Therefore, the cured product provided by such a curable composition has a small content of functional groups capable of forming new crosslinks, and therefore, after curing, T associated with the formation of new crosslinks is hardly observed even after a long period of timegIs increased.
In one aspect of the present invention, when the ratio of the sum of the epoxy functional group equivalents of the components (B) and (C) to the thiol functional group equivalent of the component (a) [ epoxy functional group equivalent ]/[ thiol functional group equivalent ] is 0.70 or more and 1.10 or less, both of the epoxy group and the thiol group in the composition participate in the reaction between the epoxy group and the thiol group at a certain ratio or more, and therefore, the properties of the resulting cured product become suitable. When the above ratio is less than 0.70, the thiol group is excessive relative to the epoxy group, so that the number of thiol groups remaining in an unreacted state in the cured product increases, and it becomes difficult to suppress T of the cured product associated with the reaction between the thiol groupsgIs increased. On the other hand, when the above ratio exceeds 1.10, the epoxy group is excessive relative to the thiol group, and therefore, in addition to the reaction between the epoxy group and the thiol group, the reaction (homopolymerization) between the excessive epoxy groups proceeds. As a result, intermolecular crosslinking by these two reactions is formed in the resulting cured product, and the crosslinking density becomes excessively high, resulting in TgAnd (4) rising. Alternatively, curing at a low temperature of 80 ℃ for 1 hour or the like becomes difficult.
If desired, the curable composition of the present invention may contain any components other than the above-mentioned components (A) to (D), for example, the following components, as required.
Stabilizers
If desired, stabilizers may be added to the epoxy resin composition of the present invention. A stabilizer may be added to the epoxy resin composition of the present invention in order to improve the storage stability and prolong the pot life. Various stabilizers known as stabilizers for one-pack adhesives mainly composed of epoxy resins can be used, and at least 1 selected from liquid boric acid ester compounds, aluminum chelates, and organic acids is preferable from the viewpoint of high effect of improving storage stability.
Examples of the liquid boric acid ester compound include: 2,2 '-oxybis (5, 5' -dimethyl-1, 3, 2-oxahexaborane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7, 10-tetraoxaundecyl) (1,4,7,10, 13-pentaoxatetradecyl) (1,4, 7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tricresyl borate, triethanolamine borate, and the like. The liquid boric acid ester compound is preferably used because it is liquid at room temperature (25 ℃ C.) and the viscosity of the composition is suppressed to a low level. As the aluminum chelate compound, for example, aluminum chelate compound A (available from Chuan Min Kogyo Co., Ltd.) can be used. As the organic acid, barbituric acid, for example, can be used.
When the stabilizer is added, the amount of the stabilizer added is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and still more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the total amount of the components (a) to (D).
Fillers
If desired, a filler may be added to the epoxy resin composition of the present invention. When the epoxy resin composition of the present invention is used as a one-pack adhesive, the moisture resistance and heat cycle resistance, particularly the heat cycle resistance, of the part to be bonded are improved by adding a filler thereto. The reason why the thermal cycle resistance is improved by adding the filler is that the linear expansion coefficient of the cured product is reduced, that is, expansion and contraction of the cured product due to thermal cycle are suppressed.
The filler is not particularly limited as long as it has an effect of reducing the linear expansion coefficient, and various fillers can be used. Specific examples of the filler include a silica filler, an alumina filler, a talc filler, a calcium carbonate filler, a Polytetrafluoroethylene (PTFE) filler, and the like. Among these, silica fillers are preferable because the loading amount can be increased.
When a filler is added, the content of the filler in the epoxy resin composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 65% by mass, and still more preferably 5 to 50% by mass of the entire epoxy resin composition.
Coupling agent
If desired, a coupling agent may be added to the epoxy resin composition of the present invention. From the viewpoint of improving the adhesive strength, it is preferable to add a coupling agent, particularly a silane coupling agent. As the coupling agent, various silane coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, mercapto and the like can be used. Specific examples of the silane coupling agent include: 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. These silane coupling agents may be used alone or in combination of two or more.
In the epoxy resin composition of the present invention, the amount of the coupling agent to be added is preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the components (a) to (D), from the viewpoint of improving the adhesive strength.
Other additives
If desired, other additives such as carbon black, titanium black, ion capturing agents, leveling agents, antioxidants, antifoaming agents, thixotropic agents, viscosity adjusting agents, flame retardants, colorants, solvents, and the like may be added to the epoxy resin composition of the present invention within a range that does not impair the gist of the present invention. The kind and amount of each additive are determined by a conventional method.
The epoxy resin composition of the present invention provides a cured product having a temperature at which the loss modulus (E') is maximized within a range of 20 ℃ to 55 ℃. The loss modulus is an imaginary part of a complex modulus representing a dynamic elastic modulus of an object in a complex number, and is a dissipation energy representing viscoelasticity in a dynamic behavior. In the present specification, unless otherwise specified, the loss modulus represents a value measured by dynamic viscoelasticity measurement (DMA) by a tensile method at a frequency of 10Hz, a temperature rise rate of 3 ℃/min, and a strain amplitude of 5.0 μm.
The amount of the components (a) to (D) constituting the epoxy resin composition of the present invention can be adjusted by those skilled in the art so that the cured product provided from the composition has a predetermined loss modulus. Further, a method of measuring the loss modulus is well known, and a person skilled in the art can easily measure the loss modulus by using a conventional dynamic viscoelasticity measuring apparatus.
As described above, the temperature at which such a loss modulus (E') is maximized in the cured product provided by the epoxy resin composition of the present invention is in the range of 20 ℃ to 55 ℃. In the case of an epoxy resin composition having a temperature outside the above range, the tensile strength of the cured product, that is, the drop impact resistance, is not sufficiently improved.
The epoxy resin composition of the present invention provides a cured product having a temperature at which the loss modulus is extremely high, preferably in the range of 20 ℃ to 50 ℃, more preferably 20 ℃ to 45 ℃.
From the viewpoint of the dynamic viscoelasticity of the cured product being as described above, the molar ratio (B)/(a) of the component (B) to the component (a) in the epoxy resin composition of the present invention is preferably 1.15 to 1.45.
For the same reason, in the epoxy resin composition of the present invention, the molar ratio (C)/(a) of the component (C) to the component (a) is 0.55 to 1.65.
The relationship between the molar ratio (B)/(a) of the component (B) and the component (a) means that the crosslinking point of the component (a) containing a thiol compound having 3 or more thiol groups is reduced, and for example, a 2-functional thiol compound or a 3-functional thiol compound is used as long as the thiol compound has 4 thiol groups. If the above ratio is less than 1.15, the amount of the polyfunctional epoxy resin as a crosslinking component is too small, and therefore, the resulting cured product may exhibit properties such as a thermoplastic resin that melts at a high temperature. On the other hand, if the above ratio exceeds 1.45, the polyfunctional epoxy resin as a crosslinking component becomes excessive, and therefore, intermolecular crosslinking due to the reaction of the components (a) and (B) may excessively form in the obtained cured product, and the crosslinking density may become too high, resulting in a decrease in tensile strength.
The relationship between the molar ratio (C)/(a) of the component (C) and the component (a) means that the thiol group of the component (a) is excessively added to the number (amount) of epoxy groups contained in the component (C). Satisfying this relationship is preferable because a cured product having an appropriate crosslink density formed by the reaction of the components (a) and (B) can be obtained.
By satisfying the relationship between the molar ratio (B)/(a) of the component (B) to the component (a) and the molar ratio (C)/(a) of the component (C) to the component (a), the thiol group of the component (a) which does not react with the component (B) reacts with the component (C), and the unreacted thiol group remaining in the cured product is reduced, so that the properties of the obtained cured product become suitable.
The cured product provided by the epoxy resin composition of the present invention exhibits excellent tensile strength particularly for an adherend selected from LCP (liquid crystal polymer), PC (polycarbonate), PBT (polybutylene terephthalate), SUS, alumina, and nickel (including those having a nickel-plated surface). These may be surface-treated by plasma or the like. In the present specification, "tensile strength" typically means the tensile strength when these adherends are made of these materials.
The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, the epoxy resin composition of the present invention can be obtained by introducing the components (a) to (D) and, if desired, other additives into an appropriate mixer simultaneously or separately, and stirring and mixing them while melting them by heating if necessary to obtain a uniform composition. The mixer is not particularly limited, and a kneader provided with a stirring device and a heating device, a henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like can be used. These devices may be used in combination as appropriate.
The epoxy resin composition thus obtained is thermosetting, and is preferably cured at a temperature of 80 ℃ within 5 hours, more preferably within 1 hour. In addition, high-temperature and ultra-short-time curing at a temperature of 150 ℃ for several seconds can be realized. When the curable composition of the present invention is used for manufacturing an image sensor module including a component that deteriorates under high temperature conditions, the composition is preferably heat-cured at a temperature of 60 to 90 ℃ for 30 to 120 minutes, or at a temperature of 120 to 200 ℃ for 1 to 300 seconds.
The epoxy resin composition of the present invention cures in a short time even under low temperature conditions and provides TgLow content of cured product. T of cured product of epoxy resin composition of the present inventiongPreferably 65 ℃ or lower, more preferably 60 ℃ or lower, and still more preferably 50 ℃ or lower. In addition, from the viewpoint of adhesion, T of cured productgPreferably 30 ℃ or higher, more preferably 32 ℃ or higher. In the present invention, TgThe strain amplitude can be determined by a stretching method using a dynamic thermomechanical measuring Device (DMA) under the conditions of a temperature range of-20 ℃ to 110 ℃, a frequency of 1 Hz to 10Hz, a temperature rise rate of 1 ℃/min to 10 ℃/min, and a strain amplitude of 5.0 μm. The preferred frequency is 10Hz, and the preferred rate of temperature rise is 3 deg.C/min. T isgThe loss tangent (tan δ) is determined from the peak temperature of the loss tangent (E ″)/storage modulus (E').
The epoxy resin composition of the present invention can be used as an adhesive, a sealing material, a dam agent or a raw material thereof for fixing, bonding or protecting, for example, a semiconductor device including various electronic components, components constituting the electronic components, or the like.
The present invention also provides a sealing material comprising the epoxy resin composition of the present invention. The sealing material of the present invention is suitable as a filling material for protecting and fixing, for example, a module, an electronic component, and the like.
The present invention also provides a cured product obtained by curing the epoxy resin composition or the sealing material of the present invention.
The present invention further provides an electronic component comprising the cured product of the present invention.
[ examples ]
The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following examples, parts and% are parts by mass and% by mass unless otherwise specified.
Examples 1 to 9 and comparative examples 1 to 3
Epoxy resin compositions were prepared by mixing predetermined amounts of the respective components using a three-roll mill in the proportions shown in tables 1 to 2. In tables 1 to 2, the amounts of the respective components are expressed in parts by mass (unit: g).
Thiol curing agent (component (A))
In examples and comparative examples, compounds used as the component (a) are shown below.
(A-1): 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Siguo Kasei Kogyo Co., Ltd., thiol equivalent: 100)
(A-2): trimethylolpropane tris (3-mercaptomercaptopropionate) (trade name: TMMP, manufactured by SC organic Chemicals, thiol equivalent: 133)
(A-3): pentaerythritol Tetrakis (3-mercaptopropionate) (trade name: PEMP, manufactured by SC organic Chemicals Co., Ltd., thiol equivalent: 122)
Epoxy resin (component (B))
In examples and comparative examples, compounds used as the component (B) are shown below.
(B-1): bisphenol F type epoxy resin (trade name: YDF-8170, made by Nissi iron Corp., epoxy equivalent: 159)
(B-2): bisphenol F epoxy resin-bisphenol A epoxy resin mixture (trade name: EXA-835 LV, manufactured by DIC Co., Ltd.; epoxy equivalent: 165)
(B-3): dicyclopentadiene type epoxy resin (trade name: EP4088L, manufactured by ADEKA Co., Ltd., epoxy equivalent 165)
(B-4): 1, 4-cyclohexanedimethanol diglycidyl ether (trade name: CDMDG, manufactured by Showa Denko K.K.: epoxy equivalent: 133)
(B-5): 1, 3-bis (3-glycidoxypropyl) -1, 1,3, 3-tetramethyldisiloxane (trade name: TSL9906, manufactured by Momentive Performance Materials Japan K.K., epoxy equivalent: 181)
Crosslinking Density adjuster (component (C))
In examples and comparative examples, compounds used as the component (C) are shown below.
(C-1): p-tert-butylphenyl glycidyl ether (trade name: ED509S, manufactured by ADEKA corporation; epoxy equivalent: 205)
(C-2): phenyl glycidyl ether (trade name: DENACOL EX141, manufactured by Nagase ChemteX, epoxy equivalent: 151)
(C-3): 2-ethylhexyl glycidyl ether (trade name: DENACOL EX121, manufactured by Nagase ChemteX, Ltd., epoxy equivalent: 187)
Curing catalyst (component (D))
In examples and comparative examples, compounds used as the component (D) are shown below.
(D-1) amine-epoxy adduct-based latent curing catalyst 1 (trade name: NOVACURE HXA9322HP, manufactured by Asahi Chemicals Co., Ltd.)
The latent curing catalyst (D-1) is provided in the form of: a dispersion liquid in which a fine particle latent curing catalyst was dispersed in an epoxy resin (a mixture of a bisphenol a type epoxy resin and a bisphenol F type epoxy resin (epoxy equivalent: 170)) (latent curing catalyst/a mixture of a bisphenol a type epoxy resin and a bisphenol F type epoxy resin: 33/67 (mass ratio)). (D-1) in tables 1 to 2 is a part by mass of a dispersion liquid containing a latent curing catalyst. The epoxy resin constituting the dispersion is treated as a substance that becomes a part of the component (B). Accordingly, the epoxy resin in (D-1) is contained in (B) of "(B)/(A) (molar ratio)" in tables 1 to 2.
Other component (E)
In examples and comparative examples, compounds used as the component (E) are shown below.
(E-1): silica Filler 1 (trade name: SE2300, average particle diameter 0.6 μm, manufactured by ADMATECHS Co., Ltd.)
(E-2): silica Filler 2 (trade name: SO-E5, average particle diameter 2.0 μm, manufactured by ADMATECHS Co., Ltd.)
In examples and comparative examples, the properties of cured products obtained by curing the epoxy resin compositions were measured in the following manner.
(preparation of cured product)
The resin compositions of examples 1 to 9 and comparative examples 1 to 3 were heated at 80 ℃ for 120 minutes to obtain cured products.
Loss modulus (E') of cured product
T according to JIS C6481gThe assay of (1). Specifically, a Teflon (registered trademark) sheet was first attached to the surface of a glass plate having a thickness of 3mm, and spacers were disposed at 2 positions on the sheet so that the thickness of the cured film was 400. + -. 150. mu.m (the sheet was formed by stacking heat-resistant tapes). Then, the resin composition was applied between the spacers, and sandwiched between separate glass plates having a teflon (registered trademark) sheet attached to the surface thereof to avoid inclusion of air bubbles, and the resultant was cured at 80 ℃ for 120 minutes to obtain a cured product. Finally, the cured product was peeled off from the glass plate to which a teflon (registered trademark) sheet was attached, and then cut into a predetermined size (10mm × 40mm) with a knife to obtain a test piece. Note that the cut was smoothed with sandpaper. The loss modulus (E) of the cured product was measured by a tensile method using a dynamic thermomechanical measuring apparatus (DMA) (manufactured by Seiko Instruments) under conditions of a temperature range of-20 ℃ to 110 ℃, a frequency of 10Hz, a temperature rise rate of 3 ℃/min, and a strain amplitude of 5.0 μm, and the temperature (. degree.C.) at which E' reaches the maximum was determined. The results are shown in tables 1 to 2.
Measured and corrected tensile Strength of cured product
Spacers (150 μm thick heat-resistant belts) were disposed at 2 positions on an alumina plate 20mm in length by 20mm in width by 1.6mm in thickness. Then, 1mg of the resin composition was applied between the spacers. A square plate (2.5g) having a thickness of 9mm square and subjected to a bright nickel plating treatment was placed on the spacer so as to contact the resin composition applied. Thereafter, the resultant was cured by heating at 80 ℃ for 120 minutes to obtain a test piece. The nut was bonded to the upper part of the thick plate of the test piece using a moisture-curable adhesive, and the thick plate and the nut were left to stand for 12 hours to sufficiently join each other in order to prevent peeling between the thick plate and the nut when the tensile strength was measured. Thereafter, the alumina plate was fixed to a precision load measuring instrument (model 1605HTP, manufactured by Aikoh Engineering) so that the adhesion surface became horizontal, and then a rope was passed through the ring of the nut, the rope was attached to a jig, and a pulling load was applied at a speed of 12 mm/min in the vertical direction at 23 ℃. The measured tensile strength was obtained by dividing the maximum load applied until the alumina plate and the thick plate were separated by the bonding area between the alumina plate and the thick plate (N6). Unit is N/mm2. Further, from the measured tensile strength, a corrected tensile strength was obtained using the following formula derived from the comparison of examples 1 and 2. Unit is N/mm2. The results are shown in tables 1 to 2.
Corrected tensile strength measured tensile strength/((100-content of component (E) (% by weight) × 1.2)/100)
The epoxy resin composition of the present invention can be used by adding the component (E) (filler) as needed, but as is clear from comparison of examples 1 and 2, the actual tensile strength of the cured product tends to decrease when the content of the component (E) (filler) increases. The corrected tensile strength is a tensile strength that cancels out the influence of the component (E).
As is clear from tables 1 to 2, in any of examples 1 to 9, the tensile strength after curing (particularly, the corrected tensile strength) was a satisfactory value.
In contrast, in comparative examples 1 to 2 in which the temperature at which the maximum E' of the cured product is reached is not within the predetermined range and comparative example 3 in which the component (C) is not contained, the tensile strength after curing is insufficient. As is clear from comparative example 3, in the epoxy resin composition having no predetermined composition, the tensile strength after curing is not sufficiently improved even if the temperature at which the maximum E ″ of the cured product is within the predetermined range.
The relationship between the corrected tensile strength and the peak temperature (maximum value) of E' in tables 1-2 is shown in FIG. 1. In FIG. 1, it is seen from the linear relationship between I and II that the tensile strength is increased as the equivalent of the epoxy functional group of the component (C) is increased relative to the equivalent of the thiol functional group of the component (A).
Industrial applicability
The epoxy resin composition of the present invention can be cured in a short time even under low temperature conditions to provide a cured product. The cured product shows a low TgHas appropriate flexibility and flexibility. Further, since the cured product exhibits high tensile strength, an electronic component having excellent drop impact resistance can be easily produced by using the epoxy resin composition of the present invention. Therefore, the epoxy resin composition of the present invention is useful as an adhesive, a sealing material, a dam agent, and the like for a semiconductor device, an electronic component, and the like, in particular, in which a plurality of components made of different materials are joined and assembled.
Claims (7)
1. An epoxy resin composition comprising the following components A to D,
component A: a thiol-based curing agent comprising at least 1 multifunctional thiol compound having 3 or more thiol groups;
component B: at least 1 multifunctional epoxy resin;
component C: a crosslink density modifier comprising at least 1 aromatic monofunctional epoxy resin; and
component D: a curing catalyst is used for curing the epoxy resin,
the epoxy resin composition provides: a cured product having a frequency of 10Hz, a temperature rise rate of 3 ℃/min, and a temperature at which the loss modulus E' is at a maximum in a DMA measurement by a stretching method, which is in the range of 20 ℃ to 55 ℃.
2. The epoxy resin composition according to claim 1, wherein,
the molar ratio B/A of the component B to the component A is 1.15 to 1.45.
3. The epoxy resin composition according to claim 1 or 2, wherein,
the molar ratio C/A of the component C to the component A is 0.55 to 1.65.
4. The epoxy resin composition according to any one of claims 1 to 3, wherein,
component C comprises an aromatic monofunctional epoxy resin.
5. A sealing material comprising the epoxy resin composition as claimed in any one of claims 1 to 4.
6. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4 or the sealing material according to claim 5.
7. An electronic component comprising the cured product according to claim 6.
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| CN113851055A (en) * | 2021-09-27 | 2021-12-28 | 京东方科技集团股份有限公司 | Display module, preparation method thereof and splicing display device |
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| WO2024024881A1 (en) * | 2022-07-29 | 2024-02-01 | 株式会社スリーボンド | Epoxy resin composition |
| WO2024090259A1 (en) * | 2022-10-28 | 2024-05-02 | ナミックス株式会社 | Resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic component |
| JP7217566B1 (en) * | 2022-10-28 | 2023-02-03 | ナミックス株式会社 | Resin compositions, adhesives, sealing materials, cured products and semiconductor devices |
| JP7217565B1 (en) * | 2022-10-28 | 2023-02-03 | ナミックス株式会社 | Resin compositions, adhesives, sealing materials, cured products, semiconductor devices and electronic components |
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| CN113851055A (en) * | 2021-09-27 | 2021-12-28 | 京东方科技集团股份有限公司 | Display module, preparation method thereof and splicing display device |
| CN113851055B (en) * | 2021-09-27 | 2023-09-29 | 京东方科技集团股份有限公司 | Display module, preparation method thereof and spliced display device |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI826714B (en) | 2023-12-21 |
| TW202116849A (en) | 2021-05-01 |
| CN112752783B (en) | 2022-08-02 |
| WO2021033329A1 (en) | 2021-02-25 |
| JP2021036021A (en) | 2021-03-04 |
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